DE102022205709A1 - Phosphorus-containing s-triazine compounds as flame retardants for polymer foam - Google Patents

Abstract

wobei mindestens R¹, R² verschieden sind zu R⁴, R⁵.
Ein vierter Aspekt der Erfindung ist ein Verfahren zur Herstellung eines Triazin-Derivats der allgemeinen Formel (I).In a first aspect, the invention relates to the use of a triazine derivative of the formula (I) as a flame retardant for a rigid polyurethane (PU) or polyisocyanurate (PIR) foam. A second aspect of the invention is a polyurethane (PU) or polyisocyanurate (PIR) rigid foam for which a triazine derivative of the formula (I) was used as a flame retardant. A third aspect of the invention relates to a triazine derivative of the formula (I)

where at least R ¹ , R ² are different from R ⁴ , R ⁵ .
A fourth aspect of the invention is a process for producing a triazine derivative of general formula (I).

Description

wobei mindestens R¹, R²verschieden sind zu R⁴, R⁵.In a first aspect, the invention relates to the use of a triazine derivative of the formula (I) as a flame retardant for a rigid polyurethane (PU) or polyisocyanurate (PIR) foam. A second aspect of the invention is a polyurethane (PU) or polyisocyanurate (PIR) rigid foam for which a triazine derivative of the formula (I) was used as a flame retardant. A third aspect of the invention relates to a triazine derivative of the formula (I)

where at least R ¹ , R ² are different from R ⁴ , R ⁵ .

A fourth aspect of the invention is a process for producing a triazine derivative of general formula (I).

CN111285990 A describes a flame-retardant polyurethane material in which 1,3,5-triazine-2,4,6-triphosphonate (TPE), 1,3,5-triazine-2,4,6-triphosphonic acid (TPA) and a corresponding metal salt of TPA are compounded. The flame retardant can be used for various types of polyurethane materials, textiles, decoration materials, wood, paper and other fields. The TPE is hydrolyzed to obtain the TPA, which in turn produces a metal salt. A synergistic effect in gas phase and condensed phase is reportedly obtained for the flame-retardant polyurethane material.

WO 93/12173 A2 discloses phosphorus-containing derivatives of 1,3,5-triazine, where at least one of the residues in positions 2, 4 or 6 is a nitrogen-containing group, and their use as flame retardants in general and as flame retardants in polyurethane foams.

Rigid polyurethane foams are used in a variety of building materials; they are the most frequently used insulation material for rafter insulation. In addition to its excellent insulating properties, rigid polyurethane foam scores particularly well with its insensitivity to moisture. The same applies to polyisocyanurate rigid foams.

The production of rigid polyurethane foams by reacting organic or modified organic di- or polyisocyanates, in particular polymeric methylene diisocyanate (pMDI) with higher molecular weight compounds with at least two reactive hydrogen atoms, in particular with polyether polyols from alkylene oxide polymerization or polyester polyols from the polycondensation of alcohols with dicarboxylic acids in the presence of polyurethane catalysts, chain extenders and/or crosslinking agents, blowing agents and other auxiliaries and additives is known and is described in numerous patent and literature publications. Polyisocyanurate (PIR) rigid foams are a variant of PU rigid foam with a higher isocyanate content. PIR typically has an MDI/polyol ratio, also referred to as an index (based on the isocyanate/polyol stoichiometry to produce urethane alone), of >180. The so-called index is defined as the excess of isocyanate relative to an equivalent reaction with all active H expressed in percent: Isocyanate index = isocyanate equivalent / polyol equivalent. Both PU and PIR rigid foams are characterized by very low thermal conductivity. The corresponding lambda values (λ values) are usually between 0.023 W/mK and 0.029 W/mK. The range of thermal conductivity is explained, among other things, by the fact that the corresponding panels - depending on the intended use - are manufactured with different raw densities. The higher the bulk density, the heavier the rigid foam is and the higher the lambda value. In contrast to soft foam, hard foam has a closed cell structure of more than 90%.

With regard to their use as a building material, the fire behavior of PU or PIR rigid foams is of essential importance. The European standard DIN EN 13501-1:2010-01 classifies building materials according to their fire behavior and thus also according to their fulfillment of the relevant building regulations requirements. The so-called small burner test is also carried out DIN EN ISO 11925-2 (2020-07) used to determine the fire resistance of building materials. For the classification of a building material into class E according to DIN EN 13501-1:2010-01 (normally flammable), if there is flame on the lower edge for 15 s, a flame height < 15 cm, no burning dripping/falling off within 600 seconds, and self-extinguishing is required.

Polyurethane and polyisocyanurate foams without flame retardants cannot be used for thermal insulation in the construction sector as insulation panels and for other applications because they do not meet the required fire protection regulations. Chlorinated phosphate esters are therefore predominantly used as effective flame retardants for polyurethane and polyisocyanurate foams. Due to their PBT potential (persistence, bioaccumulation and toxicity), these halogen-containing substances are in the European Union's 'risk assessment' and are therefore subject to public discussion. Furthermore, conventional flame retardants have problems during processing because, for example, solid flame retardants have an abrasive effect on the processing machines and sedimentation occurs.

The object of the invention was therefore to provide a PU or PIR foam which has fire behavior suitable for building materials, while avoiding or at least reducing chlorinated phosphate esters, and preferably while avoiding the use of solids.

First aspect - use of a triazine derivative of formula (I) as a flame retardant

wobei jeweils

X, Y, Z

jeweils ein Sauerstoff- oder ein Schwefelatom ist;

R1, R2

gleich sind und ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und C6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist;

R4, R5

gleich sind und ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und C6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist;

R7, R8

gleich sind und ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und C6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist;

wobei R¹, R² gleich oder verschieden sind zu R⁴, R⁵ und R⁴, R⁵ gleich oder verschieden sind zu R⁷, R⁸.The object is achieved according to a first aspect by using a triazine derivative of the formula (I) as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam

where each

X, Y, Z

each is an oxygen or a sulfur atom;

R1, R2

are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical;

R4, R5

are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical;

R7, R8

are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical;

where R ¹ , R ² are the same or different from R ⁴ , R ⁵ and R ⁴ , R ⁵ are the same or different from R ⁷ , R ⁸ .

Surprisingly, it was found that the use of a triazine made it possible to at least noticeably reduce/replace or completely eliminate chlorinated phosphate esters and also to partially omit any other flame retardant without sacrificing flame retardancy properties (fire protection properties) or fire behavior. It was also shown that by using a triazine, improved flame retardant properties (fire protection properties) could be achieved without affecting the foam quality compared to a rigid foam without flame retardants. In particular, the use of asymmetrical triazines made it possible to improve the flame retardancy properties (fire protection properties) even more than symmetrical triazines, which could be proven, for example, by a higher LOI value (LOI: Limiting Oxygen Index (LOI) test).

Furthermore, it was found that the unsymmetrical triazines in particular, which preferably contained at least one alkyl substituent with more than 2 carbons, were characterized by a liquid state of aggregation at 1013 mbar and 25 ° C. The individual components or mixtures in foam production are used in liquid form. Liquid flame retardants therefore offer significant advantages over conventional solid flame retardants, as abrasive effects on processing machines and sedimentation effects can be avoided.

Use - Symmetrical triazines

In a preferred embodiment of the use of a triazine derivative as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, R ¹ , R ² and R ⁴ , R ⁵ and R ⁷ , R ⁸ are the same (R ¹ = R ² = R ⁴ = R ⁵ = R ⁷ = R ⁸ ) and selected from the above groups.

In a further preferred embodiment of the use of a triazine derivative as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, R ¹ , R ² and R ⁴ , R ⁵ and R ⁷ , R ⁸ are the same (R ¹ = R ² = R ⁴ = R ⁵ = R ⁷ = R ⁸ ) and selected from the group consisting of branched and unbranched C4 to C20 alkyl radical.

In a further preferred embodiment of the use of a triazine derivative as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, R ¹ , R ² and R ⁴ , R ⁵ and R ⁷ , R ⁸ are the same (R ¹ = R ² = R ⁴ = R ⁵ = R ⁷ = R ⁸ ) and selected from the group consisting of branched and unbranched C4 to C17 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C16 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C15 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C14 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C13 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C12 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C11 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C10 alkyl radical.

Use - Unsymmetrical triazines

Use - Unsymmetrical triazines with at least one divergent group

In a further preferred embodiment of the use of a triazine derivative as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, R ¹ , R ² are different from R ⁴ , R ⁵ and from R ⁷ , R ⁸ (R ¹ , R ² ≠ R ⁴ , R ⁵ and R ¹ , R2 ≠ R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the groups mentioned at the beginning of formula (I) and R ⁴ , R ⁵ and R ⁷ , R ⁸ are selected from the groups mentioned at the beginning of formula (I).

In a further preferred embodiment of the use of a triazine derivative as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, R ¹ , R ² are different from R ⁴ , R ⁵ and from R ⁷ , R ⁸ (R ¹ , R ² ≠ R ⁴ , R ⁵ and R ¹ , R ² ≠ R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the group consisting of branched and unbranched C3 to C20 alkyl radical and 6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical and R ⁴ , R ⁵ and R ⁷ , R ⁸ are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and 6 to C12 Aryl radical, wherein the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical.

Use - Unsymmetrical triazines with one different and two identical groups

In a further preferred embodiment of the use of a triazine derivative as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, R ¹ , R ² are different from R ⁴ , R ⁵ and from R ⁷ , R ⁸ (R ¹ , R ² ≠ R ⁴ , R ⁵ and R ¹ , R ² ≠ R ⁷ , R ⁸ ) and R ⁴ , R ⁵ are equal to R ⁷ , R ⁸ (R ⁴ , R ⁵ = R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the groups mentioned at the beginning of formula (I) and R ⁴ , R ⁵ and R ⁷ , R ⁸ are selected from the groups mentioned at the beginning of formula (I).

In a further preferred embodiment of the use of a triazine derivative as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, R ¹ , R ² are different from R ⁴ , R ⁵ and from R ⁷ , R ⁸ (R ¹ , R ² ≠ R ⁴ , R ⁵ and R ¹ , R ² ≠ R ⁷ , R ⁸ ) and R ⁴ , R ⁵ are equal to R ⁷ , R ⁸ (R ⁴ , R ⁵ = R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the group consisting of branched and unbranched C4 to C20 alkyl radical and C6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical and R ⁴ , R ⁵ and R ⁷ , R ⁸ are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical .

In a further preferred embodiment of the use of a triazine derivative as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, R ¹ , R ² are different from R ⁴ , R ⁵ and from R ⁷ , R ⁸ (R ¹ , R ² ≠ R ⁴ , R ⁵ and R ¹ , R ² ≠ R ⁷ , R ⁸ ) and R ⁴ , R ⁵ are equal to R ⁷ , R ⁸ (R ⁴ , R ⁵ = R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the group consisting of branched and unbranched C4 to C20 alkyl radical, preferably from the group consisting of branched and unbranched C4 to C16 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C15 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C14 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C13 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C12 alkyl radical, more preferably from the group consisting from branched and unbranched C4 to C11 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C10 alkyl radical;
and R ⁴ , R ⁵ and R ⁷ , R ⁸ are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical, preferably from the group consisting of branched and unbranched C1 to C16 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C15 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C14 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C13 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C12 alkyl radical more preferably from the group consisting of branched and unbranched C1 to C11 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C10 alkyl radical.

Use - Unsymmetrical triazines with three different groups

In a further preferred embodiment of the use of a triazine derivative as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, R ¹ , R ² are different from R ⁴ , R ⁵ and from R ⁷ , R ⁸ (R ¹ , R ² ≠ R ⁴ , R ⁵ and R ¹ , R ² ≠ R ⁷ , R ⁸ ) and R ⁴ , R ⁵ are not equal to R ⁷ , R ⁸ (R ⁴ , R ⁵ ≠ R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the group consisting of branched and unbranched C3 to C20 alkyl radical and C6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical and R ⁴ , R ⁵ and R ⁷ , R ⁸ are each selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and 6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical having.

As already mentioned above, the use of unsymmetrical triazines in particular surprisingly enabled an even greater improvement in the flame retardancy properties (fire protection properties) compared to symmetrical triazines, which could be proven, for example, by a higher LOI value (LOI: Limiting Oxygen Index (LOI) test).

Furthermore, it was found that the unsymmetrical triazines in particular, which preferably contained at least one alkyl substituent with more than 2 carbons, were characterized by a liquid state of aggregation. Liquid flame retardants offer significant advantages over conventional solid flame retardants because they can be used to avoid sinking/segregation of a composition and to avoid abrasive effects on device parts.

Use - Proportion of triazine

In a further preferred embodiment of the use of a triazine derivative as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, the triazine derivative according to formula (I) is in an amount of 0.1 to 10% by weight, based on a total weight of 100% by weight of all components used in the production of the polyurethane (PU) or polyisocyanurate (PIR) rigid foam.

In a further preferred embodiment of the use of a triazine derivative as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, in particular for a PIR rigid foam, chlorinated phosphate esters are used in less than 0.1% by weight, based on a total weight of 100% by weight of all components used in the production of the polyurethane (PU) or polyisocyanurate (PIR) rigid foam.

In a further preferred embodiment of the use of a triazine derivative as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, apart from the triazine derivative of the formula (I), no other flame retardants are used in more than 0.1% by weight. , based on a total weight of 100% by weight of all components used in the production of the polyurethane (PU) or polyisocyanurate (PIR) rigid foam.

Second aspect - rigid foam

1. A) mindestens einem Polyisocyanat,
2. B) mindestens einem Polyol,
3. C) einem oder mehreren Treibmitteln,
4. D) einem oder mehreren Katalysatoren,
5. E) gegebenenfalls weiteren Hilfsmitteln oder Zusatzstoffen; und
6. F) einem Flammschutzmittel umfassend, bevorzugt bestehend aus einem oder mehreren Triazin-Derivaten der Formeln (I) wie zum ersten Aspekt der Erfindung voranstehend beschrieben.

In a second aspect, the invention relates to a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, obtained or obtainable by reacting

1. A) at least one polyisocyanate,
2. B) at least one polyol,
3. C) one or more propellants,
4. D) one or more catalysts,
5. E) if necessary, other aids or additives; and
6. F) comprising a flame retardant, preferably consisting of one or more triazine derivatives of the formulas (I) as described above for the first aspect of the invention.

The at least one polyisocyanate according to (A) is an organic compound which contains at least two reactive isocyanate groups per molecule, ie the functionality is at least 2. If the polyisocyanates used or a mixture of several polyisocyanates do not have a uniform functionality, the number-weighted average of the functionality is of the at least one polyisocyanate according to (A) at least 2. The at least one polyisocyanate according to (A) is selected from the group consisting of aliphatic, cycloaliphatic, araliphatic polyvalent isocyanates and mixtures thereof, preferably the at least one polyisocyanate according to (A) is an aromatic polyvalent isocyanate. Such polyvalent isocyanates are known per se or can be prepared using methods known per se. The polyvalent isocyanates can in particular also be used as mixtures, so that the at least one polyisocyanate according to (A) in this case contains various polyvalent isocyanates. The at least one polyisocyanate according to (A) preferably has two (hereinafter referred to as diisocyanates) or more than two isocyanate groups per molecule. Preferably, the at least one polyisocyanate according to (A) is selected from the group consisting of alkylene diisocyanates with 4 to 12 carbon atoms in the alkylene radical, in particular 1,12-dodecanediocyanate, 2-ethyltetramethylene diisocyanate-1,4,2-methylpentamethylene diisocyanate-1,5, tetramethylene diisocyanate. 1,4, and preferably hexamethylene diisocyanate-1,6; cycloaliphatic diisocyanates, in particular cyclohexane-1,3- and 1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4- and 2,6- Hexahydrotolylene diisocyanate and the corresponding isomer mixtures, 4,4'-, 2,2'- and 2,4'-dicyclohexylmethane diisocyanate and the corresponding isomer mixtures, and aromatic polyisocyanates, in particular 2,4- and 2,6-tolylene diisocyanate and the corresponding isomer mixtures, 4 4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate and the corresponding isomer mixtures, mixtures of 4,4'- and 2,2'-diphenylmethane diisocyanates, polyphenylpolymethylene polyisocyanates, mixtures of 4,4'-, 2,4 '- and 2,2'-diphenylmethane diisocyanates and polyphenylpolymethylene polyisocyanates (crude MDI) and mixtures of crude MDI and tolylene diisocyanates. More preferably, the at least one polyisocyanate according to (A) is selected from the group consisting of 2,2'-, 2,4'- and/or 4,4'-diphenylme than diisocyanate (MDI), polymeric diphenylmethane diisocyanate (pMDI), 1,5-naphthylene diisocyanate (NDI), 2,4- and/or 2,6-tolylene diisocyanate (TDI), 3,3'-dimethyl diphenyl diisocyanate, 1,2-diphenylethane diisocyanate and/or p-phenylene diisocyanate (PPDI), tri-, tetra-, penta-, hexa-, hepta- and/or octamethylene diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, 2-ethylbutylene-1,4-diisocyanate, pentamethylene -1,5-diisocyanate, butylene-1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and/or 1 ,3-Bis(isocyanatomethyl)cyclohexane (HXDI), 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and/or -2,6-cyclohexane diisocyanate and 4,4'-, 2,4'- and/or 2,2'-Dicyclohexylmethane diisocyanate and mixtures of two or more of these polyisocyanates. Modified polyisocyanates, ie products that are obtained by chemical reaction of organic polyisocyanates and that have at least two reactive isocyanate groups per molecule, are also often used. Particular mention should be made of polyisocyanates containing ester, urea, biuret, allophanate, carbodiimide, isocyanurate, uretdione, carbamate and/or urethane groups. The at least one polyisocyanate according to (A) can be used wholly or partly in the form of polyisocyanate prepolymers. These polyisocyanate prepolymers are obtainable by reacting the above-described polyisocyanates of the at least one polyisocyanate according to (A) in whole or in part in advance with polymeric compounds reactive towards isocyanates to form the isocyanate prepolymer. The reaction takes place in excess of the at least one polyisocyanate according to (A), for example at temperatures in the range from 30 to 100 ° C, preferably at about 80 ° C. Suitable polymeric compounds with groups reactive towards isocyanates are known to those skilled in the art and are described, for example, in “Plastics Handbook, 7, Polyurethanes”, Carl Hanser-Verlag, 3rd edition 1993, Chapter 3.1. Suitable polymeric compounds with isocyanate-reactive groups are basically all known compounds with at least two isocyanate-reactive hydrogen atoms, for example those with a functionality in the range from 2 to 8 and a number-average molecular weight Mn in the range from 400 to 15,000 g/mol. For example, compounds selected from the group of polyether polyols, polyester polyols or mixtures thereof can be used.

The at least one polyol according to (B) includes polyester polyol (aka polyesterol), polyether polyol (aka polyetherol), polyester ether polyol (aka polyesteretherol) and mixtures of two or more of these polyols. Polyester polyols can be prepared, for example, from organic dicarboxylic acids with 2 to 12 carbon atoms, preferably aromatic, or mixtures of aromatic and aliphatic dicarboxylic acids and polyhydric alcohols, preferably diols, with 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms. The dicarboxylic acids can be used both individually and in a mixture. Instead of the free dicarboxylic acids, the corresponding dicarboxylic acid derivatives, such as dicarboxylic acid esters of alcohols with 1 to 4 carbon atoms or dicarboxylic anhydrides, can also be used. Particularly suitable aliphatic dicarboxylic acids are: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid. Phthalic acid, phthalic anhydride, terephthalic acid and/or isophthalic acid are preferably used as aromatic dicarboxylic acids in a mixture or alone. Examples of dihydric and polyhydric alcohols, especially diols, are: ethanediol (monoethylene glycol), diethylene glycol, 1,2- or 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol , 1,10-decanediol, glycerin, trimethylolpropane and pentaerythritol. Polyester polyols made from lactones, for example ε-caprolactone or hydroxycarboxylic acids, for example co-hydroxycaproic acid, can also be used. Bio-based starting materials and/or their derivatives can also be used to produce polyester polyols, such as: B. castor oil, polyhydroxy fatty acids, ricinoleic acid, hydroxyl-modified oils, grape seed oil, black caraway oil, pumpkin seed oil, borage seed oil, soybean oil, wheat seed oil, rapeseed oil, sunflower seed oil, peanut oil, apricot kernel oil, pistachio oil, almond oil, olive oil, macadamia nut oil, avocado oil, sea buckthorn oil, sesame oil, hemp oil, Hazelnut oil, primrose oil, wild rose oil, safflower oil, walnut oil, fatty acids, hydroxyl-modified fatty acids and fatty acid esters based on myristoleic acid, palmitoleic acid, oleic acid, vaccenic acid, petroselinic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, alpha- and gama-linolenic acid, stearidonic acid, arachidonic acid, timnodonic acid , clupanodonic acid and cervonic acid. Polyether polyols can be prepared by known processes, for example by anionic polymerization of one or more alkylene oxides with 2 to 4 carbon atoms with alkali metal hydroxides, such as sodium or potassium hydroxide, alkali metal alcoholates, such as sodium methylate, sodium or sodium or potassium methylate or potassium isopropylate, or a-minic alkoxylation catalysts, such as dimethylethanolamine (DMEOA), imidazole and/or imidazole derivatives, using at least one starter molecule which contains 2 to 8, preferably 2 to 6, bonded reactive hydrogen atoms, or by cationic polymerization with Lewis acids, such as antimony pentachloride, boron fluoride etherate or bleaching earth, getting produced. Suitable alkylene oxides are, for example, tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-Butylene oxide, styrene oxide and preferably ethylene oxide and ,2-propylene oxide. The alkylene oxides can be used individually, alternating one after the other or as mixtures. Preferred alkylene oxides are propylene oxide and ethylene oxide, propylene oxide is particularly preferred. The use of alkylene oxides, in particular propylene oxide and/or ethylene oxide, in conjunction with a starter molecule is preferred. Possible starter molecules include, for example: water, organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid and terephthalic acid, aliphatic and aromatic, optionally N-mono-, N,N- and N,N'-dialkyl-substituted diamines with 1 to 4 carbon atoms in the alkyl radical , such as optionally mono- and dialkyl-substituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5- and 1,6-hexamethylenediamine, phenylenediamines, 2,3-, 2,4- and 2,6-toluenediamine and 4,4'-, 2,4'- and 2,2'-diamino-diphenylmethane. The diprimary amines mentioned, for example ethylenediamine, are particularly preferred. Also suitable as starter molecules are: alkanolamines, such as ethanolamine, N-methyl and N-ethylethanolamine, dialkanolamines, such as diethanolamine, N-methyl and N-ethyldiethanolamine, and trialkanolamines, such as triethanolamine, and ammonia. Preferably used are dihydric or polyhydric alcohols, such as ethanediol, 1,2- and 1,3-propanediol, diethylene glycol (DEG), dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose (sucrose). The polyether polyols, preferably polyoxypropylene polyols, have a functionality of preferably 2 to 6, particularly preferably 4 to 5.

Blowing agents according to (C) are selected from the group of chemical and physical blowing agents and mixtures of chemical and physical blowing agents. Chemical blowing agents are preferably water, formic acid and mixtures thereof. These react with isocyanate groups to form carbon dioxide and, in the case of formic acid, carbon dioxide and carbon monoxide. Because these blowing agents release the gas through a chemical reaction with the isocyanate groups, they are called chemical blowing agents. Physical blowing agents are preferably selected from the group of low-boiling hydrocarbons. Liquids which are inert to the at least one polyisocyanate according to (A) and have boiling points below 100 ° C, preferably below 50 ° C at 1013 mbar, are particularly suitable, so that they evaporate under the influence of the exothermic polyaddition reaction. Examples of such liquids that are preferably used are alkanes, such as heptane, hexane, n- and iso-pentane, preferably technical mixtures of n- and iso-pentanes, n- and iso-butane and propane, cycloalkanes, such as cyclopentane and / or cyclohexane, Ethers such as furan, dimethyl ether and diethyl ether, ketones such as acetone and methyl ethyl ketone, carboxylic acid alkyl esters such as methyl formate, dimethyl oxalate and ethyl acetate and halogenated hydrocarbons such as methylene chloride, dichloromonofluoromethane, difluoromethane, trifluoromethane, difluoroethane, tetrafluoroethane, chlorodifluoroethane, 1,1-dichloro-2 ,2,2-trifluoroethane, 2,2-dichloro-2-fluoroethane and heptafluoropropane. Mixtures of these low-boiling liquids with one another and/or with other substituted or unsubstituted hydrocarbons can also be used. Organic carboxylic acids, such as formic acid, acetic acid, oxalic acid, ricinoleic acid and compounds containing carboxyl groups, are also suitable. Preferably no halogenated hydrocarbons are used as blowing agents. The blowing agent(s) according to (C) are preferably selected from the group consisting of water, formic acid, formic acid-water mixtures, pentane isomers, mixtures of pentane isomers and mixtures of two or more of these blowing agents.

The catalyst(s) according to (D) used are in particular compounds which accelerate the reaction of the reactive hydrogen atoms, in particular hydroxyl groups, containing compounds of the further components, in particular the at least one polyisocyanate according to (A) and the at least one polyol according to (B). (D1), as well as those that promote the trimerization of isocyanates, ie the formation of polyisocyanurate (PIR) (D2), which are also referred to as trimerization catalysts. In a preferred embodiment, the catalysts (D1) used are basic polyurethane catalysts, for example tertiary amines, such as triethylamine, tributylamine, bis(2-dimethylaminoethyl)methylamine", dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine, N,N,N',N'-tetramethyldiaminodiethyl ether, bis -(dimethylaminopropyl)-urea, N-methyl or methyl or N-ethyl morpholine, N-cyclohexyl morpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N,N-tetramethylbutanediamine, N,N,N,N -Tetramethylhexanediamine-1,6, pentamethyldiethylenetriamine, bis(2-dimethylaminoethyl)ether, dimethylpiperazine, N-dimethylaminoethylpiperidine, 1,2-dimethylimidazole, 1-azabicyclo-(2,2,0)-octane, 1,4.Diazabicyclo.( 2,2,2).octane (Dabco) and alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyl and N-ethyldiethanolamine, dimethylaminoethanol, 2-(N,N-dimethylaminoethoxy)ethanol, N,N',N''- Tris-(dialkylaminoalkyl)hexahydrotriazines, for example N,N',N''-tris-(dimethylaminopropyl)-s-hexahydrotriazine, and triethylenediamine. However, metal salts such as iron(II) chloride, zinc chloride, and preferably tin salts such as tin dioctoate, tin diethyl hexoate and dibutyltin dilaurate and in particular mixtures of tertiary amines and organic tin salts are also suitable. Other suitable catalysts include: amidines, such as 2,3-dimethyl-3,4,5,6-tetrahydropyrimidine, tetraalkylammonium hydroxides, such as tetramethylammonium hydroxide, alkali metal hydroxides, such as sodium hydroxide and alkali metal alcoholates, such as sodium methylate and potassium isopropylate, alkali metal carboxylates and alkali metal salts of long-chain fatty acids 10 to 20 carbon atoms and optionally pendant OH groups. As Trimerization catalyst (D2) is preferably alkali and/or alkaline earth metal compounds, preferably alkali metal salts, such as potassium acetate, potassium octoate and potassium formate. Other alkali metal compounds that are preferably used include alkali metal hydroxide, such as sodium hydroxide, and alkali metal alcoholates, such as sodium methylate and potassium isopropylate, as well as alkali metal salts of long-chain fatty acids with 10 to 20 carbon atoms and, if appropriate, pendant OH groups. Potassium formate is particularly preferred as an alkali metal compound. If a larger excess of polyisocyanate is used during foaming, other possible catalysts for the trimerization reaction of the excess NCO groups with one another are: catalysts forming isocyanurate groups, for example ammonium ion or alkali metal salts, especially ammonium or alkali metal carboxylates, alone or in combination with tertiary amines. In a preferred embodiment, the catalyst(s) (D2) are used together with one or more catalyst(s) (D1), for example a combination of at least potassium formate (D1) with at least bis(2-dimethylaminoethyl)methylamine (D2) .

If necessary, further auxiliaries and/or additives according to (E) can be added to the reaction mixture for producing the polyurethane (PU) or polyisocyanurate (PIR) rigid foam. Mention may be made, for example, of surface-active substances, foam stabilizers, cell regulators, fillers, dyes, pigments, anti-hydrolysis agents, fungistatic and bacteriostatic substances. Suitable surface-active substances include, for example, compounds which serve to support the homogenization of the starting materials and may also be suitable for regulating the cell structure of the plastics. Mention may be made, for example, of emulsifiers such as the sodium salts of castor oil sulfates or of fatty acids and salts of fatty acids with amines, for example oleic diethylamine, stearic diethanolamine, ricinoleic diethanolamine, salts of sulfonic acids, for example alkali or alkali or ammonium salts of dodecylbenzene or dodecylbenzene or dinaphthylmethanedisulfonic acid and ricinoleic acid; Foam stabilizers, such as siloxane oxalkylene copolymers and other organopolysiloxanes, oxyethylated alkylphenols, oxyethylated fatty alcohols, paraffin oils, castor oil or Ricinoleic acid esters, Turkish red oil and peanut oil, and cell regulators such as paraffins, fatty alcohols and dimethylpolysiloxanes. Oligomeric acrylates with polyoxyalkylene and fluoroalkane residues as side groups are also suitable for improving the emulsifying effect, the cell structure and/or stabilization of the foam. The surface-active substances are usually used in amounts of 0.01 to 10 parts by weight, based (i.e. calculated) on 100 parts by weight of the at least one polyol according to (B). Fillers, in particular reinforcing fillers, are the known, customary organic and inorganic fillers, reinforcing agents, weighting agents, agents for improving the abrasion behavior in paints, coating agents, etc. In particular, the following may be mentioned as examples: inorganic fillers such as silicate minerals, for example layered silicates such as antigorite, serpentine, hornblende, amphibole, chrisotile and talc, metal oxides such as kaolin, aluminum oxides, titanium oxides and iron oxides, metal salts such as chalk, barite and inorganic pigments such as cadmium sulfide and zinc sulfide, as well as glass, among others. Preferably used are kaolin (China clay), aluminum silicate and coprecipitates of barium sulfate and aluminum silicate, as well as natural and synthetic fibrous minerals such as wollastonite, metal and especially glass fibers of various lengths, which may optionally be sized. Possible organic fillers include, for example: carbon, melamine, rosin, cyclopentadienyl resins and graft polymers as well as cellulose fibers, polyamide, polyacrylonitrile, polyurethane and polyester fibers based on aromatic and/or aliphatic dicarboxylic acid esters and in particular carbon fibers. Further information about the other common auxiliaries and additives mentioned above can be found in the specialist literature, for example the monograph by J.H. Saunders and K.C. Frisch “High Polymers” Volume , refer to.

The flame retardant according to (F) comprises a flame retardant comprising, preferably consisting of, one or more triazine derivatives of the formulas (I) as described in detail above for the first aspect; Embodiments and preferred embodiments of the triazine derivative of formulas (I) described above for the first aspect also apply to the second aspect of the invention. The flame retardant according to (F) comprises further flame retardants or consists of the flame retardant comprising, preferably consisting of, one or more triazine derivatives of the formulas (I) as described above. Other flame retardants are, for example, compounds containing phosphorus and/or halogen atoms, such as tricresyl phosphate, tris-(2-chloroethyl phosphate), tris-(2-chloro-iso-propyl) phosphate, 2,2-bis(chloromethyl)trimethylene-bis( bis (2-chloroethyl) phosphate), tris (1,3-dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate and tetrakis (2-chloroethyl) ethylene diphosphate, oligomeric organophosphorus compounds (for example Fyrol® PNX, Fyrolflex® RDP) and Tris-2,3-dibromopropyl phosphate. Furthermore, inorganic flame retardants, for example antimony trioxide, arsenic oxide, ammonium polyphosphate, expandable graphite and calcium sulfate / or cyanuric acid derivatives, for example melamine, can also be used to make the flame retardant PU or PIR rigid foams can be used. However, according to the invention, in particular the chlorinated phosphate esters, such as tris-(2-chloro-iso-propyl) phosphate (TCPP), should (can) be used at least in reduced proportion.

In a preferred embodiment of the polyurethane (PU) or polyisocyanurate (PIR) rigid foam, the triazine derivative(s) according to formula (I) are used in a total amount of 0.1 to 10% by weight, based on a total weight of 100% by weight of all components used in the production of the polyurethane (PU) or polyisocyanurate (PIR) rigid foam.

In a preferred embodiment of the polyurethane (PU) or polyisocyanurate (PIR) rigid foam, chlorinated phosphate esters are used in less than 0.1% by weight, based on a total weight of 100% by weight of all in the production of the polyurethane (PU) or Polyisocyanurate (PIR) rigid foam components used.

In a preferred embodiment of the polyurethane (PU) or polyisocyanurate (PIR) rigid foam, apart from the triazine derivative of the formula (I), no other flame retardants are used in more than 0.1% by weight, based on a total weight of 100% by weight. of all components used in the production of the polyurethane (PU) or polyisocyanurate (PIR) rigid foam.

Third aspect - unsymmetrical triazines

wobei jeweils

X, Y, Z

jeweils ein Sauerstoff- oder ein Schwefelatom ist;

R1, R2

gleich sind und ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und C6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist;

R4, R5

gleich sind und ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und C6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist;

R7, R8

gleich sind und ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und C6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist;

wobei mindestens R¹, R² verschieden sind zu R⁴, R⁵.In a third aspect, the invention relates to triazine derivatives of the formula (I)

where each

X, Y, Z

each is an oxygen or a sulfur atom;

R1, R2

are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical;

R4, R5

are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical;

R7, R8

are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical;

where at least R ¹ , R ² are different from R ⁴ , R ⁵ .

Unsymmetrical triazines with at least one different group

In a preferred embodiment of the triazine derivative of the formula (I), R ¹ , R ² are different from R ⁴ , R ⁵ and from R ⁷ , R ⁸ (R ¹ , R ² ≠ R ⁴ , R ⁵ and R ¹ , R ² ≠ R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the group consisting of branched and unbranched C3 to C20 alkyl radical and 6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and has unbranched C1 to C10 alkyl radical and R ⁴ , R ⁵ and R ⁷ , R ⁸ are selected from the group consisting of ver branched and unbranched C1 to C20 alkyl radical and 6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical.

Unsymmetrical triazines with one divergent and two identical groups

In a preferred embodiment of the triazine derivative of the formula (I), R ¹ , R ² are different from R ⁴ , R ⁵ and from R ⁷ , R ⁸ (R ¹ , R ² ≠ R ⁴ , R ⁵ and R ¹ , R ² ≠ R ⁷ , R ⁸ ) and R ⁴ , R ⁵ are equal to R ⁷ , R ⁸ (R ⁴ , R ⁵ = R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the group consisting of branched and unbranched C4 to C20 alkyl radical, preferably from the group consisting of branched and unbranched C4 to C16 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C15 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C14 alkyl radical , more preferably from the group consisting of branched and unbranched C4 to C13 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C12 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C11 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C10 alkyl radical
and R ⁴ , R ⁵ and R ⁷ , R ⁸ are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical, preferably from the group consisting of branched and unbranched C1 to C16 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C15 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C14 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C13 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C12 alkyl radical more preferably from the group consisting of branched and unbranched C1 to C11 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C10 alkyl radical.

In a preferred embodiment of the triazine derivative of the formula (I), R ¹ , R ² are different from R ⁴ , R ⁵ and from R ⁷ , R ⁸ (R ¹ , R ² ≠ R ⁴ , R ⁵ and R ¹ , R ² ≠ R ⁷ , R ⁸ ) and R ⁴ , R ⁵ are equal to R ⁷ , R ⁸ (R ⁴ , R ⁵ = R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the group consisting of branched and unbranched C4 to C20 alkyl radical and 6 to C12 aryl radical, wherein the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical and R ⁴ , R ⁵ and R ⁷ , R ⁸ are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and 6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical.

Unsymmetrical triazines with three distinct groups

In a preferred embodiment of the triazine derivative of the formula (I), R ¹ , R ² are different from R ⁴ , R ⁵ and from R ⁷ , R ⁸ (R ¹ , R ² ≠ R ⁴ , R ⁵ and R ¹ , R ² ≠ R ⁷ , R ⁸ ) and R ⁴ , R ⁵ are not equal to R ⁷ , R ⁸ (R ⁴ , R ⁵ ≠ R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the group consisting of branched and unbranched C3 to C20 alkyl radical and 6 to C12 aryl radical, wherein the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical and R ⁴ , R ⁵ and R ⁷ , R ⁸ are each selected from Group consisting of branched and unbranched C1 to C20 alkyl radical and 6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical.

Fourth aspect - production process triazines

1. (i) Bereitstellen einer Phosphit-Mischung umfassend
   1. (i.1) ein erstes Trialkyl- bzw. Triarylphosphit der allgemeinen Formel (A)
      
      wobei

      X

      ein Heteroatom, insbesondere ein Sauerstoff oder ein Schwefelatom, ist;

      R1, R2, R3

      gleich sind und ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und C6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist; und

   2. (i.2) ein zweites Trialkyl- bzw. Triarylphosphit der allgemeinen Formel (B)
      
      wobei

      Y

      ein Heteroatom insbesondere ein Sauerstoff oder ein Schwefelatom, ist;

      R4, R5, R6

      gleich sind und ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und C6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und C1 bis C10 Alkylrest aufweist;

      wobei R¹, R², R³ des erstes Trialkylphosphits gemäß (i.1) ungleich sind zu R⁴, R⁵, R⁶ des zweiten Trialkylphosphits gemäß (i.2); und
   3. (i.3) optional ein drittes Trialkyl- bzw. Triarylphosphit der allgemeinen Formel (C)
      
      wobei

      Z

      ein Heteroatom, insbesondere ein Sauerstoff oder ein Schwefelatom, ist;

      R7, R8, R9

      gleich sind und ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und C6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und C1 bis C10 Alkylrest aufweist;

      wobei R⁷, R⁸, R⁹ ungleich sind zu R¹, R², R³ des erstes Trialkylphosphits gemäß (i.1) und ungleich sind zu R⁴, R⁵, R⁶ des zweiten Trialkylphosphits gemäß (i.2). und
2. (ii) Bereitstellen von Cyanurchlorid;
3. (iii) Umsetzung der Phosphit-Mischung gemäß (i) mit dem Cyanurchlorid gemäß (ii), unter Erhalt mindestens eines Triazin-Derivats der allgemeinen Formel (I)
   
   , wobei die Reste R'-R⁹ und X, Y, Z die zum ersten bzw. dritten Aspekt der Erfindung wie voranstehend beschrieben angegebene Bedeutung haben.

A fourth aspect of the invention relates to a process for producing a triazine derivative of the general formula (I).

1. (i) providing a phosphite mixture
   1. (i.1) a first trialkyl or triaryl phosphite of the general formula (A)
      
      where

      X

      is a heteroatom, especially an oxygen or a sulfur atom;

      R1, R2, R3

      are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical; and

   2. (i.2) a second trialkyl or triaryl phosphite of the general formula (B)
      
      where

      Y

      a heteroatom, in particular an oxygen or a sulfur atom;

      R4, R5, R6

      are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and C1 to C10 alkyl radical;

      where R ¹ , R ² , R ³ of the first trialkyl phosphite according to (i.1) are not equal to R ⁴ , R ⁵ , R ⁶ of the second trialkyl phosphite according to (i.2); and
   3. (i.3) optionally a third trialkyl or triaryl phosphite of the general formula (C)
      
      where

      Z

      is a heteroatom, especially an oxygen or a sulfur atom;

      R7, R8, R9

      are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and C1 to C10 alkyl radical;

      where R ⁷ , R ⁸ , R ⁹ are not equal to R ¹ , R ² , R ³ of the first trialkyl phosphite according to (i.1) and are not equal to R ⁴ , R ⁵ , R ⁶ of the second trialkyl phosphite according to (i.2) . and
2. (ii) providing cyanuric chloride;
3. (iii) reacting the phosphite mixture according to (i) with the cyanuric chloride according to (ii), to obtain at least one triazine derivative of the general formula (I)
   
   , where the radicals R'-R ⁹ and X, Y, Z have the meaning given for the first and third aspects of the invention as described above.

Embodiments and preferred embodiments of the triazine derivative of formulas (I) described for the first aspect and the third aspect of the invention also apply to the fourth aspect of the invention.

In the reaction according to (iii), the trialkyl or triaryl phosphites of the general formula (A), (B) and optionally (C) contained in the phosphite mixture according to (i) are preferably used in such a way that primarily a (1) asymmetrical Triazine derivative of the general formula (I) is obtained. Details regarding molar ratios are described in detail below. When using only the first and second trialkyl or triaryl phosphite without a third trialkyl or triaryl phosphite and an approximately twice equimolar use of the first trialkyl or triaryl phosphite of the general formula (A) to the second trialkyl or triaryl phosphite of the general formula (B ), for example, an asymmetric triazine derivative of the general formula (I) is primarily obtained, in which two of the -P(=O)(QR) ₂ groups are the same and only one different -P(=O)(QR) ₂ - Group is present - "Q" stands as a placeholder for )(QR) ₂ groups to more than 50 mol%, preferably to more than 55 mol%, preferably to more than 60 mol%, preferably to more than 65 mol%, preferably to more than 70 mol% , preferably more than 75 mol%, preferably more than 80 mol%, preferably more than 85 mol%, preferably more than 90 mol%, preferably more than 95 mol%, based on 100 mol -% of the triazines contained in the mixture. When using only the first and second trialkyl or triaryl phosphite without a third trialkyl or triaryl phosphite and an approximately equimolar use of the first trialkyl or triaryl phosphite of the general formula (A) to the second trialkyl or triaryl phosphite of the general formula (B) For example, mixtures of unsymmetrical triazine derivatives of the general formula (I) are primarily obtained in which two different asymmetric triazine derivatives of the general formula (I) are present in an approximately equimolar ratio, each of which has two identical -P(=O) (QR) ₂ groups and a different -P(=O)(QR) ₂ group. When using the first, second and third trialkyl or triaryl phosphite in an approximately equimolar ratio to one another, primarily only an asymmetrical triazine derivative of the general formula (I) is obtained, in which all three -P(=O)(QR) ₂ - Groups are different from each other. Here too, “preserved with priority” means that although a mixture of triazines may be obtained, in this mixture the unsymmetrical triazine with the three different - P(=O)(QR) ₂ groups is preferred in more than 50 mol% to more than 55 mol%, preferably to more than 60 mol%, preferably to more than 65 mol%, preferably to more than 70 mol%, preferably to more than 75 mol%, preferably to more than 80 mol -%, preferably more than 85 mol%, preferably more than 90 mol%, preferably more than 95 mol%, based on 100 mol% of the triazines contained in the mixture.

In each of the variants described above, symmetrical triazines in which all three -P(=O)(QR) ₂ groups are the same are preferably obtained in amounts which are below the detection limit in the ³¹ P NMR, ie preferably less than 1 %]

In a preferred embodiment of the process for producing a triazine derivative of the general formula (I), no solvent is present in at least one of steps (i), (ii) or (iii). Preferably, no solvent is present in either (i), (ii) or (iii) (solvent-free synthesis).

In a preferred embodiment of the process for producing a triazine derivative of the general formula (I), at least one of the trialkyl or triaryl phosphite of the general formula (A), (B) or optionally (C) is liquid at 25 ° C and 1013 mbar is.

In a preferred embodiment of the process for producing a triazine derivative of the general formula (I), if at least one further is the trialkyl or triaryl phosphite of the general formula (A), (B) or optionally (C) at 25 ° C and 1013 mbar is solid that at least one further solid trialkyl or triaryl phosphite is dissolved in at least one liquid trialkyl or triaryl phosphite, so that the phosphite mixture according to (i) is liquid at 25 ° C and 1013 mbar.

molar ratios

In a preferred embodiment of the process for producing a triazine derivative of the general formula (I), the molar ratio of the sum of all in the phosphite mixture according to (i) is ent holding trialkyl or triaryl phosphite [(A) + (B) or (A) + (B) + (C)] to the cyanuric chloride in the reaction according to (iii) > 1:1, preferably in the range of 1.01: 1 to 2:1, more preferably in the range of 1.1:1 to 1.5:1.

In a preferred embodiment of the process for producing a triazine derivative of the general formula (I), the molar ratio of the first trialkyl or triaryl phosphite of the general formula (A) to the second trialkyl or triaryl phosphite of the general formula (B) is in the range from 0.5:1 to 1.5:1, preferably in the range from 0.8:1 to 1.2:1, more preferably in the range from 0.9:1 to 1.1:1, more preferably 1: 1; or the molar ratio of the first trialkyl or triaryl phosphite of the general formula (A) to the second trialkyl or triaryl phosphite of the general formula (B) is in the range from 0.7:2 to 1.3:2, preferably in the range of 0.8:2 to 1.1:2, more preferably in the range of 0.9:2 to 1.1:2, more preferably 1:2.

In a preferred embodiment of the process for producing a triazine derivative of the general formula (I), the molar ratio of the second trialkyl or triaryl phosphite of the general formula (B) to the third trialkyl or triaryl phosphite of the general formula (C) is in the range from 0.5:1: to 1.5:1, preferably in the range from 0.8:1 to 1.2:1, more preferably in the range from 0.9:1 to 1.1:1, more preferably 1 :1.

• (iii.1a) Vorlegen von gemäß (i) bereitgestelltem ersten und zweiten Trialkyl- bzw. Triarylphosphit (A), (B) und optional vom drittem Trialkyl- bzw. Triarylphosphit (C) in einem Reaktionsgefäß,
• (iii.2a) Zugabe des gemäß (ii) bereitgestellten Cyanurchlorids in das Reaktionsgefäß; oder
• (iii.1 b) Vorlegen von gemäß (ii) bereitgestelltem Cyanurchlorid in einem Reaktionsgefäß;
• (iii.2b) Zugabe des gemäß (i) bereitgestellten ersten und zweiten Trialkyl- bzw. Triarylphosphits (A), (B) und optional des dritten Trialkyl- bzw. Triarylphosphits (C) in das Reaktionsgefäß.

In a preferred embodiment of the process for producing a triazine derivative of the general formula (I), step (iii) comprises:

• (iii.1a) placing the first and second trialkyl or triaryl phosphite (A), (B) provided in accordance with (i) and optionally the third trialkyl or triaryl phosphite (C) in a reaction vessel,
• (iii.2a) adding the cyanuric chloride provided according to (ii) to the reaction vessel; or
• (iii.1 b) placing cyanuric chloride provided according to (ii) in a reaction vessel;
• (iii.2b) Adding the first and second trialkyl or triaryl phosphite (A), (B) provided according to (i) and optionally the third trialkyl or triaryl phosphite (C) into the reaction vessel.

Since at least one of the trialkyl or triaryl phosphites of the general formula (A), (B) or optionally (C) is liquid at 25 ° C and 1013 mbar, the phosphites represent the liquid phase. Cyanuric chloride, which is at 25 ° C and 1013 mbar is present as a solid, is either introduced or added. Variant (iii.1 a) + (iii.1 b), i.e. the addition of solid cyanuric chloride to the liquid phase, has the advantage that the thermal management of the reaction (removal of reaction heat) is significantly simplified. This means that large amounts of unsymmetrical triazines can be accessed quickly and easily using this variant.

1. 1. Verwendung eines Triazin-Derivats der Formel (I) als Flammschutzmittel für einen Polyurethan(PU)- oder Polyisocyanurat(PIR)-Hartschaum
   
   wobei jeweils

   X, Y, Z

   jeweils ein Sauerstoff- oder ein Schwefelatom ist;

   R1, R2

   gleich sind und ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und C6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist;

   R4, R5

   gleich sind und ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und C6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist;

   R7, R8

   gleich sind und ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und C6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist;

   wobei R¹, R² gleich oder verschieden sind zu R⁴, R⁵ und R⁴, R⁵ gleich oder verschieden sind zu R⁷, R⁸.
2. 2. Verwendung eines Triazin-Derivats gemäß Ausführungsform 1 als Flammschutzmittel für einen Polyurethan(PU)- oder Polyisocyanurat(PIR)-Hartschaum, wobei R¹, R² und R⁴, R⁵ und R⁷, R⁸ gleich sind (R¹ = R² = R⁴ = R⁵ = R⁷ = R⁸) und ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C20 Alkylrest.
3. 3. Verwendung eines Triazin-Derivats gemäß Ausführungsform 1 oder 2 als Flammschutzmittel für einen Polyurethan(PU)- oder Polyisocyanurat(PIR)-Hartschaum, wobei R¹, R² und R⁴, R⁵ und R⁷, R⁸ gleich sind (R¹ = R² = R⁴ = R⁵ = R⁷ = R⁸) und ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C17 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C16 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C15 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C14 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C13 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C12 Alkylrest weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C11 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C10 Alkylrest.
4. 4. Verwendung eines Triazin-Derivats gemäß Ausführungsform 1 als Flammschutzmittel für einen Polyurethan(PU)- oder Polyisocyanurat(PIR)-Hartschaum, wobei R¹, R² ungleich sind zu R⁴, R⁵ und zu R⁷, R⁸ (R¹, R² ≠ R⁴, R⁵ und R¹, R² ≠ R⁷, R⁸), wobei R¹, R² ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C3 bis C20 Alkylrest und 6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist und R⁴, R⁵ und R⁷, R⁸ ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und 6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist.
5. 5. Verwendung eines Triazin-Derivats gemäß Ausführungsform 1 oder 4 als Flammschutzmittel für einen Polyurethan(PU)- oder Polyisocyanurat(PIR)-Hartschaum, wobei R¹, R² ungleich sind zu R⁴, R⁵ und zu R⁷, R⁸ (R¹, R² ≠ R⁴, R⁵ und R¹, R² ≠ R⁷, R⁸) und R⁴, R⁵ gleich sind zu R⁷, R⁸ (R⁴, R⁵= R⁷, R⁸), wobei R¹, R² ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C20 Alkylrest und C6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist und R⁴, R⁵ und R⁷, R⁸ ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und C6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist.
6. 6. Verwendung eines Triazin-Derivats gemäß Ausführungsform 1 oder 4 bis 5 als Flammschutzmittel für einen Polyurethan(PU)- oder Polyisocyanurat(PIR)-Hartschaum, wobei R¹, R² ungleich sind zu R⁴, R⁵ und zu R⁷, R⁸ (R¹, R² ≠ R⁴, R⁵ und R¹, R² ≠ R⁷, R⁸) und R⁴, R⁵ gleich sind zu R⁷, R⁸ (R⁴, R⁵= R⁷, R⁸), wobei R¹, R² ausgewählt sind aus der Gruppe bestehend aus Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C20 Alkylrest, bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C16 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C15 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C14 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C13 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C12 Alkylrest weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C11 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C10 Alkylrest; und R⁴, R⁵ und R⁷, R⁸ ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest, bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C16 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C15 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C14 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C13 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C12 Alkylrest weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C11 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C10 Alkylrest.
7. 7. Verwendung eines Triazin-Derivats gemäß einer der Ausführungsformen 1 oder 4 bis 6 als Flammschutzmittel für einen Polyurethan(PU)- oder Polyisocyanurat(PIR)-Hartschaum, wobei R¹, R² ungleich sind zu R⁴, R⁵ und zu R⁷, R⁸ (R¹, R² ≠ R⁴, R⁵ und R¹, R² ≠ R⁷, R⁸) und R⁴, R⁵ ungleich sind zu R⁷, R⁸ (R⁴, R⁵ ≠ R⁷, R⁸), wobei R¹, R² ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C3 bis C20 Alkylrest und C6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist und R⁴, R⁵ und R⁷, R⁸ jeweils ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und 6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist.
8. 8. Verwendung eines Triazin-Derivats gemäß einer der Ausführungsformen 1 bis 7 als Flammschutzmittel für einen Polyurethan(PU)- oder Polyisocyanurat(PIR)-Hartschaum, wobei das Triazin-Derivat gemäß Formel (I) in einer Menge von 0,1 bis 10 Gewichts-%, bezogen auf ein Gesamtgewicht von 100 Gewichts-% aller bei der Herstellung des Polyurethan(PU)- oder Polyisocyanurat(PIR)-Hartschaum eingesetzter Komponenten verwendet wird.
9. 7. Verwendung eines Triazin-Derivats gemäß einer der Ausführungsformen 1 bis 6 als Flammschutzmittel für einen Polyurethan(PU)- oder Polyisocyanurat(PIR)-Hartschaum, insbesondere für einen PIR-Hartschaum, wobei chlorierte Phosphatester in weniger als 0,1 Gewichts-%, bezogen auf ein Gesamtgewicht von 100 Gewichts-% aller bei der Herstellung des Polyurethan(PU)- oder Polyisocyanurat(PIR)-Hartschaum eingesetzten Komponenten, verwendet werden.
10. 8. Verwendung eines Triazin-Derivats gemäß einer der Ausführungsformen 1 bis 7 als Flammschutzmittel für einen Polyurethan(PU)- oder Polyisocyanurat(PIR)-Hartschaum, wobei außer dem Triazin-Derivat der Formel (I) keine weiteren Flammschutzmittel in mehr als 0,1 Gewichts-%, bezogen auf ein Gesamtgewicht von 100 Gewichts-% aller bei der Herstellung des Polyurethan(PU)- oder Polyisocyanurat(PIR)-Hartschaum eingesetzten Komponenten, verwendet werden.
11. 9. Polyurethan(PU)- oder Polyisocyanurat(PIR)-Hartschaum, erhalten oder erhältlich durch Umsetzung von
    1. A) mindestens einem Polyisocyanat,
    2. B) mindestens einem Polyol,
    3. C) einem oder mehreren Treibmitteln,
    4. D) einem oder mehreren Katalysatoren,
    5. E) gegebenenfalls weiteren Hilfsmitteln oder Zusatzstoffen; und
    6. F) einem Flammschutzmittel umfassend, bevorzugt bestehend aus, einem oder mehreren Triazin-Derivaten der Formeln (I) gemäß einer der Ausführungsformen 1 bis 8.
12. 10. Polyurethan(PU)- oder Polyisocyanurat(PIR)-Hartschaum nach Ausführungsform 9, wobei das/die Triazin-Derivat(e) gemäß Formel (I) in einer Menge von insgesamt 0,1 bis 10 Gewichts-%, bezogen auf ein Gesamtgewicht von 100 Gewichts-% aller bei der Herstellung des Polyurethan(PU)- oder Polyisocyanurat(PIR)-Hartschaum eingesetzter Komponenten verwendet wird/werden.
13. 11. Polyurethan(PU)- oder Polyisocyanurat(PIR)-Hartschaum nach Ausführungsform 9 oder 10, wobei chlorierte Phosphatester in weniger als 0,1 Gewichts-%, bezogen auf ein Gesamtgewicht von 100 Gewichts-% aller bei der Herstellung des Polyurethan(PU)- oder Polyisocyanurat(PIR)-Hartschaum eingesetzten Komponenten, verwendet werden.
14. 12. Polyurethan(PU)- oder Polyisocyanurat(PIR)-Hartschaum, insbesondere PIR-Hartschaum, nach einer der Ausführungsformen 9 bis 11, wobei außer dem Triazin-Derivat der Formel (I) keine weiteren Flammschutzmittel in mehr als 0,1 Gewichts-%, bezogen auf ein Gesamtgewicht von 100 Gewichts-% aller bei der Herstellung des Polyurethan(PU)- oder Polyisocyanurat(PIR)-Hartschaum eingesetzten Komponenten, verwendet werden.
15. 13. Triazin-Derivat der Formel (I)
    
    wobei jeweils

    X, Y, Z

    jeweils ein Sauerstoff- oder ein Schwefelatom ist;

    R1, R2

    gleich sind und ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und C6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist;

    R4, R5

    gleich sind und ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und C6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist;

    R7, R8

    gleich sind und ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und C6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist;

    wobei mindestens R¹, R² verschieden sind zu R⁴, R⁵.
16. 14. Triazin-Derivat der Formel (I) nach Ausführungsform 13, wobei R¹, R² ungleich sind zu R⁴, R⁵ und zu R⁷, R⁸ (R¹, R² ≠ R⁴, R⁵ und R¹, R² ≠ R⁷, R⁸), wobei R¹, R² ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C3 bis C20 Alkylrest und 6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist und R⁴, R⁵ und R⁷, R⁸ ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und 6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist.
17. 15. Triazin-Derivat der Formel (I) nach Ausführungsform 13 oder 14, wobei R¹, R² ungleich sind zu R⁴, R⁵ und zu R⁷, R⁸ (R¹, R² ≠ R⁴, R⁵ und R¹, R² R⁷, R⁸) und R⁴, R⁵ gleich sind zu R⁷, R⁸ (R⁴, R⁵= R⁷, R⁸), wobei R¹, R² ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C20 Alkylrest, bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C16 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C15 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C14 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C13 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C12 Alkylrest weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C11 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C10 Alkylrest und R⁴, R⁵ und R⁷, R⁸ ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest, bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C16 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C15 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C14 Alkylrest, weiter be-vorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C13 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C12 Alkylrest weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C11 Alkylrest, weiter bevorzugt aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C10 Alkylrest.
18. 16. Triazin-Derivat der Formel (I) nach einer der Ausführungsformen 13 bis 15, wobei R¹, R² ungleich sind zu R⁴, R⁵ und zu R⁷, R⁸ (R¹, R²⁷ ≠ R⁴, R⁵ und R¹, R² ≠ R⁷, R⁸) und R⁴, R⁵ gleich sind zu R⁷, R⁸ (R⁴, R⁵ = R⁷, R⁸), wobei R¹, R² ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C4 bis C20 Alkylrest und 6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist und R⁴, R⁵ und R⁷, R⁸ ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und 6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist.
19. 17. Triazin-Derivat der Formel (I) nach einer der Ausführungsformen 13 bis 16, wobei R¹, R² ungleich sind zu R⁴, R⁵ und zu R⁷, R⁸ (R¹, R²⁷ ≠ R⁴, R⁵ und R¹, R² ≠ R⁷, R⁸) und R⁴, R⁵ ungleich sind zu R⁷, R⁸ (R⁴, R⁵ ≠ R⁷, R⁸), wobei R¹, R² ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C3 bis C20 Alkylrest und 6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist und R⁴, R⁵ und R⁷, R⁸ jeweils ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und 6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist.
20. 18. Verfahren zur Herstellung eines Triazin-Derivats der allgemeinen Formel (I) umfassend
    1. (i) Bereitstellen einer Phosphit-Mischung umfassend
       1. (i.1) ein erstes Trialkyl- bzw. Triarylphosphit der allgemeinen Formel (A)
          
          wobei

          X

          ein Heteroatom, insbesondere ein Sauerstoff oder ein Schwefelatom, ist;

          R1, R2, R3

          gleich sind und ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und C6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und verzweigtem und unverzweigtem C1 bis C10 Alkylrest aufweist; und

       2. (i.2) ein zweites Trialkyl- bzw. Triarylphosphit der allgemeinen Formel (B)
          
          wobei

          Y

          ein Heteroatom insbesondere ein Sauerstoff oder ein Schwefelatom, ist;

          R4, R5, R6

          gleich sind und ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und C6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und C1 bis C10 Alkylrest aufweist;

          wobei R¹, R², R³ des erstes Trialkylphosphits gemäß (i.1) ungleich sind zu R⁴, R⁵, R⁶ des zweiten Trialkylphosphits gemäß (i.2); und
       3. (i.3) optional ein drittes Trialkyl- bzw. Triarylphosphit der allgmeinen Formel (C)
          
          wobei

          Z

          ein Heteroatom, insbesondere ein Sauerstoff oder ein Schwefelatom, ist;

          R7, R8, R9

          gleich sind und ausgewählt sind aus der Gruppe bestehend aus verzweigtem und unverzweigtem C1 bis C20 Alkylrest und C6 bis C12 Arylrest, wobei der C6 bis C12 Arylrest mindestens einen Substituenten ausgewählt aus Wasserstoffatom und C1 bis C10 Alkylrest aufweist;

          wobei R⁷, R⁸, R⁹ ungleich sind zu R¹, R², R³ des erstes Trialkylphosphits gemäß (i.1) und ungleich sind zu R⁴, R⁵, R⁶ des zweiten Trialkylphosphits gemäß (i.2). und
    2. (ii) Bereitstellen von Cyanurchlorid;
    3. (iii) Umsetzung der Phosphit-Mischung gemäß (i) mit dem Cyanurchlorid gemäß (ii), unter Erhalt mindestens eines Triazin-Derivats der allgemeinen Formel (I)
       
       , wobei die Reste R¹-R⁹ und X, Y, Z die in einer der Ausführungsformen 1 bis 17 angegebene Bedeutung haben.
21. 19. Verfahren zur Herstellung eines Triazin-Derivats der allgemeinen Formel (I) gemäß Ausführungsform 18, wobei mindestens in (i), (ii) oder (iii) kein Lösungsmittel vorhanden, bevorzugt weder in (i) noch in (ii) noch in (iii) ein Lösungsmittel vorhanden ist (lösungsmittelfreie Synthese).
22. 20. Verfahren zur Herstellung eines Triazin-Derivats der allgemeinen Formel (I) gemäß Ausführungsform 18 oder 19, wobei mindestens eines der Trialkyl- bzw. Triarylphosphit der allgemeinen Formel (A), (B) oder optional (C) bei 25 °C und 1013 mbar flüssig ist.
23. 21. Verfahren zur Herstellung eines Triazin-Derivats der allgemeinen Formel (I) gemäß Ausführungsform 20, wobei, sofern mindestens eine weiteres der Trialkyl- bzw. Triarylphosphit der allgemeinen Formel (A), (B) oder optional (C) bei 25 °C und 1013 mbar fest ist, dass mindestens eine weitere feste Trialkyl- bzw. Triarylphosphit im mindestens einen flüssigen Trialkyl- bzw. Triarylphosphit gelöst wird, so dass die Phosphit-Mischung gemäß (i) bei 25 °C und 1013 mbar flüssig ist.
24. 22. Verfahren zur Herstellung eines Triazin-Derivats der allgemeinen Formel (I) gemäß einer der Ausführungsformen 18 bis 21, wobei das molare Verhältnis der Summe aller in der Phosphit-Mischung gemäß (i) enthaltenen Trialkyl- bzw. Triarylphosphit [(A) + (B) oder (A) + (B) + (C)] zum Cyanurchlorids bei der Umsetzung gemäß (iii) > 1:1 beträgt, bevorzugt im Bereich von 1,01: 1 bis 2:1 beträgt, weiter bevorzugt im Bereich von 1,1: 1 bis 1,5:1 beträgt.
25. 23. Verfahren zur Herstellung eines Triazin-Derivats der allgemeinen Formel (I) gemäß einer der Ausführungsformen 18 bis 22, wobei das molare Verhältnis von erstem Trialkyl- bzw. Triarylphosphit der allgemeinen Formel (A) zu zweitem Trialkyl- bzw. Triarylphosphit der allgemeinen Formel (B) im Bereich von 0,5:1 bis 1,5:1 beträgt, bevorzugt im Bereich von 0,8: 1 bis 1,2:1 beträgt, weiter bevorzugt im Bereich von 0,9:1 bis 1,1:1 beträgt, weiter bevorzugt 1:1 beträgt; oder wobei das molare Verhältnis von erstem Trialkyl- bzw. Triarylphosphit der allgemeinen Formel (A) zu zweitem Trialkyl- bzw. Triarylphosphit der allgemeinen Formel (B) im Bereich von 0,7:2 bis 1,3:2 beträgt, bevorzugt im Bereich von 0,8: 2 bis 1,1:2 beträgt, weiter bevorzugt im Bereich von 0,9:2 bis 1,1:2 beträgt, weiter bevorzugt 1:2 beträgt.
26. 24. Verfahren zur Herstellung eines Triazin-Derivats der allgemeinen Formel (I) gemäß einer der Ausführungsformen 18 bis 23, wobei das molare Verhältnis von zweitem Trialkyl- bzw. Triarylphosphit der allgemeinen Formel (B) zu drittem Trialkyl- bzw. Triarylphosphit der allgemeinen Formel (C) im Bereich von 0,5:1: bis 1,5:1 beträgt, bevorzugt im Bereich von 0,8: 1 bis 1,2:1 beträgt, weiter bevorzugt im Bereich von 0,9:1 bis 1,1:1 beträgt, weiter bevorzugt 1:1 beträgt.
27. 25. Verfahren zur Herstellung eines Triazin-Derivats der allgemeinen Formel (I) gemäß einer der Ausführungsformen 18 bis 24, wobei der Schritt (iii) umfasst:
    1. (iii. 1a) Vorlegen von gemäß (i) bereitgestelltem ersten und zweiten Trialkyl- bzw. Triarylphosphit (A), (B) und optional vom drittem Trialkyl- bzw. Triarylphosphit (C) in einem Reaktionsgefäß,
    2. (iii.2a) Zugabe des gemäß (ii) bereitgestellten Cyanurchlorids in das Reaktionsgefäß; oder
    3. (iii. 1b) Vorlegen von gemäß (ii) bereitgestelltem Cyanurchlorid in einem Reaktionsgefäß;
    4. (iii.2b) Zugabe des gemäß (i) bereitgestellten ersten und zweiten Trialkyl- bzw. Triarylphosphits (A), (B) und optional des dritten Trialkyl- bzw. Triarylphosphits (C) in das Reaktionsgefäß.

The present invention is explained in more detail by the following series of embodiments and combinations of embodiments, which result from the specified dependencies and references. In particular, it is noted that in any case where a range of embodiments is mentioned, for example in connection with a term such as “any of embodiments (1) to (4)”, each embodiment in that range will be explicitly disclosed to those skilled in the art should, ie the wording of this term is to be understood by the person skilled in the art as equivalent to “one of the embodiments (1), (2), (3) and (4)”. Furthermore, it is expressly noted that the following series of embodiments are not the scope of the claims, but rather represent an appropriately structured part of the description directed at general and preferred aspects of the present invention.

1. 1. Use of a triazine derivative of the formula (I) as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam
   
   where each

   X, Y, Z

   each is an oxygen or a sulfur atom;

   R1, R2

   are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical;

   R4, R5

   are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical;

   R7, R8

   are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical;

   where R ¹ , R ² are the same or different from R ⁴ , R ⁵ and R ⁴ , R ⁵ are the same or different from R ⁷ , R ⁸ .
2. 2. Use of a triazine derivative according to embodiment 1 as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, where R ¹ , R ² and R ⁴ , R ⁵ and R ⁷ , R ⁸ are the same (R ¹ = R ² = R ⁴ = R ⁵ = R ⁷ = R ⁸ ) and are selected from the group consisting of branched and unbranched C4 to C20 alkyl radicals.
3. 3. Use of a triazine derivative according to embodiment 1 or 2 as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, where R ¹ , R ² and R ⁴ , R ⁵ and R ⁷ , R ⁸ are the same ( R ¹ = R ² = R ⁴ = R ⁵ = R ⁷ = R ⁸ ) and are selected from the group consisting of branched and unbranched C4 to C17 alkyl radicals, more preferably from the group consisting of branched and unbranched C4 to C16 alkyl radicals, further preferably from the group consisting of branched and unbranched C4 to C15 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C14 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C13 alkyl radical, more preferably from the group consisting from branched and unbranched C4 to C12 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C11 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C10 alkyl radical.
4. 4. Use of a triazine derivative according to embodiment 1 as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, where R ¹ , R ² are different from R ⁴ , R ⁵ and from R ⁷ , R ⁸ (R ¹ , R ² ≠ R ⁴ , R ⁵ and R ¹ , R ² ≠ R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the group consisting of branched and unbranched C3 to C20 alkyl radical and 6 to C12 aryl radical, wherein the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical and R ⁴ , R ⁵ and R ⁷ , R ⁸ are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and 6 to C12 aryl radical, wherein the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical.
5. 5. Use of a triazine derivative according to embodiment 1 or 4 as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, where R ¹ , R ² are different from R ⁴ , R ⁵ and from R ⁷ , R ⁸ (R ¹ , R ² ≠ R ⁴ , R ⁵ and R ¹ , R ² ≠ R ⁷ , R ⁸ ) and R ⁴ , R ⁵ are equal to R ⁷ , R ⁸ (R ⁴ , R ⁵ = R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the group consisting of branched and unbranched C4 to C20 alkyl radical and C6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical and R ⁴ , R ⁵ and R ⁷ , R ⁸ are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical.
6. 6. Use of a triazine derivative according to embodiment 1 or 4 to 5 as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, where R ¹ , R ² are different from R ⁴ , R ⁵ and R ⁷ , R ⁸ (R ¹ , R ² ≠ R ⁴ , R ⁵ and R ¹ , R ² ≠ R ⁷ , R ⁸ ) and R ⁴ , R ⁵ are equal to R ⁷ , R 8 (R ⁴ , ^{R 5 =} R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the group consisting of branched and unbranched C4 to C20 alkyl radicals, preferably from the group consisting of branched and unbranched C4 to C16 alkyl radicals, more preferably from the group consisting of branched and unbranched C4 to C15 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C14 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C13 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C12 alkyl radical more preferably from the group consisting of branched and unbranched C4 to C11 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C10 alkyl radical; and R ⁴ , R ⁵ and R ⁷ , R ⁸ are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical, preferably from the group consisting of branched and unbranched C1 to C16 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C15 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C14 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C13 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C12 alkyl radical more preferably from the group consisting of branched and unbranched C1 to C11 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C10 alkyl radical.
7. 7. Use of a triazine derivative according to one of embodiments 1 or 4 to 6 as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, where R ¹ , R ² are different from R ⁴ , R ⁵ and R ⁷ , R ⁸ (R ¹ , R ² ≠ R ⁴ , R ⁵ and R ¹ , R ² ≠ R ⁷ , R ⁸ ) and R ⁴ , R ⁵ are not equal to R ⁷ , R ⁸ (R ⁴ , R ⁵ ≠ R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the group consisting of branched and unbranched C3 to C20 alkyl radical and C6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical and R ⁴ , R ⁵ and R ⁷ , R ⁸ are each selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and 6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical.
8. 8. Use of a triazine derivative according to one of embodiments 1 to 7 as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, the triazine derivative according to formula (I) being in an amount of 0.1 to 10 % by weight, based on a total weight of 100% by weight of all components used in the production of the polyurethane (PU) or polyisocyanurate (PIR) rigid foam.
9. 7. Use of a triazine derivative according to one of embodiments 1 to 6 as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, in particular for a PIR rigid foam, with chlorinated phosphate esters in less than 0.1% by weight. , based on a total weight of 100% by weight of all components used in the production of the polyurethane (PU) or polyisocyanurate (PIR) rigid foam.
10. 8. Use of a triazine derivative according to one of embodiments 1 to 7 as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, wherein apart from the triazine derivative of the formula (I), no other flame retardants are present in more than 0. 1% by weight, based on a total weight of 100% by weight of all components used in the production of the polyurethane (PU) or polyisocyanurate (PIR) rigid foam, can be used.
11. 9. Polyurethane (PU) or polyisocyanurate (PIR) rigid foam, obtained or obtainable by reacting
    1. A) at least one polyisocyanate,
    2. B) at least one polyol,
    3. C) one or more propellants,
    4. D) one or more catalysts,
    5. E) if necessary, other aids or additives; and
    6. F) a flame retardant comprising, preferably consisting of, one or more triazine derivatives of the formulas (I) according to one of embodiments 1 to 8.
12. 10. Polyurethane (PU) or polyisocyanurate (PIR) rigid foam according to embodiment 9, wherein the triazine derivative (s) according to formula (I) in a total amount of 0.1 to 10% by weight, based on a Total weight of 100% by weight of all components used in the production of the polyurethane (PU) or polyisocyanurate (PIR) rigid foam is/are used.
13. 11. Polyurethane (PU) or polyisocyanurate (PIR) rigid foam according to embodiment 9 or 10, wherein chlorinated phosphate esters in less than 0.1% by weight, based on a total weight of 100% by weight of all in the production of the polyurethane (PU ) or polyisocyanurate (PIR) rigid foam components can be used.
14. 12. Polyurethane (PU) or polyisocyanurate (PIR) rigid foam, in particular PIR rigid foam, according to one of embodiments 9 to 11, wherein apart from the triazine derivative of the formula (I), no other flame retardants are present in more than 0.1% by weight. %, based on a total weight of 100% by weight of all components used in the production of the polyurethane (PU) or polyisocyanurate (PIR) rigid foam.
15. 13. Triazine derivative of formula (I)
    
    where each

    X, Y, Z

    each is an oxygen or a sulfur atom;

    R1, R2

    are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical;

    R4, R5

    are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical;

    R7, R8

    are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical;

    where at least R ¹ , R ² are different from R ⁴ , R ⁵ .
16. 14. Triazine derivative of the formula (I) according to embodiment 13, where R ¹ , R ² are different from R ⁴ , R ⁵ and from R ⁷ , R ⁸ (R ¹ , R ² ≠ R ⁴ , R ⁵ and R ¹ , R ² ≠ R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the group consisting of branched and unbranched C3 to C20 alkyl radical and 6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical and R ⁴ , R ⁵ and R ⁷ , R ⁸ are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and 6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected of hydrogen atom and branched and unbranched C1 to C10 alkyl radical.
17. 15. Triazine derivative of the formula (I) according to embodiment 13 or 14, where R ¹ , R ² are different from R ⁴ , R ⁵ and from R ⁷ , R ⁸ (R ¹ , R ² ≠ R ⁴ , R ⁵ and R ¹ , R ² R ⁷ , R ⁸ ) and R ⁴ , R ⁵ are equal to R ⁷ , R ⁸ (R ⁴ , R ⁵ = R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the group consisting of branched and unbranched C4 to C20 alkyl radical, preferably from the group consisting of branched and unbranched C4 to C16 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C15 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C14 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C13 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C12 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C11 alkyl radical, more preferred from the group consisting of branched and unbranched C4 to C10 Alkyl radical and R ⁴ , R ⁵ and R ⁷ , R ⁸ are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical, preferably from the group consisting of branched and unbranched C1 to C16 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C15 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C14 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C13 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C12 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C11 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C10 alkyl radical.
18. 16. Triazine derivative of the formula (I) according to one of embodiments 13 to 15, where R ¹ , R ² are different from R ⁴ , R ⁵ and from R ⁷ , R ⁸ (R ¹ , R ²⁷ ≠ R ⁴ , R ⁵ and R ¹ , R ² ≠ R ⁷ , R ⁸ ) and R ⁴ , R ⁵ are equal to R ⁷ , R ⁸ (R ⁴ , R ⁵ = R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the group consisting of branched and unbranched C4 to C20 alkyl radical and 6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical and R ⁴ , R ⁵ and R ⁷ , R ⁸ are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and 6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical.
19. 17. Triazine derivative of the formula (I) according to one of embodiments 13 to 16, where R ¹ , R ² are different from R ⁴ , R ⁵ and from R ⁷ , R ⁸ (R ¹ , R ²⁷ ≠ R ⁴ , R ⁵ and R ¹ , R ² ≠ R ⁷ , R ⁸ ) and R ⁴ , R ⁵ are not equal to R ⁷ , R ⁸ (R ⁴ , R ⁵ ≠ R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the group consisting of branched and unbranched C3 to C20 alkyl radical and 6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical and R ⁴ , R ⁵ and R ⁷ , R ⁸ are each selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and 6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical.
20. 18. Process for producing a triazine derivative of the general formula (I).
    1. (i) providing a phosphite mixture
       1. (i.1) a first trialkyl or triaryl phosphite of the general formula (A)
          
          where

          X

          is a heteroatom, especially an oxygen or a sulfur atom;

          R1, R2, R3

          are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical; and

       2. (i.2) a second trialkyl or triaryl phosphite of the general formula (B)
          
          where

          Y

          a heteroatom, in particular an oxygen or a sulfur atom;

          R4, R5, R6

          are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and C1 to C10 alkyl radical;

          where R ¹ , R ² , R ³ of the first trialkyl phosphite according to (i.1) are not equal to R ⁴ , R ⁵ , R ⁶ of the second trialkyl phosphite according to (i.2); and
       3. (i.3) optionally a third trialkyl or triaryl phosphite of the general formula (C)
          
          where

          Z

          is a heteroatom, especially an oxygen or a sulfur atom;

          R7, R8, R9

          are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and C1 to C10 alkyl radical;

          where R ⁷ , R ⁸ , R ⁹ are not equal to R ¹ , R ² , R ³ of the first trialkyl phosphite according to (i.1) and are not equal to R ⁴ , R ⁵ , R ⁶ of the second trialkyl phosphite according to (i.2) . and
    2. (ii) providing cyanuric chloride;
    3. (iii) reacting the phosphite mixture according to (i) with the cyanuric chloride according to (ii), to obtain at least one triazine derivative of the general formula (I)
       
       , where the radicals R ¹ -R ⁹ and X, Y, Z have the meaning given in one of embodiments 1 to 17.
21. 19. A process for producing a triazine derivative of the general formula (I) according to embodiment 18, wherein no solvent is present at least in (i), (ii) or (iii), preferably neither in (i) nor in (ii) nor in (iii) a solvent is present (solvent-free synthesis).
22. 20. A process for producing a triazine derivative of the general formula (I) according to embodiment 18 or 19, wherein at least one of the trialkyl or triaryl phosphite of the general formula (A), (B) or optionally (C) at 25 ° C and 1013 mbar liquid.
23. 21. A process for producing a triazine derivative of the general formula (I) according to embodiment 20, wherein, if at least one further, the trialkyl or triaryl phosphite of the general formula (A), (B) or optionally (C) at 25 ° C and 1013 mbar is solid, that at least one further solid trialkyl or triaryl phosphite is dissolved in at least one liquid trialkyl or triaryl phosphite, so that the phosphite mixture according to (i) is liquid at 25 ° C and 1013 mbar.
24. 22. A process for producing a triazine derivative of the general formula (I) according to one of embodiments 18 to 21, wherein the molar ratio of the sum of all trialkyl or triaryl phosphite [(A) +. contained in the phosphite mixture according to (i). (B) or (A) + (B) + (C)] to the cyanuric chloride at the Reaction according to (iii) is > 1:1, preferably in the range from 1.01: 1 to 2:1, more preferably in the range from 1.1: 1 to 1.5:1.
25. 23. A process for producing a triazine derivative of the general formula (I) according to one of embodiments 18 to 22, wherein the molar ratio of the first trialkyl or triaryl phosphite of the general formula (A) to the second trialkyl or triaryl phosphite of the general formula (B) is in the range of 0.5:1 to 1.5:1, preferably in the range of 0.8:1 to 1.2:1, more preferably in the range of 0.9:1 to 1.1 :1, more preferably 1:1; or wherein the molar ratio of the first trialkyl or triaryl phosphite of the general formula (A) to the second trialkyl or triaryl phosphite of the general formula (B) is in the range from 0.7:2 to 1.3:2, preferably in the range from 0.8:2 to 1.1:2, more preferably in the range from 0.9:2 to 1.1:2, more preferably 1:2.
26. 24. A process for producing a triazine derivative of the general formula (I) according to one of embodiments 18 to 23, wherein the molar ratio of the second trialkyl or triaryl phosphite of the general formula (B) to the third trialkyl or triaryl phosphite of the general formula (C) is in the range from 0.5:1: to 1.5:1, preferably in the range from 0.8:1 to 1.2:1, more preferably in the range from 0.9:1 to 1, is 1:1, more preferably 1:1.
27. 25. A process for producing a triazine derivative of the general formula (I) according to one of embodiments 18 to 24, wherein step (iii) comprises:
    1. (iii. 1a) placing the first and second trialkyl or triaryl phosphite (A), (B) provided according to (i) and optionally the third trialkyl or triaryl phosphite (C) in a reaction vessel,
    2. (iii.2a) adding the cyanuric chloride provided according to (ii) to the reaction vessel; or
    3. (iii. 1b) placing cyanuric chloride provided according to (ii) in a reaction vessel;
    4. (iii.2b) Adding the first and second trialkyl or triaryl phosphite (A), (B) provided according to (i) and optionally the third trialkyl or triaryl phosphite (C) into the reaction vessel.

The present invention is further explained by the following reference examples, comparative examples and examples.

Examples

Methods ATR spectroscopy: ATR infrared spectra were recorded on a Nicolet 380 IR spectrometer. The measurement was carried out in a range from 4000 cm ^-1 to 600 cm ^-1 with a resolution of 4 cm ^-1 and 128 scans. Data were given in cm ^-1 . A device-related CO ₂ band (ambient air) was observed in the range of 2300 cm ^-1 . Thermogravimetric analysis (TGA): Thermogravimetric analyzes were carried out using a Netzsch TG 209 F1 under a nitrogen atmosphere and a heating rate of 10 K/min. Limiting Oxygen Index (LOI) Test: The LOI was determined using an oxygen index module from FIRE in accordance with DIN EN ISO 4589-2. Small burner test: Small burner tests were carried out based on DIN EN-ISO 11925-2 (2020-07), whereby the tested test specimens deviated from the standard and had dimensions of 190 mm x 91 mm x 20 mm. Fire behavior: DIN EN 13501-1 Class E (2010-01)

Reference example 1a: Synthesis of symmetrically substituted triazines

0.19 mol (35 g) of cyanuric chloride was placed in a 500 ml three-necked flask equipped with a dropping funnel, a reflux condenser and a Walfisch magnetic stirrer. The flask was cooled using an ice bath. 0.58 mol of alkyl or aryl phosphite were slowly added dropwise via a dropping funnel. After the addition was complete, the ice bath was slowly melted and heated further. After about 2 h of heating, the reaction could be cooled to room temperature. The product was then purified by distillation.

Liquid trialkyl and/or triaryl phosphites were used without solvents. Solid trialkyl or triaryl phosphites were used in dissolved form, dissolved in a liquid phosphite. “Liquid” and “solid” respectively referred to the physical state of the triazine at 25 °C and 1013 mbar.

Reference example 1b: Synthesis of symmetrically substituted triazines

1.99 mol of alkyl phosphite were stirred at 500 rpm in a 2 L three-neck round bottom flask with a two-neck attachment and a drying tube with a molecular sieve 4A and covered with argon. Using a solids feeder, 0.66 mol (122.5 g) of cyanuric chloride was added at an oil bath temperature of 30 ° C within 125 minutes. After the addition had ended, the mixture was gradually heated to 90 °C over four hours. The following day the mixture was heated again at 90 °C for 7 h. The product was obtained by cleaning on a rotary evaporator at 85 ° C and 4 mbar.

Liquid trialkyl and/or triaryl phosphites were used without solvents. Solid trialkyl or triaryl phosphites were used in dissolved form, dissolved in a liquid phosphite. “Liquid” and “solid” respectively referred to the physical state of the triazine at 25 °C and 1013 mbar.

Reference example 2a: Synthesis of asymmetrically substituted triazines

0.24 mol (45 g) of cyanuric chloride was placed in a 500 ml three-necked flask equipped with a dropping funnel, a reflux condenser and a Walfisch magnetic stirrer. The flask was cooled using an ice bath. A mixture of 0.25 mol of a first trialkyl or triaryl phosphite and 0.50 mol of a second trialkyl or triaryl phosphite, different from the first trialkyl or triaryl phosphite, and optionally a third, of the first and second trialkyl, were added via a dropping funnel - or triaryl phosphite, various trialkyl or triaryl phosphites, added dropwise. After the addition was complete, the ice bath was slowly melted and heated further. After about 2 h of heating, the reaction could be cooled to room temperature. The product was then purified by distillation.

Liquid trialkyl and/or triaryl phosphites were used without solvents. Solid trialkyl or triaryl phosphites were used in dissolved form, dissolved in a liquid trialkyl or triaryl phosphite, which was also a reaction partner, i.e. one of the first, second or possibly third trialkyl or triaryl phosphite. “Liquid” and “solid” respectively referred to the physical state of the triazine at 25 °C and 1013 mbar.

Reference example 2b: Synthesis of asymmetrically substituted triazines

A mixture of 0.87 mol of a first trialkyl or triaryl phosphite and 1.75 mol of a second trialkyl or triaryl phosphite, different from the first trialkyl or triaryl phosphite, was placed in a 2 L three-neck round bottom flask with a two-neck attachment and a drying tube with a molecular sieve 4A optionally a third trialkyl or triaryl phosphite, different from the first and second trialkyl or triaryl phosphite, stirred at 500 rpm and covered with argon. Using a solids feeder, 0.84 mol (157.5 g) of cyanuric chloride was added at an oil bath temperature of 30 ° C within 125 minutes. After the addition has ended, the mixture is gradually heated to 90 °C over four hours. The following day the mixture is heated again at 90 °C for 7 hours. The product was obtained by cleaning on a rotary evaporator at 85 ° C and 4 mbar.

Liquid trialkyl and/or triaryl phosphites were used without solvents. Solid trialkyl or triaryl phosphites were used in dissolved form, dissolved in a liquid trialkyl or triaryl phosphite, which was also a reaction partner, i.e. one of the first, second or possibly third trialkyl or triaryl phosphite. “Liquid” and “solid” respectively referred to the physical state of the triazine at 25 °C and 1013 mbar.

Reference example 3a: Production of flame-retardant polymer foam

Rigid foams were produced by mixing the polyol component, containing polyol, blowing agent, catalyst and stabilizer, and the isocyanate component, containing isocyanate and flame retardant.

Reference example 3b: Production of flame-retardant polymer foam

Rigid foams were produced by mixing the polyol component, containing polyol, blowing agent, catalyst, stabilizer and flame retardant, and the isocyanate component.

Example 1a: Synthesis of 2,4,6-Tris(di-ri-butoxyphosphonate)-1,3,5-triazine (symmetrical triazine)

145 g (0.58 mol) of tri-n-butyl phosphite were reacted according to Reference Example 1a. 126.80 g of the product 2,4,6-tris(di-n-butoxyphosphonate)-1,3,5-triazine were obtained as a colorless, light yellow liquid.

³¹ P NMR spectroscopy σ in (ppm): 29.86, 10.11, 7.28, 0.68 (product), 0.14, -1.06 ¹³ C NMR spectroscopy σ in (ppm): 172.6, 170.0 (CP, ¹ J _(CP) =259 Hz, ³ J _(CP) =12 Hz), 77.0 (CDCl ₃ ), 67.6 (OCH ₂ ), 31.5 (CH ₂ ), 17.7(CH ₂ ), 12.6(CH ₃ ) ¹ H NMR spectroscopy σ in (ppm ): 4.40 (q,OCH ₂ ), 1.76 (m, CH ₂ ), 1.49 (m, CH ₂ ), 0.97 (t, CH ₃ )

ATR infrared spectrum:

v = 626 (vPO); 809 (PC); 775-860 (sym-triazine); 980-1000 (sym-triazine); 1288 (vP=O); 1350-1450 (sym-triazine); 1457 (δ-CH ₃ ); 1582-1520 (sym-triazine); 2973(CC, -CH ₂ /-CH ₃ )

In thermogravimetric analysis (TGA), the product showed the following properties 5% weight loss / °C T _onset /°C Residual mass at 995 °C / % 188 245 0

Further symmetrical triazines - Examples 2 to 7 - were prepared analogously to Reference Example 1, with the other examples and the respective starting materials used and the physical state of the product obtained being listed in Table 1.

Example 1b: Synthesis of 2,4,6-Tris(di-n-butoxyphosphonate)-1,3,5-triazine (symmetrical triazine)

The production was carried out according to reference example 1b. 498.8 g (1.99 mol) of tri-n-butyl phosphite were stirred at 500 rpm and covered with argon in a 2 liter three-neck round bottom flask with a two-neck attachment and a drying tube with a molecular sieve 4A. Using a solids feeder, 122.5 g (0.66 mol) of cyanuric chloride are added at an oil bath temperature of 30 °C within 125 minutes. After the addition has ended, the mixture is gradually heated to 90 °C over four hours. The following day the mixture is heated again at 90 °C for 7 hours. The product is obtained by cleaning on a rotary evaporator at 85 °C and 4 mbar. 436.9 g of the product 2,4,6-tris(di-n-butoxyphosphonate)-1,3,5-triazine were obtained as a light yellow liquid. ³¹ P NMR spectroscopy σ in (ppm): 29.40, 9.8586, 7.0028, 0.4668 (product), 0.1014, -1.4406 ¹³ C NMR spectroscopy σ in (ppm): 172.1, 169173.2, 170.5 (CP, ¹ J _(CP) =259 Hz, ³ J _(CP) =12 Hztriazine ring), 77.05 (CDCl ₃ ), 66.968.1 (OCH ₂ ), 3132.1 (CH ₂ ), 1718.2 (CH ₂ ), 12.013.1 (CH ₃ ) ¹ H NMR -Spectroscopy σ in (ppm): 4.3901 (q,OCH ₂ ), 1.7741 (m, CH ₂ ), 1.4910 (m, CH ₂ ), 0.9759 (t, CH ₃ ) Elemental analysis # %C % H %N % Cl %P % O (calc.) product 49.04 ± 0.01 8.26 ± 0.01 6.36 ± 0.01 0.05 ± 0.01 14.06 ± 0.01 22.26 ± 0.04 theory 49.30 8.29 6.39 0 14,13 21.89

Example 8: Synthesis of 2,4,6-Tris(dimethoxy/di-n-butoxyphosphonate)-1,3,5-triazine (unsymmetrical triazine)

The production was carried out according to Reference Example 2a, using trimethyl phosphite in an amount of 31 g (0.25 mol) as the first trialkyl phosphite and tri-n-butyl phosphite in an amount of 125 g (0.50 mol) as the second trialkyl phosphite. 138.93 g of a colorless, light yellow liquid were obtained which contained 2,4,6-tris(dimethoxy/di-n-butoxyphosphonate)-1,3,5-triazine.

³¹ P-NMR spectroscopy σ in (ppm): 30.47, 10.793, 2.90-2.80 (product), 0.88, 0.78-0.67 (product) (J _(PP) =4.8 Hz & 4.6 Hz), -0.95

¹³ C NMR spectroscopy σ in (ppm): 173.3, 172.7, 171.1, 170.5 (CP, ¹ J _(CP) =260 Hz & 261 Hz, ³ J _(CP) =12.4 Hz & 12.5 Hz), 77.0 (CDCl ₃ ), 68.1 (OCH ₂ ), 54.7 (OCH ₃ ), 31.9 (CH ₂ ), 18.1 (CH ₂ ), 13.0
( _CH3 )
¹ H NMR spectroscopy σ in (ppm): 4.39 (q,OCH ₂ ), 4.09 (dd,OCH ₃ ),
1.77 (m, _CH2 ), 1.48 (m, _CH2 ), 0.97 (t, _CH3 )

ATR infrared spectrum:

v = 626 (vPO); 809 (PC); 805-820 (triazine); 1110-1160 (triazine); 1288 (vP=O); 1320-1380 (triazine); 1457 (δ-CH ₃ ); 1540-1600 (triazine); 2973(CC, -CH ₂ /-CH ₃ )

In thermoravimetric analysis (TGA) the product has the following properties 5% weight loss / °C T _onset /°C Residual mass at 995 °C / % 170 234 4

In particular, it was apparent from the ¹³ C NMR spectrum that the so-called compound 2,4,6-tris(dimethoxy/di-n-butoxyphosphonate)-1,3,5-triazine had the structure 2-(dimethoxyphosphonate)-4 ,6-di(di-n-butoxyphosphonate)-1,3,5-triazine.

Further asymmetrical triazines - Examples 9 to 20 - were prepared analogously to Reference Example 2a, with the other examples and the respective starting materials used and the physical state of the product obtained being listed in Table 1. Table 1 Triazines or products containing triazines Example number Production according to reference example 1 or 2 Triazine contained in the product Stoichiometric ratio n of P(OR) ₃ R ¹ : R ² : R3 Physical state (at 25 °C and 1013 hPa) Symmetric triazines 1 1 2,4,6-Tris(di-n-butoxyphosphonate)-1,3,5-triazine* n-Bu: n-Bu: n-Bu fluid 2 1 2,4,6-Tris(dimethoxyphosphonate)-1,3,5-triazine Me: Me: Me firmly 3 1 2,4,6-Tris(diethoxyphosphonate)-1,3,5-triazine Et: Et: Et firmly 4 1 2,4,6-Tris(di-i-propoxyphosphonate)-1,3,5-triazine i-Pr : i-Pr : i-Pr firmly 5 1 2,4,6-Tris(diphenyloxyphosphonate)-1,3,5-triazine Ph: Ph : Ph firmly 6 1 2,4,6-Tris(di-i-decyloxyphosphonate)-1,3,5-triazine iDecyl: iDecyl: iDecyl fluid 7 1 2,4,6-Tris(diolyloxyphosphonate)-1,3,5-triazine Oleyl: Oleyl: Oleyl fluid Unsymmetrical triazines or products containing unsymmetrical triazines 8th 2 2,4,6-Tris(dimethoxy/di-n-butoxyphosphonate)-1,3,5-triazine* [2-(dimethoxyphosphonate)-4,6-bis(di-n-butoxyphosphonate)-1,3,5 -triazine] Me: n-Bu 1:2 fluid 9 2 2,4,6-Tris(dimethoxy/diethoxyphosphonate)-1,3,5-triazine [approx. 1:1 mixture of 2-(dimethoxyphosphonate)-4,6-bis(diethoxyphosphonate)-1,3,5-triazine and 2,4-bis(dimethoxyphosphonate)-6-(diethoxyphosphonate)-1,3,5-triazine ] Me: Et 1:1 firmly 10 2 2,4,6-Tris(dimethoxy/diethoxyphosphonate)-1,3,5-triazine [2,4-bis(dimethoxyphosphonate)-6-(diethoxyphosphonate)-1,3,5-triazine] Me : Et 2 : 1 firmly 11 2 2,4,6-Tris(dimethoxy/diethoxyphosphonate)-1,3,5-triazine [2,4-bis(diethoxyphosphonate)-6-(dimethoxyphosphonate)-1,3,5-triazine] Me : Et 1 : 2 firmly 12 2 2,4,6-Tris(diethoxy/di-i-propoxy/din-butoxyphosphonate)-1,3,5-triazine* [2-(diethoxyphosphonate)-4-(di-/- propoxyphosphonate)-6-(di -n-butoxyphosphonate)-1,3,5-triazine] Et : i-Pr : n-Bu 1 : 1 : 1 fluid 13 2 2,4,6-Tris(dimethoxy/diethoxy/di-i-propoxyphosphonate)-1,3,5-triazine [2-(dimethoxyphosphonate)-4-(diethoxyphosphonate)-6-(di-i-propoxyphosphonate)-1 ,3,5-triazine] Me : Et : i-Pr 1:1:1 fluid 14 2 2,4,6-Tris(dimethoxy/di-i-propoxy/di-n-butoxyphosphonate)-1,3,5-triazine [2-(dimethoxyphosphonate)-4-(di-i-propoxyphosphonate)-6- Me : i-Pr: n-Bu 1 : 1 : 1 fluid (di-n-butoxyphosphonate)-1,3,5-triazine] 15 2 2,4,6-Tris(di-i-propoxy/di-n-butoxyphosphonate)-1,3,5-triazine [approx. 1:1 mixture of 2-(di-i-propoxyphosphonate)-4,6-bis(di-n-butoxyphosphonate)-1,3,5-triazine and 2,4-bis(di-i-propoxyphosphonate)-6 -(di-n-butoxyphosphonate)-1,3,5-triazine] i-Pr: n-Bu 1:1 fluid 16 2 2,4,6-Tris(di-n-butoxy/di-phenylphosphonate)-1,3,5-triazine [2,4-bis(di-n-butoxyphosphonate)-6-(di-phenylphosphonate)-1, 3,5-triazine] n-Bu:phenyl 2:1 fluid 17 2 2,4,6-Tris(di-n-butoxy/di-nonlyphenylphosphonate)-1,3,5-triazine [2,4-bis(di-n-butoxyphosphonate)-6-(dinonlyphenylphosphonate)-1,3, 5-triazine] n-Bu: nonylphenyl 2:1 fluid 18 2 2,4,6-Tris(di-n-butoxy/di-lauryl trithiophosphonate)-1,3,5-triazine [2,4-bis(di-n-butoxyphosphonate)-6-(dilauryl trithiophosphonate)-1,3, 5-triazine] n-Bu: Lauryltrithio 2:1 fluid 19 2 2,4,6-Tris(di-n-butoxy/di-p-tolylphosphonate)-1,3,5-triazine [2,4-Bis(di-n-butoxyphosphonate)-6-(ip-tolylphosphonate)- 1,3,5-triazine] n-Bu:p-tolyl 2:1 fluid 20 2 2,4,6-Tris(di-i-propoxy/di-n-butoxyphosphonate)-1,3,5-triazine [2,4-Bis(di-i-propoxyphosphonate)-6-(yne-butoxyphosphonate)- 1,3,5-triazine] i-Pr: nBu 2:1 fluid * Flame retardant results present in PIR rigid foam

In particular, the products which contained unsymmetrical triazines with at least one alkyl substituent R with more than 2 carbons were characterized by a liquid state.

Examples 21 to 32: Production of flame-retardant polymer foams

Chemicals Short name Material Polyol 1: Polyether polyol obtained by propoxylation of sorbitol with a hydroxyl number of 490 mg KOH/g Polyol 2: Polyether polyol obtained by propoxylation of a mixture of sucrose and glycerol as a starter with a hydroxyl number of 490 mg KOH/g and an average functionality of 4.3 Polyol 3: Polyether polyol obtained by propoxylation of ethylenediamine with a hydroxyl number of 753 mg KOH/g Polyol 4: Polyether polyol with a hydroxyl number of 440 mg KOH/g Polyol 5: Polyesterol based on phthalic acid, oleic acid, diethylene glycol and monoethylene glycol with a functionality of 2.0 and a hydroxyl number of 21 0 mg KOH/g Polyol 6: Polyesterol based on terephthalic acid, oleic acid, ethylene glycol and glycerin with an average functionality of 2.5 and an OH number of 242 mg KOH/g Polyol 7: Polyethylene glycol with an OH number of approx. 190 mg KOH/g Propellant 1: Mixture of 80% by weight n-pentane and 20% by weight iso-pentane Propellant 2: 85% by weight formic acid in water Propellant 3: Cyclopentane Catalyst 1: Trimerization catalyst consisting of 40% by weight of potassium formates in solution in monoethylene glycol and water Catalyst 2: 25% by weight bis(2-dimethylaminoethyl)methylamine in polypropylene glycol Catalyst 3: Mixture of polypropylene glycol, glycerin, N,N',N'Tris-dimethylaminopropylhydrotriazine and triethylamine Catalyst 4: Bis(2-dimethylaminoethyl)methylamine Flame retardant 1: Tris(2-chloro-iso-propyl)phosphate (TCPP) Flame retardant 2: Triethyl phosphate Flame retardant 3: brominated aliphatic polyether triol Flame retardant 4: 2,4,6-Tris(di-n-butoxyphosphonate)-1,3,5-triazine Flame retardant 5: 2,4,6-Tris(dimethoxy/di-n-butoxyphosphonate)-1,3,5-triazine [2-(dimethoxyphosphonate)-4,6-bis(di-n-butoxyphosphonate)-1,3,5- triazine] Flame retardant 6: 2,4,6-Tris(diethoxy/di-i-propoxy/di-n-butoxyphosphonate)-1,3,5-triazine [2-(diethoxyphosphonate)-4-(di-i-propoxyphosphonate)-6-( di-n-butoxyphosphonate)-1,3,5-triazine] Stabilizer: Silicone based stabilizer Additives: Mixture comprising 60% by weight water, 30% by weight diethylene glycol and 10% by weight glycerin Isocyanate: polymeric MDI (pMDI) Water: Water

Examples 21 and 22: PU rigid foams with reduction in the content of chlorinated polyphosphates / replacement by triazines

PU rigid foams were produced according to reference example 3a. The test specimens for the small burner test were produced by foaming a box shape measuring 20 cm x 20 cm x 20 cm - the dimensions of the test specimens obtained were 190 mm x 91 mm x 20 mm. The amount of blowing agent was chosen so that the free-foamed bulk density was 40 ± 1 g/liter. The small burner test was carried out in accordance with DIN EN-ISO 11925-2 (2020-07). The composition of the starting materials used as well as the isocyanate index, density and results of the small burner test are shown in Table 2 below. All percentages by weight are based on 100% by weight of isocyanate. Table 2 Educt quantities and properties for PU foams Material Comparative example 1 Example 21 Example 22 [% by weight] [% by weight] [% by weight] Polyol component Polyol 1 27 27 27 Polyol 2 18.63 18.63 18.63 Polyol 3 4 4 4 Propellant 6.3 6.3 6.3 Additives 2.3 2.3 2.3 Water 0.47 0.47 0.47 Catalyst 3 2.8 2.8 2.8 stabilizer 1.4 1.4 1.4 Isocyanate component isocyanate 100 100 100 Flame retardants 1 19.5 15.25 11 Flame retardants 2 4 4 4 Flame retardants 3 25 25 25 Flame retardants 4 0 4.25 8.5 Index* 125 125 125 Density [g/l] 40.4 39.8 40.4 Small burner test fire length [cm] failed 15.3 failed 15.3 passed 15.0 * Index: Excess of isocyanate relative to an equivalent reaction with all active H expressed in percent: Isocyanate index = isocyanate equivalent / polyol equivalent

It was shown that the use of a triazine made it possible to noticeably reduce chlorinated phosphate esters such as flame retardant 1 (tris(2-chloroisopropyl) phosphate) without suffering any loss in fire protection properties or fire behavior. In particular, when replacing chlorinated phosphate ester with equal amounts by weight of triazine, in particular when replacing up to 45% of the weight amount of chlorinated phosphate ester with triazine, almost identical fire protection properties and almost identical fire behavior were achieved.

Examples 23 and 24: PIR rigid foams with reduction in the content of chlorinated polyphosphates / replacement by triazines and without the addition of further flame retardants

PIR rigid foams were produced according to reference example 3a. The test specimens for the small burner test were produced by foaming a box shape measuring 20 cm x 20 cm x 20 cm - the dimensions of the test specimens were 190 mm x 91 mm x 20 mm. The amount of blowing agent was chosen so that the free-foamed density was 40 ± 1 g/liter. The small burner test was carried out in accordance with DIN EN-ISO 11925-2 (2020-07). The composition of the educts used as well as the isocyanate index, density and results of the small burner test are shown in Table 3 below. All percentages by weight are based on 100% by weight of isocyanate. Table 3 Educts, quantities and properties for PIR foams Material Comparative example 2 Example 23 Example 24 [% by weight] [% by weight] [% by weight] Polyol component Polyol 6 76.4 76.4 76.4 Polyol 7 7.8 7.8 7.8 stabilizer 2 2 2 Propellant 2 2 2 2 Catalyst 1 1.55 1.55 1.55 Catalyst 2 2.6 2.6 2.6 Propellant 1 12.2 12.2 12.2 Isocyanate component isocyanate 100 100 100 Flame retardants 1 12 6 0 Flame retardants 4 0 6 12 Index* 333 333 333 Density [g/l] 40.7 40.9 40.7 Small burner test fire length [cm] passed passed passed 9.7 8.7 9.3

It was shown that the use of a triazine made it possible to noticeably reduce chlorinated phosphate esters such as flame retardant 1 (tris(2-chloroisopropyl) phosphate) or to eliminate them completely without suffering any loss in fire protection properties or fire behavior.

Examples 25 and 26: PU rigid foams without other flame retardants

Rigid PU foams were produced according to reference example 3b from polyol 4 and isocyanate, as well as with and without flame retardants 4 or 5 - apart from flame retardants 4 and 5, no other flame retardants were used. The test specimens for the LOI test were obtained by foaming a paper cup with a height of 11 cm and a diameter of 8.7 cm and sawing it. The starting materials used and their amounts, as well as the results, are shown in Table 4. Table 4 Educts, quantities and flame retardancy results in rigid PU foam Material Comparative example 3 Example 25 Example 26 [% by weight] [% by weight] [% by weight] Polyol component Polyol 4 69.93 69.93 69.93 stabilizer 1.40 1.40 1.40 Catalyst 4 0.35 0.35 0.35 Water 1.05 1.05 1.05 Isocyanate component isocyanate 100 100 100 Flame retardants 4 0 9.1 0 Flame retardants 5 0 0 9.1 Foam quality good good good LOI/O ₂ % 18.9 ± 0.38 20.8 ± 0.27 21.3 ± 0.27 ρFoam [g/l] 85.9 90.8 102.8

It was shown that by using a triazine, improved flame retardant properties (fire protection properties) could be achieved without affecting the foam quality compared to PU foam without flame retardants. The differences in foam density are due to the flame retardants used and the non-optimized foam formulation. In particular, the use of asymmetrical triazines (flame retardant 5) enabled an even greater improvement in the flame retardant properties (fire retardant properties) compared to the symmetrical triazine (flame retardant 4) - Example 26 has a slightly higher LOI value compared to Example 25.

Examples 27 to 31: PIR rigid foams without other flame retardants

PIR rigid foams were produced according to reference example 3a (comparative examples 4 and 5, examples 27, 28, 30, 31) and 3b (example 29) from polyol 5, isocyanate, blowing agent 3 and with and without flame retardants 4 and 6 - except flame retardant 4 or 6, no further flame retardants were used. The test specimens for the LOI test were obtained by foaming a paper cup with a height of 11 cm and a diameter of 8.7 cm and sawing it (Comparative Example 4 and Examples 27, 28, 29). The test specimens for the DIN EN 13501-1 Class E (2010-01) test (comparative example 5 and examples 30, 31) were obtained by foaming a box shape measuring 30 cm x 30 cm x 30 cm and sawing it to size. The starting materials used and their amounts, as well as the results, are shown in Table 5. Table 5 Educts, quantities and flame retardancy results in PIR rigid foam Material Comparative example 4 Example 27 Example 28 Example 29 [% by weight] [% by weight] [% by weight] [weight%] Polyol component Polyol 5 34.72 35.95 34.59 34.23 stabilizer 0.72 0.75 0.72 0.71 Catalyst 1 0.56 0.58 0.56 0.55 Catalyst 2 0.65 0.67 0.64 0.64 Water 0.54 0.56 0.54 0.53 Propellant 3 4.4 8.4 5.1 4.3 Flame retardants 6 0 0 0 7.3 Isocyanate component isocyanate 100 100 100 100 Flame retardants 4 0 7.5 7.5 0 Foam quality good good good good LOI/O ₂ % 21.3 ± 0.27 22.3 ± 0.27 23.3 ± 0.27 24.9 ± 0.38 ρFoam [g/l] 51.3 51.9 61.1 61.4 Material Comparative example 5 Example 30 Example 31 --- [% by weight] [% by weight] [% by weight] --- Polyol component Polyol 5 34.99 34.90 34.91 --- stabilizer 0.73 0.73 0.73 --- Catalyst 1 0.56 0.56 0.56 --- Catalyst 2 0.65 0.65 0.65 --- Water 0.54 0.54 0.54 --- Propellant 3 4.5 9.1 4.4 --- Isocyanate component isocyanate 100 100 100 --- Flame retardants 4 0 7.7 7.5 --- Foam quality good good good --- ρFoam [g/l] 39.8 34.5 49.3 --- Fire behavior according to DIN EN Class E not achieved Class E achieved Class E achieved --- 13501-1 Class E (2010-01)

It was shown that the use of a triazine made it possible to omit chlorinated phosphate esters, but also any other flame retardants, while still achieving good flame retardant properties (fire protection properties) without affecting the foam quality compared to a PIR foam without flame retardants. The differences in foam density are due to the flame retardants used and the non-optimized foam formulation. In particular, the use of asymmetrical triazines (flame retardant 6) enabled an even greater improvement in the fire protection properties compared to the symmetrical triazine (flame retardant 4) - Example 29 has a higher LOI value compared to Examples 27 and 28.

Referenced literature

• - CN111285990 A
• - WO 93/12173 A2
• - “Plastics Handbook, 7, Polyurethanes”, Carl Hanser-Verlag, 3rd edition 1993, Chapter 3.1
• -J.H. Saunders and K.C. Frisch “High Polymers” Volume XVI, Polyurethanes, Parts 1 and 2, Interscience Publishers 1962 and 1964, respectively
• - “Plastics Handbook, 7, Polyurethanes”, Carl Hanser-Verlag, 3rd edition, 1993, Chapter 3.4

QUOTES INCLUDED IN THE DESCRIPTION

This list of documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• CN 111285990 A [0003, 0087]
• WO 9312173 A2 [0004, 0087]

Non-patent literature cited

• DIN EN 13501-1:2010-01 [0007]
• DIN EN-ISO 11925-2 [0007]

Claims (15)

Use of a triazine derivative of the formula (I) as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam

where each X, Y, Z is each an oxygen or a sulfur atom; R ¹ , R ² are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical; R ⁴ , R ⁵ are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical; R ⁷ , R ⁸ are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical; where R ¹ , R ² are the same or different from R ⁴ , R ⁵ and R ⁴ , R ⁵ are the same or different from R ⁷ , R ⁸ . Use of a triazine derivative according to Claim 1 as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, where R ¹ , R ² and R ⁴ , R ⁵ and R ⁷ , R ⁸ are the same (R ¹ = R ² = R ⁴ = R ⁵ = R ⁷ = R ⁸ ) and are selected from the group consisting of branched and unbranched C4 to C20 alkyl radicals. Use of a triazine derivative according to Claim 1 as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, where R ¹ , R ² are different from R ⁴ , R ⁵ and from R ⁷ , R ⁸ (R ¹ , R ²⁷ ≠ R ⁴ , R ⁵ and R ¹ , R ² ≠ R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the group consisting of branched and unbranched C3 to C20 alkyl radical and 6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected of hydrogen atom and branched and unbranched C1 to C10 alkyl radical and R ⁴ , R ⁵ and R ⁷ , R ⁸ are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and 6 to C12 aryl radical, where the C6 to C12 aryl radical is at least has a substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical. Use of a triazine derivative according to Claim 1 or 3 as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, where R ¹ , R ² are different from R ⁴ , R ⁵ and from R ⁷ , R ⁸ (R ¹ , R ²⁷ ≠ R ⁴ , R ⁵ and R ¹ , R ² ≠ R ⁷ , R ⁸ ) and R ⁴ , R ⁵ are equal to R ⁷ , R ⁸ (R ⁴ , R ⁵ = R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the group consisting of branched and unbranched C4 to C20 alkyl radical and C6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical and R ⁴ , R ⁵ and R ⁷ , R ⁸ are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical. Use of a triazine derivative according to one of Claims 1 or 3 until 4 as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, where R ¹ , R ² are different from R ⁴ , R ⁵ and from R ⁷ , R ⁸ (R ¹ , R ²⁷ ≠ R ⁴ , R ⁵ and R ¹ , R ² ≠ R ⁷ , R ⁸ ) and R ⁴ , R ⁵ are not equal to R ⁷ , R ⁸ (R ⁴ , R ⁵ ≠ R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the group consisting of branched and unbranched C3 to C20 alkyl radical and C6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical and R ⁴ , R ⁵ and R ⁷ , R ⁸ are each selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and 6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical . Use of a triazine derivative according to one of Claims 1 until 5 as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, the triazine derivative according to formula (I) in an amount of 0.1 to 10% by weight, based on a total weight of 100% by weight of all components used in the production of the polyurethane (PU) or polyisocyanurate (PIR) rigid foam. Use of a triazine derivative according to one of Claims 1 until 6 as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, in particular for a PIR rigid foam, with chlorinated phosphate esters in less than 0.1% by weight, based on a total weight of 100% by weight of all in production components used in the polyurethane (PU) or polyisocyanurate (PIR) rigid foam. Use of a triazine derivative according to one of Claims 1 until 7 as a flame retardant for a polyurethane (PU) or polyisocyanurate (PIR) rigid foam, with the exception of the triazine derivative of the formula (I) being no other flame retardants in more than 0.1% by weight, based on a total weight of 100% by weight. of all components used in the production of the polyurethane (PU) or polyisocyanurate (PIR) rigid foam. Polyurethane (PU) or polyisocyanurate (PIR) rigid foam, obtained or obtainable by reacting A) at least one polyisocyanate, B) at least one polyol, C) one or more blowing agents, D) one or more catalysts, E) optionally further auxiliaries or additives; and F) a flame retardant comprising, preferably consisting of, one or more triazine derivatives of the formulas (I) according to one of Claims 1 until 8th . Polyurethane (PU) or polyisocyanurate (PIR) rigid foam Claim 9 , where the triazine derivative(s) according to formula (I) is present in a total amount of 0.1 to 10% by weight, based on a total weight of 100% by weight of all in the production of the polyurethane (PU) or Polyisocyanurate (PIR) rigid foam components are used. Triazine derivative of formula (I)

where each X, Y, Z is each an oxygen or a sulfur atom; R ¹ , R ² are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical; R ⁴ , R ⁵ are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical; R ⁷ , R ⁸ are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical; where at least R ¹ , R ² are different from R ⁴ , R ⁵ . Triazine derivative of the formula (I). Claim 11 , where R ¹ , R ² are not equal to R ⁴ , R ⁵ and to R ⁷ , R ⁸ (R ¹ , R ² ≠ R ⁴ , R ⁵ and R ¹ , R ² R ⁷ , R ⁸ ) and R ⁴ , R ⁵ are the same as R ⁷ , R ⁸ (R ⁴ , R ⁵ = R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the group consisting of branched and unbranched C4 to C20 alkyl radical, preferably from the group consisting from branched and unbranched C4 to C16 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C15 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C14 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C13 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C12 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C11 alkyl radical, more preferably from the group consisting of branched and unbranched C4 to C10 alkyl radical and R ⁴ , R ⁵ and R ⁷ , R ⁸ are selected from the group consisting of branched and unbranched C1 to C20 alkyl radicals, preferably from the group consisting of branched and unbranched C1 to C16 alkyl radicals, more preferably from the group consisting of branched and unbranched C1 to C16 alkyl radicals C15 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C14 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C13 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C12 alkyl radical, more preferably from the group consisting of branched and unbranched C1 to C11 alkyl radicals, more preferably from the group consisting of branched and unbranched C1 to C10 alkyl radicals. Triazine derivative of the formula (I). Claim 12 , where R ¹ , R ² are not equal to R ⁴ , R ⁵ and to R ⁷ , R ⁸ (R ¹ , R ²⁷ ≠ R ⁴ , R ⁵ and R ¹ , R ² ≠ R ⁷ , R ⁸ ) and R ⁴ , R ⁵ are different from R ⁷ , R ⁸ (R ⁴ , R ⁵ ≠ R ⁷ , R ⁸ ), where R ¹ , R ² are selected from the group consisting of branched and unbranched C3 to C20 alkyl radical and 6 to C12 aryl radical , wherein the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical and R ⁴ , R ⁵ and R ⁷ , R ⁸ are each selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and 6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 alkyl radical. Process for producing a triazine derivative of the general formula (I) comprising (i) providing a phosphite mixture comprising (i.1) a first trialkyl or triarylohosphite of the general formula (A)

where X is a heteroatom, especially an oxygen or a sulfur atom; R ¹ , R ² , R ³ are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and branched and unbranched C1 to C10 has alkyl radical; and (i.2) a second trialkyl or triaryl phosphite of the general formula (B)

where Y is a heteroatom, in particular an oxygen or a sulfur atom; R ⁴ , R ⁵ , R ⁶ are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, the C6 to C12 aryl radical having at least one substituent selected from hydrogen atom and C1 to C10 alkyl radical; where R ¹ , R ² , R ³ of the first trialkyl phosphite according to (i.1) are not equal to R ⁴ , R ⁵ , R ⁶ of the second trialkyl phosphites according to (i.2); and (i.3) optionally a third trialkyl or triaryl phosphite of the general formula (C)

where Z is a heteroatom, in particular an oxygen or a sulfur atom; R ⁷ , R ⁸ , R ⁹ are the same and are selected from the group consisting of branched and unbranched C1 to C20 alkyl radical and C6 to C12 aryl radical, where the C6 to C12 aryl radical has at least one substituent selected from hydrogen atom and C1 to C10 alkyl radical; where R ⁷ , R ⁸ , R ⁹ are not equal to R ¹ , R ² , R ³ of the first trialkyl phosphite according to (i.1) and are not equal to R ⁴ , R ⁵ , R ⁶ of the second trialkyl phosphite according to (i.2) ; and (ii) providing cyanuric chloride; (iii) reacting the phosphite mixture according to (i) with the cyanuric chloride according to (ii), to obtain at least one triazine derivative of the general formula (I)

, where the radicals R ¹ -R ⁹ and X, Y, Z are in one of the Claims 1 until 8th have the stated meaning. Process for producing a triazine derivative of the general formula (I). Claim 14 , wherein step (iii) comprises: (iii. 1a) presenting the first and second trialkyl or triaryl phosphite (A), (B) provided according to (i) and optionally the third trialkyl or triaryl phosphite (C) in one Reaction vessel, (iii.2a) adding the cyanuric chloride provided according to (ii) into the reaction vessel; or (iii. 1b) placing cyanuric chloride provided according to (ii) in a reaction vessel; (iii.2b) Adding the first and second trialkyl or triaryl phosphite (A), (B) provided according to (i) and optionally the third trialkyl or triaryl phosphite (C) into the reaction vessel.