Use of specific catalysts for the preparation of polyurethane coatings

Abstract

The invention relates to a compound for use as a catalyst in the preparation of polyisocyanate polyaddition products, to the preparation thereof and to the use thereof as a catalyst, preferably a thermolatent catalyst, for the preparation of polyisocyanate polyaddition products. The invention also relates to a formulation as well as to method for the preparation of polyisocyanate polyaddition products, each using the claimed compound, as well as to a polyisocyanate polyaddition product obtained or obtainable by said process. Finally, the invention relates to a coating agent for coating a substrate, which comprises or consists of the claimed polyisocyanate polyaddition product.

Description

[0001] Use of special catalysts for the production of polyurethane coatings

[0002] The present invention relates to a compound for use as a catalyst in the preparation of polyisocyanate polyaddition products, to its preparation, and to its use as a catalyst, preferably as a thermolatent catalyst, for the preparation of polyisocyanate polyaddition products. Furthermore, the invention relates to a formulation and a process for preparing polyisocyanate polyaddition products, each using the compound of the invention, as well as to a polyisocyanate polyaddition product obtained or obtainable by this process. Finally, the invention relates to a coating composition for coating a substrate, which comprises or consists of the polyisocyanate polyaddition product of the invention.

[0003] State of the art

[0004] Polyurethane coatings have been known for a long time and are used in many areas. They are usually produced from a polyisocyanate and a hydroxyl component by mixing them immediately before application (2-component (2K) technology). For lightfast coatings, polyisocyanate components based on aliphatic polyisocyanates are generally used, which react with the hydroxyl component much more slowly than products with aromatically bound isocyanate groups. In most cases, the reaction therefore has to be catalyzed. If possible, heating is also used to further accelerate the reaction. Organic tin compounds, particularly dibutyltin dilaurate (DBTL), have proven effective as catalysts. These have the general disadvantage of an unfavorable ecological profile, which, among other things,has already led to the complete ban on organotin compounds from ship paints to which they were added as biocides.

[0005] A general disadvantage of 2K technology is that the reaction of the NCO with the OH groups proceeds slowly even at room temperature, which means that only a narrow processing window is available for the processing of the finished mixture of such a 2K system, the so-called pot life, which is further shortened by the presence of the catalyst.

[0006] There has therefore been no lack of attempts to develop catalysts that hardly accelerate the crosslinking reaction during the production of the 2K mixture, but significantly accelerate it after its application, so-called latent catalysts.

[0007] A particularly promising technology is thermolatent catalysis (TLC) using inorganic tin compounds, as described, for example, in WO 2011 / 051247 A1. A disadvantage of the TLC systems mentioned in the prior art is the relatively high catalyst requirement and the sometimes unsatisfactory stability of the polyisocyanate hardeners, for example, with regard to yellowing and / or viscosity increase, usually accompanied by a decrease in the isocyanate content (NCO loss).

[0008] This effect occurs particularly in polyisocyanates containing iminooxadiazinedione groups, for example, obtainable according to the teaching of EP 798 299 B1, EP 3 337 836 A1 or EP 3 107 948 A1, so that it has so far been practically impossible to equip this class of substances with thermolatent catalysts.

[0009] Object of the invention

[0010] The object of the present invention was therefore to provide a compound for use as a catalyst in the production of polyisocyanate polyaddition products. In particular, the compound should enable a long pot life and sufficient hardness of the products produced, as well as a lower catalyst loading or, with an identical catalyst loading, higher reactivity, while maintaining an otherwise unchanged or even improved property profile. Furthermore, the compound should enable a yellowing tendency and / or viscosity increase / NCO decrease of the products at least at the level of existing state-of-the-art systems. Pot life is the time within which the viscosity of the finished coating formulation has increased to an unacceptable extent. It is determined, for example, indirectly by doubling the flow time of the finished coating formulation in a DIN 4 cup.These improved catalyst systems should also be free of toxic ingredients such as cadmium, mercury, lead, and / or organotin compounds, and should be producible from inexpensive, readily available starting materials. Organotin compounds are defined as species with at least one Sn-C bond in the molecule.

[0011] Solution to the task

[0012] These objects were surprisingly achieved by a compound having the general formula (I) or (II) for use as a catalyst in the preparation of polyisocyanate polyaddition products, ,

[0013] (I) (II) where

[0014] Ri, R2, R3, R4, Rs, R9, Rio and Rn independently of one another represent hydrogen or optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0015] Rs and Rn independently of one another represent optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0016] Re and R7 independently of one another represent -OH, -SH, -OR13, halogens, -OC(=O)Ru, -SR15, -OC(=S)Ri6, -OS(=O)2ORi7, -OS(=O)2Ri8 or -NR19R20, where R13 to R20 independently of one another represent optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0017] V, W, X and Y independently of one another represent oxygen, sulfur, -OC(=O)-, -OC(=S)-, -SC(=O)-, -SC(=S)-, -OS(=O)2O-, -OS(=O)2- or -N(R2i)-, where R21 represents optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0018] D1 and D2 independently of one another represent oxygen, sulfur or nitrogen; characterized in that in formula (I) at least one of the radicals R1, R2, R3 or R4 is hydrogen and at least one of these radicals is not hydrogen, where the carbon atoms C' and C" do not carry the same radicals and in formula (II) at least one of the radicals R1, R2, R3, R4, Rs, R9, R10 or Rn is hydrogen and at least one of these radicals is not hydrogen, where the carbon atoms C' and C" and / or C'" and C"" do not carry the same radicals.

[0019] Furthermore, the invention relates to a process for preparing the compound according to the invention having the general formula (I) by reacting either

[0020] • a tin-containing compound of the type IClUSnZ:; with

[0021] • a compound of general formula (III);

[0022] HV-C' (Ri;R2)-CH2-DI (R5)-CH2-C” (R3;R4)-WH (III) or

[0023] • a tin-containing compound of the type SnZ4; with

[0024] • a compound of general formula (III); and

[0025] HV-C' (R1;R2)-CH2-DI (R5)-CH2-C” (R3;R4)-WH (III) • then with compounds of the general formulas (IV) and (V);

[0026] R6-A (IV) R7-A (V) where

[0027] Ri, R2, R3, R4 independently of one another represent hydrogen or optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0028] R5 independently of one another represent optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals.

[0029] Re and R7 independently of one another represent -OH, -SH, -OR13, halogens, -OC(=O)Ru, -SR15, -OC(=S)Ri6, -OS(=O)2ORI7, -OS(=O)2Ri8 or -NR19R20, where R13 to R20 independently of one another represent optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0030] V and W independently of one another represent oxygen, sulfur, -OC(=O)-, -OC(=S)-, -SC(=O)-, -SC(=S)-, -OS(=O)2O-, -OS(=O)2- or -N(R2i)-, where R21 represents optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0031] Di for oxygen, sulfur or nitrogen;

[0032] A represents leaving groups, preferably -OH, -SH, N(R22)H- or halogens, where R22 represents optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0033] Z represents halogens, alkoxides or mixtures thereof; characterized in that at least one of the radicals R1, R2, R3 or R4 is hydrogen and at least one of these radicals is not hydrogen, where the carbon atoms C' and C" do not carry the same radicals.

[0034] The invention also relates to processes for preparing the compound according to the invention having the general formula (II) by reacting elemental tin or a tin-containing compound with

[0035] • a compound with the general formula (III); and

[0036] HV-C ' (Ri ;R2)-CH2-DI (R5)-CH2-C' ' (R3;Rr)- WH (III) a compound with the general formula (IV); HX-C' ' ' (R8;R9)-CH2-D2(R 12 )-CH2-C” ” (RIO;RI i)-YH (VI); where

[0037] Ri, R2, R3, R4, R8, R9, Rio and Rn independently of one another represent hydrogen or optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0038] Rs and RJ2 independently of one another represent optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals.

[0039] V, W, X and Y independently of one another represent oxygen, sulfur, -OC(=O)-, -OC(=S)-, -SC(=O)-, -SC(=S)-, -OS(=O)2O-, -OS(=O)2- or -N(R2I)-, where R2I represents optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0040] D1 and D2 independently of one another represent oxygen, sulfur or nitrogen; characterized in that at least one of the radicals R1, R2, R3, R4, R8, R9, R10 or Rn is hydrogen and at least one of these radicals is not hydrogen, where the carbon atoms C' and C" and / or C'" and C"" do not carry the same radicals.

[0041] The invention further relates to the use of a compound according to the invention as a catalyst, preferably as a thermolatent catalyst for the production of polyisocyanate polyaddition products, in particular polyurethanes, preferably polyurethane foams, polyurethane coatings, polyurethane paints or polyurethane adhesives.

[0042] Furthermore, the invention relates to a formulation for producing polyisocyanate polyaddition products, comprising or consisting of the following components: a) at least one optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic polyisocyanate; b) at least one compound according to the invention as catalyst; c) optionally further catalysts different from b); d) optionally auxiliaries and / or additives, wherein the ratio of the weight of the tin from component b) and the weight of component a) is preferably at most 1000 ppm if component a) is an aliphatic and / or (cyclo)aliphatic polyisocyanate and at most 50 ppm if component a) is an aromatic polyisocyanate.The invention further relates to a process for the preparation of polyisocyanate polyaddition products by reacting a composition: comprising or consisting of at least one formulation according to claim 16 and at least one NCO-reactive compound, wherein the reaction is preferably carried out at an isocyanate number of 80 to 150; or comprising or consisting of the following components:.

[0043] A) at least one optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic polyisocyanate;

[0044] B) at least one NCO reactive compound;

[0045] C) at least one compound according to the invention as catalyst;

[0046] D) optionally further catalysts different from C);

[0047] E) optionally auxiliaries and / or additives, wherein the ratio of the weight of the tin from component C) and the weight of component A) is preferably at most 1000 ppm when component A) is an aliphatic and / or (cyclo)aliphatic polyisocyanate and at most 50 ppm when component A) is an aromatic polyisocyanate.

[0048] Furthermore, the invention relates to a polyisocyanate polyaddition product obtained or obtainable by the aforementioned process according to the invention.

[0049] Finally, the invention relates to a coating agent for coating a substrate, comprising or consisting of at least one polyisocyanate polyaddition product according to the invention, wherein the substrate is preferably a plastic part, a metal part or a shaped body made of wood.

[0050] The compound according to the invention

[0051] The invention provides a compound of general formula (I) or (II) for use as a catalyst in the preparation of polyisocyanate polyaddition products, where Ri, R2, R3, R4, Rs, R9, Rio and Rn independently of one another represent hydrogen or optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0052] Rs and Rn independently of one another represent optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0053] Re and R7 independently of one another represent -OH, -SH, -OR13, halogens, -OC(=O)Ru, -SR15, -OC(=S)Ri6, -OS(=O)2ORi7, -OS(=O)2Ri8 or -NR19R20, where R13 to R20 independently of one another represent optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0054] V, W, X and Y independently of one another represent oxygen, sulfur, -OC(=O)-, -OC(=S)-, -SC(=O)-, -SC(=S)-, -OS(=O)2O-, -OS(=O)2- or -N(R2i)-, where R21 represents optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0055] D1 and D2 independently of one another represent oxygen, sulfur or nitrogen; characterized in that in formula (I) at least one of the radicals R1, R2, R3 or R4 is hydrogen and at least one of these radicals is not hydrogen, where the carbon atoms C' and C" do not carry the same radicals and in formula (II) at least one of the radicals R1, R2, R3, R4, Rs, R9, R10 or Rn is hydrogen and at least one of these radicals is not hydrogen, where the carbon atoms C' and C" and / or C'" and C"" do not carry the same radicals.

[0056] Preferably, the at least one radical Ri, R2, R3 or RHn in formula (I) which is not hydrogen and the at least one radical Ri, R2, R3, R4, Rs, R9, Rio or Rn in formula (II) which is not hydrogen are aliphatic, preferably a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl radical.

[0057] Furthermore, it is preferred that R5 and / or R12 is a methyl, ethyl, propyl, butyl, pentyl, hexyl or octyl radical, more preferably a methyl, butyl or ethyl radical.

[0058] V, W, X and Y preferably represent oxygen and / or Di and D2 represent nitrogen.

[0059] Furthermore, it is preferred that Re and R7 are identical.

[0060] In a preferred embodiment, the compound according to formula (II) is characterized in that the at least one radical Ri, R2, R3, R4, Rs, R9, Rio or Rn in formula (II) which is not hydrogen is a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl radical, preferably a methyl radical, and that Rs and R12 independently of one another represent optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals, are preferably identical and represent a methyl, ethyl, propyl, butyl, pentyl, hexyl or octyl radical and more preferably are identical and represent a methyl, butyl or ethyl radical, and that V, W, X and Y represent oxygen and D1 and D2 represent nitrogen.

[0061] In a preferred embodiment, the compound according to formula (II) is characterized in that

[0062] Ri is a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl radical, preferably a methyl radical, and the radicals R2, R3, R4, R5, R9, Rio and Rn are hydrogen, or

[0063] Ri and R2 are the same or different and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl radical, preferably are the same and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl radical and more preferably represent a methyl radical, and the radicals R3, Rr, Rs, R9, Rio and Rn represent hydrogen, or

[0064] Ri and Rio are the same or different and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl radical, preferably are the same and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl radical and more preferably represent a methyl radical, and the radicals R2, R3, R4, R5, R9 and Rn represent hydrogen, or

[0065] Ri, R2 and Rio are the same or different and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl radical, preferably are the same and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl radical and more preferably represent a methyl radical, and the radicals R3, R4, R5, R9 and Rn represent hydrogen, or

[0066] Ri, R2, Rio and Ri1 are the same or different and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl radical, preferably are the same and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl radical and more preferably represent a methyl radical, and the radicals R3, R4, R5 and R9 represent hydrogen, and that R5 and R12 independently of one another represent optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals, preferably are the same and represent a methyl, ethyl, propyl, butyl, pentyl, hexyl or octyl radical and more preferably are the same and represent a methyl, butyl or ethyl radical, and that V, W, X and Y represent oxygen and D1 and D2 represent nitrogen.

[0067] In a preferred embodiment, the compound according to the invention is selected from the

[0068] Gruppe, umfassend oder bestehend aus • 2,2-dichloro-4,6-dimethyl-l ,3,6,2-dioxazastannocan, 2,2-dibromo-4,6-dimethyl- 1,3,6,2-dioxazastannocan, 2,2-dimethoxy-4,6-dimethyl-l,3,6,2-dioxazastannocan, 4,6- dimethyl-l,3,6,2-dioxazastannocan-2,2-diyl dibenzoat, 6-ethyl-4-methyl-l, 3,6,2- dioxazastannocan-2,2-diyl dibenzoat, 6-butyl-4-methyl-l,3,6,2-dioxazastannocan-2,2- diyl dibenzoat, 2,4,12-trimethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro[7.7]pentadekan, 2,2,4,12-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro[7.7]pentadekan, 2,4,10,12-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro[7.7]pentadekan, 2,2,4,10,12-pentamethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro[7.7]pentadekan, 2,2,4,10,10,12-hexamethyl-l,7,9,15-tetraoxa-4,12-diaza- 8-stannaspiro[7.7]pentadekan, 2,2,4,6,10,10,12-heptamethyl-l,7,9,15-tetraoxa-4,12- diaza-8-stannaspiro[7.7]pentadekan, 2,2,4,6,6,10,10,12-octamethyl-l,7,9,15-tetraoxa-

[0069] 4.12-diaza-8-stannaspiro[7.7]pentadekan, 2,2,4,6,6,10,10,12,14-nonamethyl-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2-methyl-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2-dimethyl-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,10-dimethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2,10- trimethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-

[0070] 2.2.10.10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan,

[0071] 4.12-diethyl-2,2,6,10,10-pentamethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2,6,6,10,10-hexamethyl-l,7,9,15-tetraoxa-

[0072] 4.12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2,6,6,10,10,14-heptamethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2-methyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,2-dimethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,10- dimethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-

[0073] 2.2.10-trimethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12- dibutyl-2,2, 10, 10-tetramethyl- 1 ,7,9, 15-tetraoxa-4, 12-diaza-8- stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,2,6,10,10-pentamethyl-l,7,9,15-tetraoxa-

[0074] 4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,2,6,6,10,10-hexamethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl- 2,2,6,6,10,10,14-heptamethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro[7.7]pentadekan,4,12-dibutyl-2-(trifluoromethyl)-l,7,9,15-tetraoxa-4,12- diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,10-bis(trifluoromethyl)-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7] , 4,12-dipropyl-2,2,10,10-tetramethyl-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dipentyl-2,2,10,10- tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dihexyl-

[0075] 2.2.10.10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4.12-dioctyl-2,2,10,10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro[7.7]pentadekan oder Mischungen davon,

[0076] • bevorzugt 2,4,12-trimethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan,

[0077] 2.2.4.12-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadecane,

[0078] 2.4.10.12-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadecane,

[0079] 2.2.4.10.12-pentamethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadecane,

[0080] 2.2.4.10.10.12-hexamethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadecane,

[0081] 2.2.4.6.10.10.12-heptamethyl-l,7,9,15-tetaoxa-4,12-diaza-8- stannaspiro [7.7] pentadekan, 2,2,4,6,6,10,10,12-octamethyl-l,7,9,15-tetraoxa-4,12- diaza-8-stannaspiro[7.7]pentadekan, 2,2,4,6,6,10,10,12,14-nonamethyl-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2-methyl-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2-dimethyl-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,10-dimethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2,10- trimethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-

[0082] 2.2.10.10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan,

[0083] 4.12-diethyl-2,2,6,10,10-pentamethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro [7.7] pentadekan, 4,12-diethyl-2,2,6,6,10,10-hexamethyl-l,7,9,15-tetraoxa-

[0084] 4.12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2,6,6,10,10,14-heptamethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2-methyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,2-dimethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,10- dimethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-

[0085] 2.2.10-trimethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12- dibutyl-2,2, 10, 10-tetramethyl- 1 ,7,9, 15-tetraoxa-4, 12-diaza-8- stannaspiro [7.7] pentadekan, 4,12-dibutyl-2,2,6,10,10-pentamethyl-l,7,9,15-tetraoxa-

[0086] 4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,2,6,6,10,10-hexamethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl- 2,2,6,6,10,10,14-heptamethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro [7.7] pentadekan, 4, 12-dipropyl-2,2, 10, 10-tetramethyl- 1 ,7,9, 15-tetraoxa-

[0087] 4,12-diaza-8-stannaspiro[7.7]pentadekan, 4, 12-dipentyl-2,2, 10, 10-tetramethyl - l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dihexyl-2,2,10,10- tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dioctyl-

[0088] 2.2.10.10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan oder Mischungen davon,

[0089] • besonders bevorzugt 2,2,4,10,10,12-hexamethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro [7.7] pentadekan, 4,12-diethyl-2,2,10,10-tetramethyl-l,7,9,15-tetraoxa-4,12- diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,2,10,10-tetramethyl-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dipropyl-2,2,10,10- tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dipentyl- 2,2,10,10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan,

[0090] 4.12-dihexyl-2,2,10,10-tetramethyl-l,7,9,15-tetaoxa-4,12-diaza-8- stannaspiro[7.7]pentadekan, 4,12-dioctyl-2,2,10,10-tetamethyl-l,7,9,15-tetraoxa-

[0091] 4.12-diaza-8-stannaspiro[7.7]pentadekan oder Mischungen davon,

[0092] • very particularly preferably 2,2,4,10,10,12-hexamethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadecane, 4,12-diethyl-2,2,10,10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadecane, 4,12-dibutyl-2,2,10,10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadecane or mixtures thereof.

[0093] The compound of the invention can be used in particular as a catalyst, particularly preferably as a thermolatent catalyst, for the production of polyisocyanate polyaddition products, in particular polyurethanes, preferably polyurethane foams, polyurethane coatings, polyurethane lacquers, or polyurethane adhesives. As a thermolatent catalyst, the compound of the invention preferably develops its activity by increasing the temperature, for example, to 60 to 100°C. Formula (I):

[0094] The compound according to the invention with the general formula (I) can be prepared by reaction either

[0095] • a tin-containing compound of the type KRvSnZ?; with

[0096] • a compound of general formula (III);

[0097] HV-C' (Ri ;R2)-CH2-D, (R5)-CH2-C” (R3;R4)-WH (III) or

[0098] • a tin-containing compound of the type SnZ4; with

[0099] • a compound of general formula (III); and

[0100] HV-C' (Ri;R2)-CH2-D, (R5)-CH2-C” (R3;R4)-WH (III) subsequently with compounds of the general formulas (IV) and (V);

[0101] Rö-A (IV) R7-A (V) can be produced, whereby

[0102] Ri, R2, R3, R4 independently of one another represent hydrogen or optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0103] R5 independently of one another represent optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals.

[0104] Re and R7 independently of one another represent -OH, -SH, -OR13, halogens, -OC(=O)Ru, -SR15, -OC(=S)Ri6, -OS(=O)2ORi7, -OS(=O)2Ri8 or -NR19RM, where R13 to R2o independently of one another represent optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0105] V and W independently of one another represent oxygen, sulfur, -OC(=O)-, -OC(=S)-, -SC(=O)-, -SC(=S)-, -OS(=O)2O-, -OS(=O)2- or -N(R2I)-, where R2I represents optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0106] Di for oxygen, sulfur or nitrogen;

[0107] A for leaving groups, preferably -OH, -SH, N(R 22 )H- or halogens, where R 22represents optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0108] Z represents halogens, alkoxides or mixtures thereof; characterized in that at least one of the radicals R1, R2, R3 or R4 is hydrogen and at least one of these radicals is not hydrogen, where the carbon atoms C' and C" do not carry the same radicals.

[0109] It is preferred that

[0110] • the compound of general formula (III) 2,2'-(methylazanediyl)bis(ethan-1-ol), 2,2'-(ethylazanediyl)bis(ethan-1-ol), 2,2'-(butylazanediyl)bis(ethan-1-ol), 1-((2-hydroxyethyl)(methyl)amino)propan-2-ol, l-(ethyl(2-hydroxyethyl)amino)propan-2-ol, 1-(butyl(2-hydroxyethyl)amino)propan-2-ol, 1,1'-(methylazanediyl)bis(propan-2-ol), l,l'-(ethylazanediyl)bis(propan-2-ol), l,l'-(butylazanediyl)bis(propan-2-ol), l-((2-hydroxyethyl)(methyl)amino)-2-methylpropan-2-ol, l-(ethyl(2-hydroxyethyl)amino)-2-methylpropan-2-ol, 1-(butyl(2-hydroxyethyl)amino)-2-methylpropan-2-ol, 1-(ethyl(2-hydroxypropyl)amino)-2-methylpropan-2-ol, l-(butyl(2-hydroxypropyl)amino)-2-methylpropan-2-ol or mixtures thereof, preferably l-((2- hydroxyethyl)(methyl)amino)-2-methylpropan-2-ol, l-(ethyl(2-hydroxyethyl)amino)-2-methylpropan-2-ol, 1-(butyl(2-hydroxyethyl)amino)-2-methylpropan-2-ol or

[0111] mixtures thereof; and / or

[0112] • the compound of general formula (IV) and / or general formula (V) comprises or consists of halogen, halides, alkoxides, carboxylates, peroxides, disulfides or mixtures thereof.

[0113] Preferably, the tin-containing compound of the SnZ4 type is selected from the group comprising or consisting of tin tetrachloride, tin tetrabromide, tin tetra-tert-alkoxide, in particular tin tetra-tert-butoxide, or mixtures thereof. Furthermore, it is preferred that the molar ratio of tin-containing compound to the sum of the compounds of general formula (III), (IV), and (V) is from 1:1 to 1:4, preferably from 1:1 to 1:2.1.

[0114] Preferably, Z in the tin-containing compound of the type R6R?SnZ2 represents halogens, such as chlorine (ReRvSnCh).

[0115] Compounds with the general formula (II):

[0116] The compound of the invention having the general formula (II) can be prepared by reacting elemental tin or a tin-containing compound with

[0117] • a compound with the general formula (III); and

[0118] HV-C ' (Ri ;R2)-CH2-D, (R5)-CH2-C' ' (R3;Rr)- WH (III)

[0119] • a compound with the general formula (IV);

[0120] HX-C' ' ' (R8;R9)-CH2-D2(R 12 )-CH2-C” ” (RIO;RI i)-YH (VI) ;, where

[0121] Ri, R2, R3, Rr, R8, R9, Rio and Rn independently of one another represent hydrogen or optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0122] Rs and RI2 independently of one another represent optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals.

[0123] V, W, X and Y independently of one another represent oxygen, sulfur, -OC(=O)-, -OC(=S)-, -SC(=O)-, -SC(=S)-, -OS(=O)2O-, -OS(=O)2- or -N(R2I)-, where R2I represents optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0124] D1 and D2 independently of one another represent oxygen, sulfur or nitrogen; characterized in that at least one of the radicals R1, R2, R3, R4, R5, R9, R10 or Rn is hydrogen and at least one of these radicals is not hydrogen, where the carbon atoms C' and C" and / or C'" and C"" do not carry the same radicals.

[0125] It is preferred that the compound of general formula (III) and / or the compound of general formula (VI) 2,2'-(methylazanediyl)bis(ethan-1-ol), 2,2'-(ethylazanediyl)bis(ethan-1-ol), 2,2'-(butylazanediyl)bis(ethan-1-ol), 1-((2-hydroxyethyl)(methyl)amino)propan-2-ol, 1-(ethyl(2-hydroxyethyl)amino)propan-2-ol, 1-(butyl(2-hydroxyethyl)amino)propan-2-ol, 1,1'-(methylazanediyl)bis(propan-2-ol), 1,1'-

[0126] (butylazanediyl)bis(propan-2-ol), 1 -((2-hydroxyethyl)(methyl)amino)-2-methylpropan-2-ol, 1 -

[0127] (ethyl(2-hydroxyethyl)amino)-2-methylpropan-2-ol, l-(butyl(2-hydroxyethyl)amino)-2-methylpropan-2-ol, 1-(ethyl(2-hydroxypropyl)amino)-2-methylpropan-2-ol, 1-(butyl(2-hydroxypropyl)amino)-2-methylpropan-2-ol or mixtures thereof, preferably 1-((2-hydroxyethyl)(methyl)amino)-2-methylpropan-2-ol, 1-(ethyl(2-hydroxyethyl)amino)-2-methylpropan-2-ol and 1-(butyl(2-hydroxyethyl)amino)-2-methylpropan-2-ol or mixtures thereof, wherein it is preferred if the compound of the general formula (III) and the compound of the general formula (VI) are identical. The compounds of the general formulas (III) and (VI) are accessible via customary synthetic routes.For example, in the case of alkanolamines, these are accessible, for example, by reacting corresponding geminally substituted epoxides with the respective radicals (Ri, R2, R3, R4 or Rs, R9, Rio, Ri 1) with NH-functional compounds of the general formula H2NR5 or H2NR12 consecutively, optionally with isolation of the NH-functional intermediate of the formulas R5N(H)CH2C(RI,R2)OH or Ri2N(H)CH2C(Rs,R9)OH, according to processes known to the person skilled in the art.

[0128] Tin-containing compounds suitable according to the invention are generally tin(IV)-containing compounds. In a further embodiment of the process according to the invention, Sn(II) compounds can also be used. In this case, an oxidative treatment of the resulting Sn(II) complex follows. Suitable processes for this are known per se to the person skilled in the art. The tin-containing compound is particularly preferably selected from the group comprising or consisting of tin tetrachloride, tin tetrabromide, tin tetraalkoxide, in particular tin tetra-tert-butoxide, or mixtures thereof. Very particular preference is given to using tin tetra-tert-butoxide or tin tetrachloride according to the invention. Furthermore, it is preferred that the molar ratio of elemental tin or tin-containing compound to the sum of the compounds having the general formula (III) and (VI) is from 1:1 to 1:4, preferably from 1:1 to 1:2.1.

[0129] Compounds with the general formula (II), particularly tin(IV) alkoxides, can also be prepared using elemental tin (tin powder). The preparation of tin(IV) alkoxides starting from elemental tin is described, for example, in DE 10 2010 012 237 Al.

[0130] It is preferred that the compounds of general formula (III) and (VI) are provided or initially charged in a suitable reactor (for example, stirred reactors with appropriate devices for the addition of reaction components, etc.), optionally in a solvent, at a suitable temperature. Suitable solvents are, for example, selected from the group consisting of alcohols, preferably methanol, ethanol, propanol, in particular isopropanol, or mixtures thereof, ethers, preferably diethyl ether, tetrahydrofuran, tert-butyl methyl ether or mixtures thereof, halogenated solvents, preferably dichloromethane, chloroform or mixtures thereof, aromatic solvents, preferably toluene, and mixtures thereof. The process according to the invention is preferably carried out in the temperature range between -30 to +150 °C, more preferably -10 to 100 °C, most preferably at -10 °C to room temperature.Furthermore, it is preferred if the process according to the invention is carried out under an inert atmosphere, for example under nitrogen. In addition to the compounds of general formula (III) and (VI), further components may optionally be initially introduced. These are selected, for example, from auxiliary bases, e.g., alkoxides, and mixtures containing them.

[0131] Particularly preferably, the compounds of general formula (III) and (VI) are identical and are reacted with a tin-containing compound to obtain the catalyst of general formula (II).

[0132] In a particularly preferred embodiment of the process according to the invention, the at least one tin-containing compound is placed in a corresponding reactor and the compound of the general formula (III) and the compound of the general formula (VI) are added in diluted form.

[0133] The resulting reaction solution can be processed by methods known to the person skilled in the art, for example by filtration, distillative separation of the solvent, crystallization, etc.

[0134] Formulation for the production of polyisocyanate polyaddition products

[0135] The invention also relates to a formulation for the preparation of polyisocyanate polyaddition products, comprising or consisting of the following components: a) at least one optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic polyisocyanate; b) at least one compound according to the invention as catalyst; c) optionally further catalysts different from b); d) optionally auxiliaries and / or additives, wherein the ratio of the weight of the tin from component b) and the weight of component a) is preferably at most 1000 ppm if component a) is an aliphatic and / or (cyclo)aliphatic polyisocyanate and at most 50 ppm if component a) is an aromatic polyisocyanate.

[0136] The formulation preferably contains

[0137] • 5 to 80 wt.% of component a);

[0138] • 0.0001 to 2.0 wt% of component b);

[0139] • optionally 0.01 to 2.0 wt.% of component c);

[0140] • optionally 5 to 50 wt.% of component d), based on the total weight of the formulation.

[0141] Process for the preparation of polyisocyanate polyaddition products

[0142] The compounds according to the invention can be used to prepare polyisocyanate polyaddition products. The present invention therefore provides a process for preparing polyisocyanate polyaddition products by reacting a composition comprising or consisting of at least one formulation according to claim 16 or 17 and at least one NCO-reactive compound, wherein the reaction preferably takes place at an isocyanate number of 80 to 150, or comprising or consisting of the following components:

[0143] A) at least one optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic polyisocyanate;

[0144] B) at least one NCO reactive compound;

[0145] C) at least one compound according to the invention as catalyst;

[0146] D) optionally further catalysts different from C);

[0147] E) optionally auxiliaries and / or additives, wherein the ratio of the weight of the tin from component C) to the weight of component A) is preferably at most 1000 ppm when component A) is an aliphatic and / or (cyclo)aliphatic polyisocyanate and at most 50 ppm when component A) is an aromatic polyisocyanate.

[0148] Preferably, the composition contains

[0149] • 5 to 80 wt% of component A);

[0150] • 5 to 80 wt% of component B);

[0151] • 0.0001 to 2.0 wt% of component C);

[0152] • optionally 0.01 to 2.0 wt.% of component D);

[0153] • optionally 5 to 50% by weight of component E); based on the total weight of the composition and / or the reaction takes place at an isocyanate number of 80 to 150.

[0154] By the above-mentioned process, a polyisocyanate polyaddition product is / is obtained / obtainable.

[0155] The isocyanate index (also called index, NCO / OH index, or isocyanate index) is the quotient of the actual amount of isocyanate groups used [mol] and the actual amount of isocyanate-reactive groups used [mol], multiplied by 100. In other words, the index indicates the percentage ratio of the actual amount of isocyanate used to the stoichiometric amount of isocyanate, i.e., the amount calculated for the conversion of the OH equivalents. An equivalent amount of NCO groups and NCO-reactive hydrogen atoms corresponds to an NCO / OH index of 100.

[0156] Index = [(mol isocyanate groups) / (mol isocyanate-reactive groups)] * 100

[0157] The polyisocyanate polyaddition products are preferably polyurethanes. The individual components of the polyisocyanate polyaddition product according to the invention, in particular polyurethanes, are described in detail below.

[0158] The optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic polyisocyanates a) or A) (hereinafter also referred to as polyisocyanate components) suitable for the preparation of polyisocyanate polyaddition products and / or the formulation are the organic polyisocyanates known per se to the person skilled in the art, preferably with at least two isocyanate groups per molecule, and mixtures thereof. Examples of such polyisocyanates are di- or triisocyanates, for example butane diisocyanate, pentane diisocyanate (pentamethylene diisocyanate, PDI), hexane diisocyanate (hexamethylene diisocyanate, HDI), 4-isocyanatomethyl-1,8-octane diisocyanate (triisocyanatononane, TIN), 4,4'-methylenebis(cyclohexyl isocyanate) (HnMDI), 3,5,5-trimethyl-1-isocyanato-3-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane (HeXDI), 1,5-naphthalene diisocyanate, diisocyanatodiphenylmethane (2,2'-, 2,4'- and 4,4'-MDI or mixtures thereof), diisocyanatomethylbenzene (2,4- and 2,6-tolylene diisocyanate, TDI) and technical mixtures of the two isomers, as well as 1,3-bis(isocyanatomethyl)benzene (XDI), 3,3'-dimethyl-4,4'-biphenyl diisocyanate (TODI), 1,4-paraphenylene diisocyanate (PPDI) and cyclohexyl diisocyanate (CHDI), and the higher molecular weight oligomers containing biuret, uretdione, isocyanurate, iminooxadiazinedione, allophanate, urethane, and carbodiimide / uretonimine structural units, available individually or as a mixture. Polyisocyanates based on aliphatic and cycloaliphatic diisocyanates are very preferably used.

[0159] The polyisocyanate component a) and / or A) can be present in a suitable solvent. Suitable solvents are those that have sufficient solubility of the polyisocyanate component and are free of isocyanate-reactive groups. Examples of such solvents are acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, methyl isoamyl ketone, diisobutyl ketone, ethyl acetate, n-butyl acetate, ethylene glycol diacetate, butyrolactone, diethyl carbonate, propylene carbonate, ethylene carbonate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, methylal, ethylal, butylal, 1,3-dioxolane, glycerol formal, benzene, toluene, n-hexane, cyclohexane, solvent naphtha, 2-methoxypropyl acetate (MPA), and mixtures thereof.

[0160] The isocyanate component may also contain conventional auxiliaries and additives, for example rheology improvers (for example ethylene carbonate, propylene carbonate, dibasic esters, citric acid esters), stabilizers (for example Broenstedt and Lewis acids, such as hydrochloric acid, phosphoric acid, benzoyl chloride, organomineral acids such as dibutyl phosphate, further adipic acid, malic acid, succinic acid, grape acid or citric acid), UV protectants (for example 2,6-dibutyl-4-methylphenol), hydrolysis stabilizers (for example sterically hindered carbodiimides), emulsifiers and catalysts (for example trialkylamines, diazabicyclooctane, tin dioctoate, dibutyltin dilaurate, N-alkylmorpholine, lead, zinc, tin, calcium, magnesium octoate, the corresponding naphthenates and p-nitrophenolate and / or mercury phenyl neodecanoate) and fillers (for example chalk),possibly contain dyes (which have Zerewitinoff-active hydrogen atoms) and / or color pigments that can be incorporated into the polyurethane / polyurea to be formed later.

[0161] As NCO-reactive compounds B), it is preferred to use all compounds known to the person skilled in the art which have an average OH or NH functionality of at least 1.5. These can be, for example, low molecular weight diols (e.g. 1,2-ethanediol, 1,3- or 1,2-propanediol, 1,4-butanediol), triols (e.g. glycerol, trimethylolpropane) and tetraols (e.g. pentaerythritol), short-chain polyamines but also higher molecular weight polyhydroxy compounds such as polyether polyols, polyester polyols, polycarbonate polyols, polysiloxane polyols, polyamines and polyether polyamines as well as polybutadiene polyols. Polyether polyols are accessible in a conventional manner by alkoxylation of suitable starter molecules under base catalysis or using double metal cyanide compounds (DMC compounds).Suitable starter molecules for the production of polyether polyols are, for example, simple, low-molecular-weight polyols, water, organic polyamines with at least two NH bonds, or any mixtures of such starter molecules. Preferred starter molecules for the production of polyether polyols by alkoxylation, in particular by the DMC process, are, in particular, simple polyols such as ethylene glycol, propylene glycol-1,3- and butanediol-1,4-, hexanediol-1,6-, neopentyl glycol, 2-ethylhexanediol-1,3-, glycerol, trimethylolpropane, pentaerythritol, as well as low-molecular-weight, hydroxyl-containing esters of such polyols with dicarboxylic acids of the type exemplified below, or low-molecular-weight ethoxylation or propoxylation products of such simple polyols, or any mixtures of such modified or unmodified alcohols.Alkylene oxides suitable for alkoxylation are, in particular, ethylene oxide and / or propylene oxide, which can be used in any order or in a mixture during the alkoxylation.

[0162] Polyester polyols can be prepared in a known manner by polycondensation of low molecular weight polycarboxylic acid derivatives, such as succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride,

[0163] Glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimer fatty acid, trimer fatty acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, citric acid or trimellitic acid, with low molecular weight polyols, for example ethylene glycol, diethylene glycol, neopentyl glycol, hexanediol, butanediol, propylene glycol, glycerin, trimethylolpropane, 1,4-hydroxymethylcyclohexane, 2-methyl-1,3-propanediol, 1,2,4-butanetriol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycol, or by ring-opening polymerization of cyclic carboxylic acid esters, such as s-caprolactone. In addition, hydroxycarboxylic acid derivatives such as lactic acid, cinnamic acid, or co-hydroxycaproic acid can be polycondensed to form polyester polyols. However, polyester polyols of oleochemical origin can also be used.Such polyester polyols can be prepared, for example, by complete ring opening of epoxidized triglycerides of an at least partially olefinically unsaturated fatty acid-containing fat mixture with one or more alcohols having 1 to 12 C atoms and by subsequent partial transesterification of the triglyceride derivatives to alkyl ester polyols having 1 to 12 C atoms in the alkyl radical.

[0164] The preparation of suitable polyacrylate polyols is known per se to the person skilled in the art. They are obtained by radical polymerization of olefinically unsaturated monomers containing hydroxyl groups or by radical copolymerization of olefinically unsaturated monomers containing hydroxyl groups with, optionally, other olefinically unsaturated monomers, for example ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, styrene, acrylic acid, acrylonitrile, and / or methacrylonitrile. Suitable olefinically unsaturated monomers containing hydroxyl groups are in particular 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, the hydroxypropyl acrylate isomer mixture obtainable by addition of propylene oxide to acrylic acid and the hydroxypropyl methacrylate isomer mixture obtainable by addition of propylene oxide to methacrylic acid.Suitable radical initiators are those from the group of azo compounds, for example azoisobutyronitrile (AIBN), or from the group of peroxides, for example di-tert-butyl peroxide.

[0165] Component B) preferably comprises higher molecular weight polyhydroxy compounds, for example with a molecular weight of 500 to 10,000 g / mol, preferably 1,000 to 10,000 g / mol.

[0166] Component B) can be present in a suitable solvent. Suitable solvents are those that have sufficient solubility for the component. Examples of such solvents are acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, methyl isoamyl ketone, diisobutyl ketone, ethyl acetate, n-butyl acetate, ethylene glycol diacetate, butyrolactone, diethyl carbonate, propylene carbonate, ethylene carbonate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, methylal, ethylal, butylal, 1,3-dioxolane, glycerol formal, benzene, toluene, n-hexane, cyclohexane, solvent naphtha, 2-methoxypropyl acetate (MPA), and mixtures thereof. Furthermore, the solvents can also contain groups that are reactive toward isocyanates. Examples of such reactive solvents are those that have an average functionality of at least 1.8 towards isocyanate-reactive groups. These can be, for example, low molecular weight diols (e.g., 1,2-ethanediol, 1,3- or1,2-propanediol, 1,4-butanediol), triols (e.g. glycerol, trimethylolpropane), but also low molecular weight diamines, such as polyaspartic acid esters.

[0167] In order to obtain the polyisocyanate polyaddition product according to the invention and / or the formulation according to the invention, at least one compound according to the invention is used as catalyst as component b) or C).

[0168] The statements made regarding the catalyst according to the invention, particularly regarding preferred embodiments, apply here accordingly. The catalyst according to the invention can be added to the reaction mixture via the NCO-reactive compound (polyol), dissolved in a solvent, and / or pre-dissolved in the polyisocyanate.

[0169] The polyisocyanate polyaddition products according to the invention or the

[0170] Formulations are further obtained with the optional use of component D) or c), further catalysts and / or activators different from C) or b), in particular acids, amines, sterically hindered phenols, phospite, etc. These are known per se to the person skilled in the art and are described, for example, in WO 2014 / 048879 A1. Furthermore, the catalyst according to the invention can be combined with other catalysts / activators known from the prior art; for example, titanium-, zirconium-, bismuth-, tin(II)- and / or iron-containing catalysts can be used, as described, for example, in WO 2005 / 058996. Addition of amines or amidines is also possible. Furthermore, acidic compounds, for example 2-ethylhexanoic acid or alcohols, can also be added to the polyisocyanate polyaddition reaction to control the reaction.

[0171] The polyisocyanate polyaddition products according to the invention and / or the formulation according to the invention are further obtained with the optional use of component E) or d) fillers, pigments, additives, thickeners, defoamers, and / or other auxiliaries and additives. Substances particularly suitable as component E) / d) are selected from the group consisting of conventional rheology improvers, stabilizers, UV stabilizers, hydrolysis stabilizers, emulsifiers, fillers, optionally incorporable dyes, i.e., dyes containing Zerewitinoff-active hydrogen atoms, color pigments, and mixtures thereof. Preferred auxiliaries and additives are blowing agents, fillers, chalk, carbon black, or zeolites, flame retardants, color pastes, water, microbial protection agents, flow improvers, thixotropic agents, surface modifiers, and retarders in the preparation of the polyisocyanate polyaddition products.Other auxiliaries and additives include defoamers, emulsifiers, foam stabilizers, and cell regulators. An overview can be found in G. Oertel, Polyurethane Handbook, 2. nd Edition, Carl Hanser Verlag, Munich, 1994, Chapter 3.4.

[0172] Coating agents

[0173] The polyisocyanate polyaddition products according to the invention can be used in a wide variety of applications. In particular, the present invention provides a coating composition for coating a substrate, comprising or consisting of at least one polyisocyanate polyaddition product according to the invention, wherein the substrate is preferably a plastic part, a metal part, or a shaped body made of wood.

[0174] The system according to the invention comprising the above-mentioned components can generally be applied to the substrate to be coated by any method known to those skilled in the art, for example, in solution or from the melt, or in the case of powder coatings in solid form, by methods such as brushing, rolling, pouring, spraying, dipping, fluidized-bed processes, or by electrostatic spraying. Suitable substrates include, for example, materials such as metals, wood, plastics, or ceramics. Embodiments:

[0175] The present invention particularly relates to the following embodiments:

[0176] According to a first embodiment, the invention relates to a compound, in particular a catalyst for the preparation of polyisocyanate polyaddition products, having the general formula (I) or (II),

[0177] (I) (II) where

[0178] Ri, R2, R3, R4, Rs, R9, Rio and Rn independently of one another represent hydrogen or optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0179] Ri and Rn independently of one another represent optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0180] Re and R7 independently of one another represent -OH, -SH, -OR13, halogens, -OC(=O)Ru, -SR15, -OC(=S)Ri6, -OS(=O)2ORi7, -OS(=O)2Ri8 or -NR19R20, where R13 to R20 independently of one another represent optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0181] V, W, X and Y independently of one another represent oxygen, sulfur, -OC(=O)-, -OC(=S)-, -SC(=O)-, -SC(=S)-, -OS(=O)2O-, -OS(=O)2- or -N(R2i)-, where R21 represents optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0182] D1 and D2 independently of one another represent oxygen, sulfur or nitrogen; characterized in that in formula (I) at least one of the radicals R1, R2, R3 or R4 is hydrogen and at least one of these radicals is not hydrogen, where the carbon atoms C' and C" do not carry the same radicals, and in formula (II) at least one of the radicals R1, R2, R3, R4, Rs, R9, R10 or Rn is hydrogen and at least one of these radicals is not hydrogen, where the carbon atoms C' and C" and / or C'" and C"" do not carry the same radicals. According to a second embodiment, the invention relates to a compound having the general formula (I) or (II) for use as a catalyst in the preparation of polyisocyanate polyaddition products,

[0183] (I) (II) where

[0184] Ri, R2, R3, R4, Rs, R9, Rio and Rn independently of one another represent hydrogen or optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0185] Ri and Rn independently of one another represent optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0186] Re and R7 independently of one another represent -OH, -SH, -OR13, halogens, -OC(=O)Ru, -SR15, -OC(=S)Ri6, -OS(=O)2ORi7, -OS(=O)2Ri8 or -NR19R20, where R13 to R20 independently of one another represent optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0187] V, W, X and Y independently of one another represent oxygen, sulfur, -OC(=O)-, -OC(=S)-, -SC(=O)-, -SC(=S)-, -OS(=O)2O-, -OS(=O)2- or -N(R2i)-, where R21 represents optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0188] D1 and D2 independently of one another represent oxygen, sulfur or nitrogen; characterized in that in formula (I) at least one of the radicals R1, R2, R3 or R4 is hydrogen and at least one of these radicals is not hydrogen, where the carbon atoms C' and C" do not carry the same radicals and in formula (II) at least one of the radicals R1, R2, R3, R4, Rs, R9, R10 or Rn is hydrogen and at least one of these radicals is not hydrogen, where the carbon atoms C' and C" and / or C'" and C"" do not carry the same radicals.

[0189] According to a third embodiment, the invention relates to a compound according to embodiment 1 or 2, characterized in that the at least one radical Ri, R2, R3 or Ron of formula (I) which is not hydrogen and the at least one radical Ri, R2, R3, R4, Rs, R9, Rio or Rn in formula (II) which is not hydrogen is aliphatic, preferably a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl radical.

[0190] According to a fourth embodiment, the invention relates to a compound according to any one of the preceding embodiments, characterized in that Rs and / or R is a methyl, ethyl, propyl, butyl, pentyl, hexyl or octyl radical, preferably a methyl, butyl or ethyl radical.

[0191] According to a fifth embodiment, the invention relates to a compound according to any one of the preceding embodiments, characterized in that V, W, X and Y represent oxygen and / or D2 and D2 represents nitrogen.

[0192] According to a sixth embodiment, the invention relates to a compound according to any one of the preceding embodiments, characterized in that Re and R7 are identical.

[0193] According to a seventh embodiment, the invention relates to a compound according to formula (II) according to embodiment 1, characterized in that the at least one radical Ri, R2, R3, R4, Rs, R9, Rio or Rn in formula (II) which is not hydrogen is a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl radical, preferably a methyl radical, and in that R5 and R12 independently of one another represent optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals, are preferably identical and represent a methyl, ethyl, propyl, butyl, pentyl, hexyl or octyl radical and more preferably are identical and represent a methyl, butyl or ethyl radical, and in that V, W, X and Y represent oxygen and D1 and D2 represent nitrogen.

[0194] According to an eighth embodiment, the invention relates to a compound according to formula (II) according to embodiment 1, characterized in that

[0195] Ri is a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl radical, preferably a methyl radical, and the radicals R2, R3, R4, R5, R9, Rio and Rn are hydrogen, or

[0196] Ri and R2 are the same or different and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl radical, preferably are the same and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl radical and more preferably represent a methyl radical, and the radicals R3, R4, R5, R9, Rio and Rn represent hydrogen, or

[0197] Ri and Rio are the same or different and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl radical, preferably are the same and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl radical and more preferably represent a methyl radical, and the radicals R2, R3, R4, R5, R9 and Rn represent hydrogen, or

[0198] Ri, R2 and Rio are the same or different and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl radical, preferably are the same and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl radical and more preferably represent a methyl radical, and the radicals R3, R4, R5, R9 and Rn represent hydrogen, or

[0199] Ri, R2, Rio and Ri1 are the same or different and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl radical, preferably are the same and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl radical and more preferably represent a methyl radical, and the radicals R3, R4, R5 and R9 represent hydrogen, and that R5 and R12 independently of one another represent optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals, preferably are the same and represent a methyl, ethyl, propyl, butyl, pentyl, hexyl or octyl radical and more preferably are the same and represent a methyl, butyl or ethyl radical, and that V, W, X and Y represent oxygen and D1 and D2 represent nitrogen.

[0200] According to a ninth embodiment, the invention relates to a compound according to embodiment 1, characterized in that the compound is selected from the group comprising or consisting of

[0201] • 2,2-dichloro-4,6-dimethyl-l ,3,6,2-dioxazastannocan, 2,2-dibromo-4,6-dimethyl- 1,3,6,2-dioxazastannocan, 2,2-dimethoxy-4,6-dimethyl-l,3,6,2-dioxazastannocan, 4,6- dimethyl-l,3,6,2-dioxazastannocan-2,2-diyl dibenzoat, 6-ethyl-4-methyl-l, 3,6,2- dioxazastannocan-2,2-diyl dibenzoat, 6-butyl-4-methyl-l,3,6,2-dioxazastannocan-2,2- diyl dibenzoat, 2,4,12-trimethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro [7.7] pentadekan, 2,2,4,12-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro [7.7] pentadekan, 2,4,10,12-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro [7.7] pentadekan, 2,2,4,10,12-pentamethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro [7.7] pentadekan, 2,2,4,10,10,12-hexamethyl-l,7,9,15-tetraoxa-4,12-diaza- 8-stannaspiro[7.7]pentadekan, 2,2,4,6,10,10,12-heptamethyl-l,7,9,15-tetraoxa-4,12- diaza-8-stannaspiro[7.7]pentadekan, 2,2,4,6,6,10,10,12-octamethyl-l,7,9,15-tetraoxa- 4,12-diaza-8-stannaspiro[7.7]pentadekan, 2,2,4,6,6,10,10,12,14-nonamethyl-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2-methyl-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2-dimethyl-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,10-dimethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2,10- trimethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-.

[0202] 2.2.10.10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan,

[0203] 4.12-diethyl-2,2,6,10,10-pentamethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2,6,6,10,10-hexamethyl-l,7,9,15-tetraoxa-

[0204] 4.12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2,6,6,10,10,14-heptamethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2-methyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,2-dimethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,10- dimethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-

[0205] 2.2.10-trimethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12- dibutyl-2,2, 10, 10-tetramethyl- 1 ,7,9, 15-tetraoxa-4, 12-diaza-8- stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,2,6,10,10-pentamethyl-l,7,9,15-tetraoxa-

[0206] 4.12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,2,6,6,10,10-hexamethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl- 2,2,6,6,10,10,14-heptamethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro[7.7]pentadekan,4,12-dibutyl-2-(trifluoromethyl)-l,7,9,15-tetraoxa-4,12- diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,10-bis(trifluoromethyl)-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dipropyl-2,2,10,10- tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dipentyl-

[0207] 2.2.10.10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan,

[0208] 4.12-dihexyl-2,2,10,10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro[7.7]pentadekan, 4,12-dioctyl-2,2,10,10-tetramethyl-l,7,9,15-tetraoxa-

[0209] 4.12-diaza-8-stannaspiro[7.7]pentadekan oder Mischungen davon,

[0210] • bevorzugt 2,4,12-trimethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan,

[0211] 2.2.4.12-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadecane,

[0212] 2.4.10.12-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadecane,

[0213] 2.2.4.10.12-pentamethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadecane,

[0214] 2.2.4.10.10.12-hexamethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadecane,

[0215] 2.2.4.6.10.10.12-heptamethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro [7.7] pentadekan, 2,2,4,6,6,10,10,12-octamethyl-l,7,9,15-tetraoxa-4,12- diaza-8-stannaspiro[7.7]pentadekan, 2,2,4,6,6,10,10,12,14-nonamethyl-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2-methyl-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2-dimethyl-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,10-dimethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2,10- trimethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-

[0216] 2,2,10,10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4.12-diethyl-2,2,6,10,10-pentamethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2,6,6,10,10-hexamethyl-l,7,9,15-tetraoxa-

[0217] 4.12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2,6,6,10,10,14-heptamethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2-methyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,2-dimethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,10- dimethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-

[0218] 2.2.10-trimethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12- dibutyl-2,2, 10, 10-tetramethyl- 1 ,7,9, 15-tetraoxa-4, 12-diaza-8- stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,2,6,10,10-pentamethyl-l,7,9,15-tetraoxa-

[0219] 4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,2,6,6,10,10-hexamethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl- 2,2,6,6,10,10,14-heptamethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro[7.7]pentadekan, 4, 12-dipropyl-2,2, 10, 10-tetramethyl- 1 ,7,9, 15-tetraoxa-

[0220] 4.12-diaza-8-stannaspiro[7.7]pentadekan, 4, 12-dipentyl-2,2, 10, 10-tetramethyl - l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dihexyl-2,2,10,10- tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dioctyl-

[0221] 2.2.10.10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan oder Mischungen davon,

[0222] • besonders bevorzugt 2,2,4,10,10,12-hexamethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro [7.7] pentadekan, 4,12-diethyl-2,2,10,10-tetramethyl-l,7,9,15-tetraoxa-4,12- diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,2,10,10-tetramethyl-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dipropyl-2,2,10,10- tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dipentyl-

[0223] 2.2.10.10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan,

[0224] 4.12-dihexyl-2,2,10,10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro [7.7]pentadecane, 4,12-dioctyl-2,2,10,10-tetramethyl-l,7,9,15-tetraoxa-

[0225] 4.12-diaza-8-stannaspiro[7.7]pentadecane or mixtures thereof,

[0226] • very particularly preferably 2,2,4,10,10,12-hexamethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadecane, 4,12-diethyl-2,2,10,10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadecane, 4,12-dibutyl-2,2,10,10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadecane or mixtures thereof.

[0227] According to a tenth embodiment, the invention relates to a process for preparing a compound having the general formula (I) according to any one of embodiments 1 to 9 by reacting either a tin-containing compound of the type R6R7SnZ2; with

[0228] • a compound of general formula (III);

[0229] HV-C' (Ri ;R2)-CH2-D, (R5)-CH2-C” (R3;R4)-WH (III) or

[0230] • a tin-containing compound of the type SnZ4; with

[0231] • a compound of general formula (III); and

[0232] HV-C' (Ri ;R2)-CH2-D, (R5)-CH2-C” (R3;R4)-WH (III)

[0233] • subsequently with compounds of the general formulas (IV) and (V);

[0234] R6-A (IV) R7-A (V) where

[0235] Ri, R2, R3, R4independently of one another represent hydrogen or optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0236] Rs independently of one another represent optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals.

[0237] Re and R7 independently of one another represent -OH, -SH, -ORI3, halogens, -OC(=O)RI4, -SR15, -OC(=S)Ri6, -OS(=O)2ORi7, -OS(=O)2Ri8 or -NRi9R2o, where RJ3 to R2o independently of one another represent optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0238] V and W independently of one another represent oxygen, sulfur, -OC(=O)-, -OC(=S)-, -SC(=O)-, -SC(=S)-, -OS(=O)2O-, -OS(=O)2- or -N(R2I)-, where R2I represents optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0239] Di for oxygen, sulfur or nitrogen;

[0240] A for leaving groups, preferably -OH, -SH, N(R 22 )H- or halogens, where R 22 represents optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0241] Z represents halogens, alkoxides or mixtures thereof; characterized in that at least one of the radicals R1, R2, R3 or R4 is hydrogen and at least one of these radicals is not hydrogen, where the carbon atoms C' and C" do not carry the same radicals.

[0242] According to an eleventh embodiment, the invention relates to a method according to embodiment 10, characterized in that

[0243] • the compound of general formula (III) 2,2'-(methylazanediyl)bis(ethan-l-ol),

[0244] 2,2'-(ethylazanediyl)bis(ethan-1-ol), 2,2'-(butylazanediyl)bis(ethan-1-ol), 1-((2-hydroxyethyl)(methyl)amino)propan-2-ol, l-(ethyl(2-hydroxyethyl)amino)propan-2-ol, l-(butyl(2-hydroxyethyl)amino)propan-2-ol, 1.1'-

[0245] (methylazanediyl)bis(propan-2-ol), 1, 1'-(ethylazanediyl)bis(propan-2-ol), 1,1'-

[0246] (butylazanediyl)bis(propan-2-ol), l-((2-hydroxyethyl)(methyl)amino)-2-methylpropan-2-ol, 1 -(ethyl(2-hydroxyethyl)amino)-2-methylpropan-2-ol, 1 -

[0247] (butyl(2-hydroxyethyl)amino)-2-methylpropan-2-ol, l-(ethyl(2-hydroxypropyl)amino)-2-methylpropan-2-ol, l-(butyl(2-hydroxypropyl)amino)-2-methylpropan-2-ol or mixtures thereof, preferably l-((2-hydroxyethyl)(methyl)amino)-2-methylpropan-2-ol, 1-(ethyl(2-hydroxyethyl)amino)-2-methylpropan-2-ol, l-(butyl(2-hydroxyethyl)amino)-2-methylpropan-2-ol or mixtures thereof; and / or

[0248] • the compound of general formula (IV) and / or general formula (V) comprises or consists of halogen, halides, alkoxides, carboxylates, peroxides, disulfides or mixtures thereof.

[0249] According to a twelfth embodiment, the invention relates to a process according to embodiment 10 or 11, characterized in that the tin-containing compound of the type SnZ4 is selected from the group comprising or consisting of tin tetrachloride, tin tetrabromide, tin tetra-tert-alkoxide, in particular tin tetra-tert-butoxide, or mixtures thereof.

[0250] According to a thirteenth embodiment, the invention relates to a process according to one of embodiments 10 to 12, characterized in that the molar ratio of tin-containing compound to the sum of the compounds having the general formula (III), (IV) and (V) is from 1:1 to 1:4, preferably from 1:1 to 1:2.1.

[0251] According to a fourteenth embodiment, the invention relates to a process for preparing a compound having the general formula (II) according to any one of embodiments 1 to 9 by reacting elemental tin or a tin-containing compound with • a compound having the general formula (III); and

[0252] HV-C ' (Ri ;R2)-CH2-D, (R5)-CH2-C' ' (R3; t)- WH (III)

[0253] • a compound with the general formula (IV);

[0254] HX-C' ' ' (R8;R9)-CH2-D2(RI2)-CH2-C” ” (RIO;RI i)-YH (VI) ; where

[0255] Ri, R2, R3, >, R8, R9, Rio and Rn independently of one another represent hydrogen or optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0256] Rs and RJ2 independently of one another represent optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals.

[0257] V, W, X and Y independently of one another represent oxygen, sulfur, -OC(=O)-, -OC(=S)-, -SC(=O)-, -SC(=S)-, -OS(=O)2O-, -OS(=O)2- or -N(R2I)-, where R2I represents optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic radicals;

[0258] D1 and D2 independently of one another represent oxygen, sulfur or nitrogen; characterized in that at least one of the radicals R1, R2, R3, R4, R8, R9, R10 or Rn is hydrogen and at least one of these radicals is not hydrogen, where the carbon atoms C' and C" and / or C'" and C"" do not carry the same radicals.

[0259] According to a fifteenth embodiment, the invention relates to a process according to embodiment 14, characterized in that the compound of the general formula (III) and / or the compound of the general formula (VI) is 2,2'-(methylazanediyl)bis(ethan-1-ol), 2,2'-(ethylazanediyl)bis(ethan-1-ol), 2,2'-(butylazanediyl)bis(ethan-1-ol), 1-((2-hydroxyethyl)(methyl)amino)propan-2-ol, 1-(ethyl(2-hydroxyethyl)amino)propan-2-ol, 1-(butyl(2-hydroxyethyl)amino)propan-2-ol, 1,1'-(methylazanediyl)bis(propan-2-ol), 1,1'-

[0260] (ethylazanediyl)bis(propan-2-ol), 1,1'-(butylazanediyl)bis(propan-2-ol), 1-((2-hydroxyethyl)(methyl)amino)-2-methylpropan-2-ol, l-(ethyl(2-hydroxyethyl)amino)-2-methylpropan-2-ol, 1-(butyl(2-hydroxyethyl)amino)-2-methylpropan-2-ol, 1-(ethyl(2-hydroxypropyl)amino)-2-methylpropan-2-ol, l-(butyl(2-hydroxypropyl)amino)-2-methylpropan-2-ol or mixtures thereof, preferably l-((2-hydroxyethyl)(methyl)amino)-2-methylpropan-2-ol, l-(ethyl(2-hydroxyethyl)amino)-2-methylpropan-2-ol and l-(butyl(2-hydroxyethyl)amino)-2-methylpropan-2-ol or mixtures thereof, wherein it is preferred if the compound of general formula (III) and the compound of general formula (VI) are identical.

[0261] According to a sixteenth embodiment, the invention relates to a process according to embodiment 14 or 15, characterized in that the tin-containing compound is selected from the group comprising or consisting of tin tetrachloride, tin tetrabromide, tin tetraalkoxide, in particular tin tetra-tert-butoxide, or mixtures thereof.

[0262] According to a seventeenth embodiment, the invention relates to a process according to one of embodiments 14 or 16, characterized in that the molar ratio of elemental tin or tin-containing compound to the sum of the compounds having the general formula (III) and (VI) is from 1:1 to 1:4, preferably from 1:1 to 1:2.1.

[0263] According to an eighteenth embodiment, the invention relates to the use of a compound according to one of embodiments 1 to 9 as a catalyst, preferably as a thermolatent catalyst for the preparation of polyisocyanate polyaddition products, in particular polyurethanes, preferably polyurethane foams, polyurethane coatings, polyurethane lacquers or polyurethane adhesives.

[0264] According to a nineteenth embodiment, the invention relates to a formulation for producing polyisocyanate polyaddition products, comprising or consisting of the following components: a) at least one optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic polyisocyanate; b) at least one compound according to one of embodiments 1 to 9 as catalyst; c) optionally further catalysts different from b); d) optionally auxiliaries and / or additives, wherein the ratio of the weight of the tin from component b) and the weight of component a) is preferably at most 1000 ppm if component a) is an aliphatic and / or (cyclo)aliphatic polyisocyanate and at most 50 ppm if component a) is an aromatic polyisocyanate.

[0265] According to a twentieth embodiment, the invention relates to a formulation according to embodiment 19, characterized in that the formulation

[0266] 5 to 80 wt.% of component a);

[0267] 0.0001 to 2.0% by weight of component b); optionally 0.01 to 2.0% by weight of component c); • optionally 5 to 50% by weight of component d); based on the total weight of the formulation.

[0268] According to a twenty-first embodiment, the invention relates to a process for the preparation of polyisocyanate polyaddition products by reacting a composition: comprising or consisting of at least one formulation according to embodiment 19 or 20 and at least one NCO-reactive compound, wherein the reaction is preferably carried out at an isocyanate number of 80 to 150 or comprising or consisting of the following components:

[0269] A) at least one optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic polyisocyanate;

[0270] B) at least one NCO reactive compound;

[0271] C) at least one compound according to any one of embodiments 1 to 9 as catalyst;

[0272] D) optionally further catalysts different from C);

[0273] E) optionally auxiliaries and / or additives, wherein the ratio of the weight of the tin from component C) and the weight of component A) is preferably at most 1000 ppm when component A) is an aliphatic and / or (cyclo)aliphatic polyisocyanate and at most 50 ppm when component A) is an aromatic polyisocyanate.

[0274] According to a twenty-second embodiment, the invention relates to a method according to embodiment 21, characterized in that the composition

[0275] • 5 to 80 wt% of component A);

[0276] • 5 to 80 wt% of component B);

[0277] • 0.0001 to 2.0 wt% of component C);

[0278] • optionally 0.01 to 2.0 wt.% of component D);

[0279] • optionally 5 to 50 wt.% of component E), based on the total weight of the composition and / or that the reaction takes place at an isocyanate number of 80 to 150.

[0280] According to a twenty-third embodiment, the invention relates to a polyisocyanate polyaddition product obtained or obtainable by a process according to embodiment 21 or 22.

[0281] According to a twenty-fourth embodiment, the invention relates to a coating composition for coating a substrate, comprising or consisting of at least one polyisocyanate polyaddition product according to embodiment 22, wherein the substrate is preferably a plastic part, a metal part or a shaped body made of wood.

[0282] Examples and comparison examples:

[0283] The present invention is discussed below with reference to examples, but is not limited to them.

[0284] In the examples, all percentages are by weight unless otherwise stated. All reactions were carried out under a dry nitrogen atmosphere. The preparation of the inventive and comparative catalysts listed in Table 1, the synthesis of the ligands used for their preparation, and the preparation of the thermolatently catalyzed polyisocyanate curing agent formulations used are described in detail in WO 2021 / 249887 A1.

[0285] To improve comparability of the activity of the catalysts used according to the invention and the catalysts from the comparative examples, the catalyst quantity was expressed as mg Sn per kg polyisocyanate hardener (ppm). The polyisocyanate hardener used was the commercial product Desmodur ultra N 3300 (HC content 5 ppm) from Covestro AG, Everkusen, Germany, NCO content 21.8%. The model compound for the isocyanate-reactive component ('polyol') was exactly one equivalent, based on the free isocyanate groups of the polyisocyanate hardener, triethylene glycol monomethyl ether (a product from Aldrich, Taufkirchen, Germany). The addition of 10% (based on Desmodur ultra N 3300) n-butyl acetate ensured that sufficiently low-viscosity samples could be obtained throughout the entire reaction, allowing precise determination of the NCO content by titration according to DIN 53 185.The NCO content calculated at the beginning of the reaction without any NCO-OH reaction amounts to 11.1% and is standardized here to 100% as the starting value. All titrated values ​​in Table 2 are standardized to this value.

[0286] Comparative experiment 1 at a constant 30°C shows the extremely slow decrease in the NCO content of the mixture in the uncatalyzed case (Table 2, Experiment 1). To enable a comparison of the reaction acceleration at a reaction temperature of 50°C (referred to as the 'curing temperature' in the real Eack system), a series of experiments was also carried out at an initial constant 30°C (2 h) and then at 50°C, also initially uncatalyzed (Table 2, Experiment 2). All comparative experiments 3 to 7 as well as the inventive examples (from 8 onwards) were run according to the same regime: initially 2 h at 30°C to assess thermolatency and then 50°C to assess reactivity at the 'curing temperature'. Table 1 Overview of the catalysts used, 1-3 comparison, from 4 onwards according to the invention

[0287] 11 The lUPAC names were generated using the program ChemDraw Professional Version 20.1.1125 and manually translated into German.

[0288] Table 2 Overview of the tests carried out

[0289] (Examples 1 - 7: comparative examples, examples 8 - 15: according to the invention)

[0290] Sn [ppm] on polyisocyanate hardener 2) constant 30°C 3) first 2 hours 30°C, then 50°C - see text

[0291] As can be seen from the results presented in Table 2, all systems—regardless of whether they are in accordance with the invention or not—are sufficiently unreactive at 30°C to be considered thermolatent. However, the systems according to the invention with an "asymmetric" ligand environment of the central atom exhibit, in some cases, significantly higher activity at 50°C than that observed in the comparison systems based on catalysts 1-3. Given the very low reactivity of compound 3 and the moderate reactivity of compound 1, it is surprising that compound 4, which has, so to speak, a "combination" of the ligand environments of 1 and 3, is significantly more reactive than both comparison catalysts. The skilled person would have expected a reactivity between that of 1 and 3. Examples 16 - 21: Measurement series for assessing color stability

[0292] Catalysts 1, 2 and 4 according to Table 1 were dissolved on the one hand in hexamethylene diisocyanate (HC content 25 ppm), whereby the catalyst concentration was selected so that mixtures containing a uniform 0.1% tin were obtained (Examples 16 - 18) and on the other hand as 10% solutions in n-butyl acetate (BA) in the heat (50°C) with the polyisocyanate Desmodur N 3900 (HC content 16 ppm) from Covestro containing iminooxadiazinedione groups in such an amount that a uniform 750 ppm of tin on solvent-free Desmodur N 3900 resulted, which were then diluted to 90% solids by adding further butyl acetate (Examples 19 - 21).

[0293] The Hazen color number was measured spectrophotometrically according to DIN EN ISO 6271-2:2005-03 using a LICO 400 spectrophotometer from Lange, Germany.

[0294] These mixtures were stored at 50°C under nitrogen and the color development was monitored, see Table 3.

[0295] Table 3 Overview of the tests carried out on the color development of HDI (0.1% Sn) and Desmodur N 3900 (750 ppm Sn on polyisocyanate)

[0296] (Examples 16 and 17 and 19 and 20: comparative examples, Examples 18 and 21: according to the invention)

[0297] As can be seen, the system according to the invention based on catalyst 4 is significantly superior to the structurally similar comparison systems (catalyst 2 is merely a positional isomer of 4!), also with regard to the color stability of the isocyanate adducts. Examples 22 - 27: Measurement series for assessing color stability

[0298] Catalysts 1, 2, 4 and 9 according to Table 1 were dissolved in bis(4-isocyanatocyclohexyl)methane (isomer mixture, product Desmodur W from Covestro, HC content < 5 ppm, detection limit of the selected method), whereby the catalyst concentration was selected such that mixtures containing a uniform 0.1% tin were obtained (Examples 22 - 25). On the other hand, catalysts 2 and 4 were mixed as 10% solutions in n-butyl acetate (BA) at warm temperature (50°C) with the polyisocyanate Desmodur CQ UN 7300 (HC content 12 ppm) from Covestro in such an amount that a uniform 750 ppm tin was obtained on solvent-free Desmodur CQ UN 7300, which were then diluted to 90% solids by adding further butyl acetate (Examples 26 - 29).

[0299] The Hazen color number was measured spectrophotometrically according to DIN EN ISO 6271-2:2005-03 using a LICO 400 spectrophotometer from Lange, Germany.

[0300] These mixtures were stored at 50°C under nitrogen and the color development was monitored, see Table 4.

[0301] Table 4 Overview of the tests carried out on the color development of Desmodur W (0.1% Sn) and Desmodur CQ UN 7300 (750 ppm Sn on polyisocyanate)

[0302] (Examples 22, 23 and 26: comparative examples, Examples 24, 25 and 27: according to the invention)

[0303]

[0304] As can be seen, the inventive products based on catalysts 4 and 9 are also significantly superior to the structurally similar comparison products (catalyst 2 is merely a positional isomer of 4!) with regard to the color stability of these isocyanate adducts. Without wishing to be bound by theory, it seems plausible to assume that the lower residual halogen contents (determined by the HC content) of the isocyanates used here (compare in particular the results obtained with Desmodur W and HDI) generally have a positive effect on color stability, with the catalysts (4 and 9) used according to the invention again showing significantly better results than the prior art comparison systems (1 and 2).

Claims

Patent claims 1. Compound of general formula (I) or (II) for use as a catalyst in the production of polyisocyanate polyaddition products, (I) (II) where Ri, R2, R3, R4, Rs, R9, Rio and Rn independently of each other for hydrogen or for, optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic residues; Ri and Rn independently of each other for, optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic residues; Re and R7 independently represent -OH, -SH, -OR13, halogens, -OC(=O)Ru, -SR15, -OC(=S)Ri6, -OS(=O)2ORi7, -OS(=O)2Ri8 or -NR19R20, where R13 to R20 independently represent, optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic residues; V, W, X and Y independently represent oxygen, sulfur, -OC(=O)-, -OC(=S)-, -SC(=O)-, -SC(=S)-, -OS(=O)2O-, -OS(=O)2- or -N(R2i)-, where R21 represents, optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic residues; Di and D2 independently represent oxygen, sulfur, or nitrogen; characterized by the fact that In formula (I), at least one of the residues Ri, R2, R3, or R4 is hydrogen and at least one of these residues is not hydrogen, wherein the carbon atoms C' and C" do not carry the same residues, and in formula (II), at least one of the residues Ri, R2, R3, R4, Rs, R9, Rio, or Rn is hydrogen and at least one of these residues is not hydrogen, wherein the carbon atoms C' and C'' and / or C'' and C"" do not carry the same residues. A compound according to claim 1, characterized in that the at least one residue Ri, R2, R3, or R4 in formula (I) that is not hydrogen and the at least one residue Ri, R2, R3, R4, Rs, R9, Rio, or Rn in formula (II) that is not hydrogen is aliphatic, preferably a methyl, ethyl, propyl, butyl, hexyl, octyl, or perfluoroalkyl residue. A compound according to claim 1 or 2, characterized in that R5 and / or R12 is a methyl, ethyl, propyl, butyl, pentyl, hexyl or octyl residue, preferably a methyl, butyl or ethyl residue.A compound according to any one of the preceding claims, characterized in that V, W, X and Y represent oxygen and / or Di and D2 represent nitrogen. A compound according to any one of the preceding claims, characterized in that Re and R7 are identical. Compound according to formula (II) according to claim 1, characterized in that the at least one residue Ri, R2, R3, R4, Rs, R9, Rio or Rn in formula (II), which is not hydrogen, is a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl residue, preferably a methyl residue, and that R5 and R12 independently represent, optionally substituted and / or heteroatom-bearing, aliphatic, (cyclo)aliphatic or aromatic residues, preferably are the same and represent a methyl, ethyl, propyl, butyl, pentyl, hexyl or octyl residue, and more preferably are the same and represent a methyl, butyl or ethyl residue, and that V, W, X and Y represent oxygen and Di and D2 represent nitrogen.Compound according to formula (II) according to claim 1, characterized in that. Ri is a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl group, preferably a methyl group, and the groups R2, R3, R4, Rs, R9, Rio and Rn represent hydrogen, or Ri and R2 are the same or different and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl group, preferably are the same and represent a methyl, ethyl, Propyl, butyl, hexyl, octyl, or perfluoroalkyl residues, and more preferably a methyl residue, and residues R3, R4, Rs, R9, Rio, and Rn represent hydrogen, or Ri and Rio are the same or different and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl group, preferably are the same and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl group, and more preferably represent a methyl group, and the groups B . P i, R4, Rs, R9 and Rn represent hydrogen, or Ri, R2 and Rio are the same or different and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl group, preferably are the same and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl group, and more preferably represent a methyl group, and the groups R3, R4, Rs, R9 and Rn represent hydrogen, or Ri, R2, Rio and Rn are the same or different and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl group, preferably are the same and represent a methyl, ethyl, propyl, butyl, hexyl, octyl or perfluoroalkyl group, and more preferably represent a methyl group, and the groups R3, R4, Rs and R9 represent hydrogen, and that Rs and R12 independently represent, optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic or aromatic groups, preferably are the same and represent a methyl, ethyl, propyl, butyl, pentyl, hexyl or octyl group, and more preferably are the same and represent a methyl, butyl or ethyl group, and that V, W, X and Y represent oxygen and Di and D2 represent nitrogen.

8. Compound according to claim 1, characterized in that the compound is selected from the group comprising or consisting of • 2,2-dichloro-4,6-dimethyl-l ,3,6,2-dioxazastannocan, 2,2-dibromo-4,6-dimethyl- 1,3,6,2-dioxazastannocan, 2,2-dimethoxy-4,6-dimethyl-l,3,6,2-dioxazastannocan, 4,6- dimethyl-l,3,6,2-dioxazastannocan-2,2-diyl dibenzoat, 6-ethyl-4-methyl-l, 3,6,2- dioxazastannocan-2,2-diyl dibenzoat, 6-butyl-4-methyl-l,3,6,2-dioxazastannocan-2,2- diyl dibenzoat, 2,4,12-trimethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro [7.7] pentadekan, 2,2,4,12-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro [7.7] pentadekan, 2,4,10,12-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro [7.7] pentadekan, 2,2,4,10,12-pentamethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro [7.7] pentadekan, 2,2,4,10,10,12-hexamethyl-l,7,9,15-tetraoxa-4,12-diaza- 8-stannaspiro[7.7]pentadekan, 2,2,4,6,10,10,12-heptamethyl-l,7,9,15-tetraoxa-4,12- diaza-8-stannaspiro[7.7]pentadekan, 2,2,4,6,6,10,10,12-octamethyl-l,7,9,15-tetraoxa- 4.12-diaza-8-stannaspiro[7.7]pentadekan, 2,2,4,6,6,10,10,12,14-nonamethyl-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2-methyl-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2-dimethyl-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,10-dimethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2,10- trimethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl- 2.2.10.10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4.12-diethyl-2,2,6,10,10-pentamethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2,6,6,10,10-hexamethyl-l,7,9,15-tetraoxa- 4.12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2,6,6,10,10,14-heptamethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2-methyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,2-dimethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,10- dimethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl- 2.2.10-trimethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12- dibutyl-2,2, 10, 10-tetramethyl- 1 ,7,9, 15-tetraoxa-4, 12-diaza-8- stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,2,6,10,10-pentamethyl-l,7,9,15-tetraoxa- 4.12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,2,6,6,10,10-hexamethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl- 2,2,6,6,10,10,14-heptamethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro[7.7]pentadekan,4,12-dibutyl-2-(trifluoromethyl)-l,7,9,15-tetraoxa-4,12- diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,10-bis(trifluoromethyl)-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dipropyl-2,2,10,10- tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dipentyl- 2.2.10.10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4.12-dihexyl-2,2,10,10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro[7.7]pentadekan, 4,12-dioctyl-2,2,10,10-tetramethyl-l,7,9,15-tetraoxa- 4.12-diaza-8-stannaspiro[7.7]pentadekan oder Mischungen davon, • bevorzugt 2,4,12-trimethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 2.2.4.12-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 2.4.10.12-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 2.2.4.10.12-pentamethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 2.2.4.10.10.12-hexamethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 2.2.4.6.10.10.12-heptamethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro [7.7] pentadekan, 2,2,4,6,6,10,10,12-octamethyl-l,7,9,15-tetraoxa-4,12- diaza-8-stannaspiro[7.7]pentadekan, 2,2,4,6,6,10,10,12,14-nonamethyl-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2-methyl-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2-dimethyl-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,10-dimethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2,10- trimethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl- 2.2.10.10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4.12-diethyl-2,2,6,10,10-pentamethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2,6,6,10,10-hexamethyl-l,7,9,15-tetraoxa- 4.12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-diethyl-2,2,6,6,10,10,14-heptamethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2-methyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,2-dimethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,10- dimethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl- 2.2.10-trimethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12- dibutyl-2,2, 10, 10-tetramethyl- 1 ,7,9, 15-tetraoxa-4, 12-diaza-8- stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,2,6,10,10-pentamethyl-l,7,9,15-tetraoxa- 4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,2,6,6,10,10-hexamethyl- l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl- 2,2,6,6,10,10,14-heptamethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro[7.7]pentadekan, 4, 12-dipropyl-2,2, 10, 10-tetramethyl- 1 ,7,9, 15-tetraoxa- 4.12-diaza-8-stannaspiro[7.7]pentadekan, 4, 12-dipentyl-2,2, 10, 10-tetramethyl - l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dihexyl-2,2,10,10- tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dioctyl- 2.2.10.10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan oder Mischungen davon, • besonders bevorzugt 2,2,4,10,10,12-hexamethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro [7.7] pentadekan, 4,12-diethyl-2,2,10,10-tetramethyl-l,7,9,15-tetraoxa-4,12- diaza-8-stannaspiro[7.7]pentadekan, 4,12-dibutyl-2,2,10,10-tetramethyl-l,7,9,15- tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dipropyl-2,2,10,10- tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4,12-dipentyl- 2.2.10.10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadekan, 4.12-dihexyl-2,2,10,10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8- stannaspiro [7.7]pentadecane, 4,12-dioctyl-2,2,10,10-tetramethyl-l,7,9,15-tetraoxa- 4.12-diaza-8-stannaspiro[7.7]pentadecane or mixtures thereof, • most particularly preferably 2,2,4,10,10,12-hexamethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro [7.7]pentadecane, 4,12-diethyl-2,2,10,10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadecane, 4,12-dibutyl-2,2,10,10-tetramethyl-l,7,9,15-tetraoxa-4,12-diaza-8-stannaspiro[7.7]pentadecane or mixtures thereof. Use of a compound according to any one of claims 1 to 8 as a catalyst, preferably as a thermolatent catalyst for the production of polyisocyanate polyaddition products, in particular polyurethanes, preferably polyurethane foams, polyurethane coatings, polyurethane varnishes or polyurethane adhesives.A formulation for the production of polyisocyanate polyaddition products, comprising or consisting of the following components: a) at least one, optionally substituted and / or heteroatom-containing, aliphatic, (cyclo)aliphatic, or aromatic polyisocyanate; b) at least one compound according to any one of claims 1 to 8 as a catalyst; c) optionally further catalysts different from b); d) optionally auxiliary and / or additives, wherein the ratio of the weight of tin from component b) to the weight of component a) is preferably at most 1000 ppm if component a) is an aliphatic and / or (cyclo)aliphatic polyisocyanate, and at most 50 ppm if component a) is an aromatic polyisocyanate. A formulation according to claim 10, characterized in that the formulation. • 5 to 80 wt. -% of component a); • 0.0001 to 2.0 wt.% of component b); • if necessary, 0.01 to 2.0 wt.% of component c); • optionally 5 to 50 wt% of component d); contains, based on the total weight of the formulation. Process for the preparation of polyisocyanate polyaddition products by reacting a composition: comprising or consisting of at least one formulation according to claim 10 or 11 and at least one NCO reactive compound, wherein the reaction preferably takes place at an isocyanate number of 80 to 150 or comprising or consisting of the following components: A) at least one aliphatic, (cyclo)aliphatic or aromatic polyisocyanate, optionally substituted and / or containing a heteroatom; B) at least one NCO reactive compound; C) at least one compound according to any one of claims 1 to 8 as a catalyst; D) possibly further catalysts different from C); E) optionally auxiliary and / or additive substances, wherein the ratio of the weight of the tin from component C) and the weight of component A) is preferably at most 1000 ppm if component A) is an aliphatic and / or (cyclo)aliphatic polyisocyanate and at most 50 ppm if component A) is an aromatic polyisocyanate. The method according to claim 12, characterized in that the composition • 5 to 80 wt.% of component A); • 5 to 80 wt.% of component B); • 0.0001 to 2.0 wt.% of component C); • if necessary, 0.01 to 2.0 wt.% of component D); • optionally 5 to 50 wt.% of component E); contains, based on the total weight of the composition and / or, that the reaction takes place at an isocyanate number of 80 to 150. Polyisocyanate polyaddition product obtained or obtainable by a process according to claim 12 or 13. Coating composition for coating a substrate, comprising or consisting of at least one polyisocyanate polyaddition product according to claim 14, wherein the substrate is preferably a plastic part, a metal part or a molded wooden body.

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