METAL-SILOXANE-SILANOL(ATE) COMPOUND AS GEL CATALYST

Abstract

The invention relates to the use of at least one metal-siloxane-silanol(ate) compound for selective catalysis of the gel reaction in a system for the production of polyurethanes, preferably of unfoamed polyurethanes, flexible foams or rigid foams and/or in the two-component (2K) system according to the invention, and to processes for producing foamed or unfoamed polyurethanes, especially flexible foams or rigid foams, and to use in the CASE sector (coatings, adhesives, sealants and elastomers), furniture, mattresses, car seats, seal materials or acoustic materials, for insulation of district heating pipes, tanks and pipelines, and for production of all kinds of refrigeration units. In a further aspect, the invention relates to unfoamed polyurethanes, flexible foams and/or rigid foams each produced through the inventive use of at least one metal-siloxane-silanol(ate) compound for selective catalysis of the gel reaction.

Description

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a National Stage of International Application No. PCT/EP2020/057877 filed on Mar. 20, 2020, claiming priority based on European Patent Application No. 19165363.3 filed on Mar. 26, 2019 and European Patent Application No. 19206679.3 filed on Oct. 31, 2019.

The present invention relates to the field of production of polyurethanes, especially by means of two-component (2K) systems, preferably to the production of unfoamed polyurethanes and/or of rigid foams and flexible foams (PU foams), and to the use thereof in CASE sectors (coatings, adhesives, sealants and elastomers). The invention especially relates to the use of a gel catalyst in the production of polyurethanes, and also to the composition thereof and to processes for producing polyurethanes.

One of the most important chemical reactions of relevance in the production of polyurethanes, especially of rigid and flexible foams, coatings, adhesives, sealant materials and elastomers (CASE), is the reaction of an isocyanate-containing component with a compound containing an active hydrogen, as is the case, for example, in polyols and/or water. According to the progression of the reaction and choice of catalyst, it is possible to catalyse what is called the gel reaction (1). The urethane linkage through reaction of an isocyanate-containing component with an isocyanate-reactive component (e.g. hydroxy-functionalized polymer or polyol) permits the formation of polyurethanes

R—NCO+HO—R′→R—NH—CO—OR′(gel reaction)  (1)

The reaction of an isocyanate-containing component with water, by contrast, leads to formation of an unstable carbamic acid that breaks down to give a primary amine and CO₂ (2).

R—NCO+H—OH→[R—NH—CO—OH]→R—NH2+CO₂↑(blow reaction)  (2)

R′—NH2+R—NCO→R′—NH—CO—NH—R  (3)

The primary amine formed reacts with an isocyanate-containing component to give symmetric urea derivatives.

This reaction (2) is referred to as blow reaction. The CO₂ that forms assumes the function here of a blowing gas, for example in the production of polyurethane foams.

In the case of production of unfoamed polyurethanes, this reaction is undesirable. It is generally desirable for the person skilled in the art to be able to control reactions and the progression thereof. This is fundamentally also the case in the production of rigid and flexible foams. In that case too, it may be advantageous to control the blow reaction, such that, for example, no foaming or no excessive or undesirable foaming of the material takes place.

The person skilled in the art is aware, in particular, of organic tin complexes, especially dibutyltin dilaurate (DBTL) and tertiary amines, especially triethylenediamine (DABCO (=TEDA)) catalysts in polyurethane production.

Unwanted blow reactions can also set in on account of residual moisture in the reactants (for example in polyols, fillers, solvents, auxiliaries etc.) or on account of ambient humidity in the production and curing process. It is known that this can be countered by the use of water scavengers or desiccants. The use of additional raw materials—that are usually hazardous to health—such as water scavengers, for example vinyltrimethoxysilane (VTMO or Dynasilan®) leads to a further increase in production costs.

It is accordingly an object of the invention to provide an improved process for producing polyurethanes.

This object is achieved according to claim 1. Advantageous developments are the subject of the dependent claims or of the further independent claims.

The core of the invention is to use the new and surprising finding that metal-siloxane-silanol(ate) compounds selectively catalyse the gel reaction for the production of polyurethanes, especially of unfoamed polyurethanes, flexible foams or rigid foams. One aspect of the invention is thus the use of metal-siloxane-silanol(ate) compounds as gel catalyst.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts the foaming characteristics of the elastomer products EP1 (reference) and EP4-EP6 (water content 0.1%).

FIG. 2 depicts the foaming characteristics of the elastomer products EP1 (reference) and EP7-EP9 (water content 0.2%).

FIG. 3 depicts the foaming characteristics of the elastomer products EP1 (reference) and EP10-EP12 (water content 0.4%).

FIG. 4 depicts the foaming characteristics of the elastomer products EP1 (reference) and EP13-EP15 (water content 0.6%).

FIG. 5 depicts the foaming characteristics of the elastomer products EP1 (reference) and EP16-EP18 (water content 0.8%).

In the context of the present invention, the term “gel catalyst” (or “gelation catalyst”) is understood to mean a catalyst that preferentially catalyses the gel reaction (1) compared to the blow reaction, i.e. urethane linkage by reaction of an isocyanate-containing component with an isocyanate-reactive component (hydroxy-functionalized polymer or polyol). The formation of the urethane bond (R—NH—CO—OR′), in the presence of at least one metal-siloxane-silanol(ate) compound, is accordingly preferred over the formation of the urea bond (R′—NH—CO—NH—R).

The term “selectivity” (or “gel/blow reaction selectivity”), in the context of the present invention, thus describes the property of a catalyst of the degree to which it preferentially catalyses the gel reaction over the blow reaction. If neither of the reactions is preferred, the selectivity is 1, i.e. the ratio of gel reaction to blow reaction is 1:1. The greater the value, the more the catalyst catalyses the gel reaction compared to the blow reaction.

In a preferred embodiment of the invention, the metal-siloxane-silanol(ate) compound has a selectivity of >1, preferably >5, more preferably >10, further preferably >30, most preferably >40. Preferred metal-siloxane-silanol(ate) compounds are specified below. Particular preference is given to the metal-siloxane-silanol(ate) compounds according to claim 17, especially compounds according to claim 18. In claim 18, particular preference is given to the compounds TiPOSS and SnPOSS.

The selectivity of the metal-siloxane-silanol(ate) compounds became apparent to the inventors for the first time through comparison with the previously known catalysts DBTL and DABCO. In comparative experiments (Example I below), test compositions (EP1-EP18) for unfoamed polyurethanes that differ in their water content and the respective catalyst were used. The inventors found here that, in the presence of TiPOSS, the blow reaction only set in at a higher amount of water compared to the customary catalysts. The onset of the blow reaction was identified by the foaming (by the gaseous CO2↑ formed) of the material. This means that, when TiPOSS is used in the production of polyurethanes, the Shore hardness and density of the material remain essentially unchanged in the presence of water within particular limits.

The selectivity of catalysts for the gel reaction with respect to the blow reaction in the production of polyurethanes can be verified by an essay according to Example I below.

In addition, the person skilled in the art is aware of methods of determining the selectivity of catalysts in the production of polyurethanes, for example the titration method according to Farkas described below in Example III (A. Farkas and K. G. Flynn, J. Am. Chem. Soc., 82, 642, 1960) or the method according to R. van Maris et al. (J. Cel. Plastics, 41, 305-322, 2005). The titration method compares the respective reaction during a standardized conversion of an isocyanate component with a diol component (including alcohol) in the presence of different catalysts.

It is fundamentally the case that the properties of the resulting polyurethanes can be more accurately adjusted with more specific steering and control of the gel reaction and/or blow reaction. Thus, the inventive use of metal-siloxane-silanol(ate) compounds enables, for example, more constant densities in unfoamed polyurethanes, or elevated tensile strengths in foamed polyurethanes. It is advantageously additionally possible to dispense with the addition of water scavengers, or else to reduce the proportion of water scavengers, since the risk of an unwanted blowing reaction falls with the selectivity of the catalyst used for the gel reaction.

In a particularly advantageous embodiment of the invention, the metal-siloxane-silanol(ate) compound(s) are used in the production of unfoamed polyurethanes, especially in the production of elastomers or thermosets. In one aspect, the invention thus relates to the use of at least one metal-siloxane-silanol(ate) compound, especially a mononuclear metallized silsesquioxane such as TiPOSS or SnPOSS, for the production of unfoamed polyurethanes, especially for the production of elastomers or encapsulating compounds

In the context of the invention, “unfoamed polyurethane” is understood to mean a polyurethane (also “polyurethane material”) having a density of ≥800 kg/m³. Unfoamed polyurethanes are, for example, elastomers and thermosets. These may be encapsulating compounds or casting systems.

In a preferred embodiment, the unfoamed polyurethane produced/producible in accordance with the invention has a density in the range of ≥800 to 2000 kg/m³, preferably in the range from 950 to 1750 kg/m³, more preferably in the range from 980 to 1650 kg/m³, most preferably in the range from 990 to 1600 kg/m³.

“Density” indicates the ratio of mass to volume of a material—i.e. the quotient of the mass m of a material and its volume V. According to the invention, the density of unfoamed polyurethane, especially of elastomers and encapsulating compounds, and foamed polyurethane, especially flexible and rigid foams, is determined according to DIN EN ISO 845:2009-10.

The unfoamed polyurethanes producible in accordance with the invention, preferably with the densities as described above, have advantageous hardnesses. These can be classified and defined with the Shore hardnesses known to the person skilled in the art (see the definitions and methods for the purpose below). Advantageously, the unfoamed polyurethanes have the following hardnesses:

• • Shore 00 hardness in the range of 40-100, preferably in the range from 45 to 95, preferably in the range from 50 to 90, more preferably in the range from 55 to 85, and/or
  • Shore A hardness in the range of 0-100, preferably in the range from 5 to 95, preferably in the range from 10 to 90, more preferably in the range from 15 to 85, and/or
  • Shore D hardness in the range of 0-100, preferably in the range from 5 to 95, preferably in the range from 10 to 90, more preferably in the range from 15 to 85.

“Shore hardness” is a material index, for example for elastomers or plastics. It is directly related to the penetration depth of a body into the material to be tested, and hence is a measure of the hardness thereof. The penetration body (indenter) used is a spring-loaded stylus made of hardened steel. In these methods, the respective indenter is pushed into the test specimen with a spring force. The penetration depth is thus a measure of the Shore hardness. The method of testing varies according to the force and sample head and can be expressed inter alia in the Shore hardnesses Shore 00, Shore A and Shore D. According to the invention, the Shore hardnesses, whether Shore 00, Shore A or Shore D hardness, are determined according to standard ASTM D2240-15.

As set out, it is possible in accordance with the invention preferably to produce unfoamed polyurethanes, especially elastomers and thermosets, for example encapsulating compounds and/or casting systems.

Elastomers are generally notable for their fixed but elastically deformable tactile properties. Elastomers deform under tensile and compressive stress, but return to their original, undeformed shape after the respective stress. Elastomers find use, inter alia, as material for tyres, rubber bands, gasket rings, etc.

Encapsulating compounds, especially polyurethane encapsulating compounds, are used in the specialist field for potting or encapsulating components and devices, inter alia. Their good flexibility, even at low temperatures, excellent water resistance and wide range of possible curing options make encapsulating compounds composed of polyurethane ideal for sensitive components and/or complex geometries. According to the invention, Shore 00/ND hardnesses and densities for encapsulating compounds are within the abovementioned ranges for casting systems.

Casting systems, on account of their high thermal and chemical stability, are used predominantly in adhesive and sealant systems. Casting systems are non-foaming 2-component encapsulating compounds based on polyurethane that have a low level of or are free of solvent.

According to the invention, in one embodiment, preference is given to producing filled casting systems. These may preferably have a filler content of 5% to 70%, Shore A or Shore D hardnesses of 90, and densities between 1.1 and 1.8 g/cm³. Unfilled casting systems (filler content=0%) preferably have a Shore A hardness of 10, a Shore D hardness of 90, and a density of 0.85 to 1.2 g/cm³.

In a further aspect of the invention, the metal-siloxane-silanol(ate) compound is advantageously used in the production of foamed polyurethanes. The polyurethanes thus produced preferably have advantageous tensile strengths. Thus, the inventors, in comparative experiments with conventional catalysts according to Example II (GF1-GF15) and (RF1-RF2) found, that foamed polyurethanes with elevated tensile strengths are producible using TiPOSS. In this aspect of the invention, therefore, at least one metal-siloxane-silanol(ate) compound, especially at least one mononuclear metallized silsesquioxane such as TiPOSS or SnPOSS, is used for the production of foamed polyurethanes having elevated strengths, especially flexible and/or rigid foams.

In the context of the invention, “foamed polyurethane” refers to a polyurethane having a density of ≤800 kg/m³. In the production of foamed polyurethanes, a blowing catalyst is optionally used in addition to the gel catalyst. In the production of foamed polyurethanes, the blowing agent comes either from the reaction (in situ) or from an external source (external gas supply, for example by a gas cartridge).

“Blowing agent” is a gaseous substance, or substance that releases a gas, or substance composition which is added to a composition in order to generate pores therein in the course of further processing. The use of blowing agents thus serves to impart a desired porosity to a different material or to reduce material density. A blowing agent may be formed in situ, for example by reaction of two substances, as in the blowing reaction by the reaction of an isocyanate-containing component with water (here: gaseous CO₂↑), or alternatively be supplied to the material from an external source. One example of the latter variant is the supply of a gas, for example CO₂, N₂, Ar, H₂, O₂ or other gases or mixtures thereof, for example by means of gas cartridges and/or introduction pipes or nozzles. A “blowing gas” is a blowing agent.

In this inventive use of the metal-siloxane-silanol(ate) compound, it has been found that the foams produced in this way, especially flexible and rigid foams, feature a homogeneous pore structure. The rigid foams also show a fine-cell or fine-pore distribution of the cavities in the material. This results in advantageous properties with regard to thermal conductivity. The invention therefore also relates, in one aspect, to the production of foams for the provision of materials for thermal insulation.

In a preferred embodiment of this inventive use of the metal-siloxane-silanol(ate) compound, it is preferably possible to produce foamed polyurethanes of a density in the range from 100 to 900 kg/m³, preferably in the range from 150 to 850 kg/m³, more preferably in the range from 200 to 750 kg/m³, most preferably in the range from 200 to 650 kg/m³.

It is possible with preference in accordance with the invention to obtain foamed polyurethanes having the following Shore hardnesses (definitions as above):

• • Shore 00 hardness in the range of 10-100, preferably in the range from 10 to 90, preferably in the range from 20 to 80, more preferably in the range from 35 to 75, and/or
  • Shore A hardness in the range of 0-100, preferably in the range from 20 to 95, preferably in the range from 20 to 60, more preferably in the range from 20 to 50, and/or
  • Shore D hardness in the range of 0-90, preferably in the range from 10 to 90, preferably in the range from 20 to 80, more preferably in the range from 35 to 75.

In a further aspect of the invention, the metal-siloxane-silanol(ate) compound is used in accordance with the invention especially for production of flexible foams. Flexible foams typically have a long lifetime, good resilience and good deformability. The density of flexible foams produced/producible in accordance with the invention varies between about 5 and 650 kg/m³, and that of slabstock foams between 25 and 300 kg/m³.

In a particularly advantageous embodiment, according to the invention, a flexible foam having a Shore A hardness of ≥20 is produced. Especially preferred is the production of a flexible foam having a Shore A hardness between 20 and 100, preferably between 20 and 60, more preferably between 20 and 50.

The flexible foams producible/produced in accordance with the invention advantageously have a tensile strength of ≥200 kPa. Especially preferred are flexible foams having a tensile strength between 200 and 350 kPa. Tensile strength and methods for determination thereof are defined below. They are known to the person skilled in the art.

In a particularly preferred embodiment of the invention, the flexible foams have a Shore A hardness between 20 and 50 and a tensile strength between 200 and 350 kPa.

In a further advantageous embodiment, the metal-siloxane-silanol(ate) compound is used as catalyst for the production of rigid polyurethane foams. Rigid foams generally feature a long lifetime, high shape and dimensional stability, and low thermal conductivities and low mold cavity pressures.

The inventive use of the metal-siloxane-silanol(ate) compound can especially be used for production of rigid foams of density in the range from 25 to 900 kg/m³. These foams preferably serve for thermal insulation, for example in buildings, cooling equipment, heat and cold reservoirs, and some pipe systems (outer plastic composite pipe, flexible composite pipes). In this aspect, the inventive use therefore relates to the production of insulation material.

In a preferred embodiment, the rigid foams have a Shore D hardness of ≥10. Further preferably, Shore D hardness is between 15 and 100, preferably between 20 and 95, most preferably between 25 and 90.

In a further preferred embodiment, the rigid foams have a tensile strength of ≥100 kPa, especially of 200 to 2000 kPa. The tensile strength here is preferably ≥350 kPa.

It is most preferable to use the metal-siloxane-silanol(ate) compound for production of rigid foams of Shore D hardness between 25 and 90 and tensile strength between 350 and 2000 kPa.

“Tensile strength” is a strength index of a material. Tensile strength describes the maximum mechanical tension that a material withstands. When the tensile strength is exceeded, the material breaks, tears or shatters. The dimension for tensile strength is force per unit area—the units of measurement used are N/mm² or kPa/MPa. The test methods for determination of tensile strength and elongation at break are known to the person skilled in the art. For flexible foams they can preferably be conducted according to DIN EN ISO 1798:2008-04, and for rigid foams according to ISO 1926:2009-12.

In a particularly preferred embodiment, at least one metal-siloxane-silanol(ate) compound is used for selective catalysis of the gel reaction in a two-component (2K) system. The (2K) system comprises a component A and a component B. Component A comprises at least one hydroxy-functionalized polymer. Component B comprises at least one compound having one or more isocyanate groups. The metal-siloxane-silanol(ate) compound(s) may be formulated or included in one of the two components or in both components. Preference is given to formulating or including the metal-siloxane-silanol(ate) compound(s) with component A.

It additionally follows for the gel reaction from the selectivity of the metal-siloxane-silanol(ate) compounds that have been found by the inventors that the metal-siloxane-silanol(ate) compounds make it possible to reduce the level of or dispense with water scavengers that are added additionally. This in turn results in the conservation of resources and lowering of the costs through saving of material. The use according to the invention further permits the use of raw materials that do not have to undergo any particular or additional drying. Furthermore, the use according to the invention makes the mixtures in question more storage-stable.

The use of at least one metal-siloxane-silanol(ate) compound for selective catalysis of the gel reaction in a system for the production of polyurethanes results in a reduction in unwanted or uncontrolled side reactions (for example the blowing reaction). The product yield is accordingly greater in the use according to the invention without disruptive side reactions.

Surprisingly, reaction mixtures with inventive use of the blowing catalyst do not require any further or additional catalysts for curing in production of polyurethanes. The use of the gel catalyst according to the invention therefore makes it possible to reduce the level of or entirely dispense with tin-containing (gel) catalysts and/or amine catalysts.

In addition to dispensing with water scavengers and further catalysts, it is also possible to use a lower level of isocyanate-containing compounds, since these, by virtue of the use according to the invention, no longer have to be added in an elevated excess (beyond the reaction stoichiometry required). In the prior art, they occasionally also serve as water scavengers and to maintain the stability and reactivity of reaction mixtures for production of polyurethanes.

In a further aspect of the invention, it is thus possible to generally further reduce the use of substances harmful to health and to make employment more user-friendly for the end user.

According to the invention, “water scavengers” are compounds or substances that are added to a mixture of constituents with the aim of themselves reacting with/depleting water or binding water. The addition of water scavengers in the main application avoids the unwanted presence of water, for example on account of problematic or unwanted reactions of water with further mixture constituents.

The high selectivity coupled with a high catalytic activity of the metal-siloxane-silanol(ate) compounds in use for selective catalysis of the gel reaction for the production of polyurethanes (PU) also allows the catalyst input to be reduced overall. According to the reactants and reaction regime used for production of polyurethane materials, the amounts of catalyst required may be in the range from 10 to 75 000 ppm, preferably in the range from 15 to 10 000 ppm or in the range from 20 to 5000 ppm.

In the context of the invention, “polyurethanes” are also polyurethane materials, polyurethane substances or polyurethane systems, or polymers comprising urethane linkages. Alternatively, the abbreviation “PU” is likewise used for polyurethane. In a generally customary manner and in accordance with the invention, polyurethanes are divided into unfoamed and foamed polyurethanes.

According to the invention, “urethane linkage” or else “urethane bond” is used for the urethane units or groups that form in the production of polyurethanes. The urethane unit or group itself is shown here in bold type: R—NH—CO—OR′. This can form, for example, through a reaction or linkage of an isocyanate group (—N═C═O) in an isocyanate-containing compound with a hydroxyl group (—OH) in a hydroxy-functionalized polymer or polyol.

According to the invention, isocyanate-reactive compounds are those that can react with an isocyanate. These compounds may have one or more NH, OH or SH functions.

The isocyanate-reactive compounds especially include the class of the hydroxy-functional compounds. Polyols are hydroxy-functional compounds, especially hydroxy-functional polymers. Suitable polyols for the preparation of polyurethane polymers are especially polyether polyols, polyester polyols and polycarbonate polyols, and mixtures of these polyols.

“Polyethers” are a class of polymers. They are long-chain compounds comprising at least two identical or different ether groups. According to the invention, polyethers also include those where the polymeric ether groups are interrupted by another group (for example by copolymerized/incorporated isocyanates or further polymer or oligomeric units of a different monomer origin).

“Polymers” are chemical compounds composed of chain or branched molecules (macromolecules) but in turn consist of a number of identical/equivalent or else different units, called the monomers. Polymers also include oligomers. Oligomers are polymers having a smaller number of units. Unless explicitly defined differently, oligomers are included in the concept of polymers in accordance with the invention. Polymers may occur as homopolymers (=consisting only of one monomer unit), copolymers (=consisting of two or more monomer units) or as a polymer mixture (=polymer alloy, polymer blends, i.e. mixtures of different polymers and copolymers).

Suitable polyether polyols, also called polyoxyalkylene polyols or oligoetherols, are especially those that are polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, oxetane, tetrahydrofuran or mixtures thereof, optionally polymerized with the aid of a starter molecule having two or more

active hydrogen atoms, for example water, ammonia or compounds having multiple OH or NH groups, for example ethane-1,2-diol, propane-1,2- and -1,3-diol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, cyclohexane-1,3- and -1,4-dimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, pentaerythritol, sorbitol, sugar, dipentaerythritol, glycerol, aniline, and mixtures of the compounds mentioned.

It is possible to use either polyoxyalkylene polyols having a low degree of unsaturation (measured in accordance with ASTM D-2849-69 and expressed in milliequivalents of unsaturation per gram of polyol (mEq/g)), produced for example using so-called double metal cyanide complex catalysts (DMC catalysts), or polyoxyalkylene polyols having a relatively high degree of unsaturation, produced for example using anionic catalysts such as NaOH, KOH, CsOH or alkali metal alkoxides. Polyoxyethylene polyols and polyoxypropylene polyols are particularly suitable, especially polyoxyethylene diols, polyoxypropylene diols, polyoxyethylene triols, and polyoxypropylene triols.

Especially suitable are polyoxyalkylene diols or polyoxyalkylene triols having a degree of unsaturation lower than 0.02 mEq/g and having a molecular weight within a range from 1000 g/mol to 30 000 g/mol, as are polyoxyethylene diols, polyoxyethylene triols, polyoxypropylene diols, and polyoxypropylene triols having a molecular weight of 200 to 20 000 g/mol. Likewise particularly suitable are so-called ethylene oxide-terminated (“EO-endcapped”, ethylene oxide-endcapped) polyoxypropylene polyols. The latter are special polyoxypropylene polyoxyethylene polyols that are obtained for example when pure polyoxypropylene polyols, in particular polyoxypropylene diols and triols, are at the end of the polypropoxylation reaction further alkoxylated with ethylene oxide and thus have primary hydroxyl groups. Preference in this case is given to polyoxypropylene polyoxyethylene diols and polyoxypropylene polyoxyethylene triols. Also suitable are hydroxyl-terminated polybutadiene polyols, for example those produced by polymerization of 1,3-butadiene and allyl alcohol or by oxidation of polybutadiene and also the hydrogenation products thereof. Also suitable are styrene-acrylonitrile grafted polyether polyols such as those commercially available for example under the trade name Lupranol® from Elastogran GmbH, Germany.

Suitable polyester polyols include in particular polyesters that bear at least two hydroxyl groups and are produced by known processes, in particular polycondensation of hydroxycarboxylic acids or polycondensation of aliphatic and/or aromatic polycarboxylic acids with dihydric or polyhydric alcohols.

Especially suitable are polyester polyols produced from dihydric to trihydric alcohols such as ethane-1,2-diol, diethylene glycol, propane-1,2-diol, dipropylene glycol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, neopentyl glycol, glycerol, 1,1,1-trimethylolpropane or mixtures of the abovementioned alcohols with organic dicarboxylic acids or the anhydrides or esters thereof, for example succinic acid, glutaric acid, adipic acid, trimethyladipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, dimer fatty acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, dimethyl terephthalate, hexahydrophthalic acid, trimellitic acid and trimellitic anhydride or mixtures of the abovementioned acids, as are polyester polyols formed from lactones such as ε-caprolactone. Particularly suitable are polyester diols, in particular those produced from adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, dimer fatty acid, phthalic acid, isophthalic acid and terephthalic acid as the dicarboxylic acid or from lactones such as ε-caprolactone and from ethylene glycol, diethylene glycol, neopentyl glycol, butane-1,4-diol, hexane-1,6-diol, dimer fatty acid diol, and cyclohexane-1,4-dimethanol as the dihydric alcohol.

Suitable polycarbonate polyols include in particular those obtainable by reaction for example of the abovementioned alcohols used to form the polyester polyols with dialkyl carbonates such as dimethyl carbonate, diaryl carbonates such as diphenyl carbonate, or phosgene. Polycarbonate diols, in particular amorphous polycarbonate diols, are particularly suitable. In addition, polycarbonate diols or polyether polycarbonate diols may be obtainable via polymerization of propylene oxide with CO₂.

Further suitable polyols are poly(meth)acrylate polyols.

Also suitable are polyhydroxy-functional fats and oils, for example natural fats and oils, in particular castor oil, or so-called oleochemical polyols obtained by chemical modification of natural fats and oils, the epoxy polyesters or epoxy polyethers obtained for example by epoxidation of unsaturated oils and subsequent ring opening with carboxylic acids or alcohols respectively, or polyols obtained by hydroformylation and hydrogenation of unsaturated oils. Also suitable are polyols obtained from natural fats and oils by degradation processes such as alcoholysis or ozonolysis and subsequent chemical linking, for example by transesterification or dimerization, of the thus obtained degradation products or derivatives thereof. Suitable breakdown products of natural fats and oils are in particular fatty acids and fatty alcohols and also fatty acid esters, in particular the methyl esters (FAME), which can be derivatized to hydroxy fatty acid esters, for example by hydroformylation and hydrogenation.

Likewise suitable are, in addition, polyhydrocarbon polyols, also referred to as oligohydrocarbonols, for example polyhydroxy-functional ethylene-propylene, ethylene-butylene or ethylene-propylene-diene copolymers, for example those produced by Kraton Polymers, USA, or polyhydroxy-functional copolymers of dienes, such as 1,3-butadiene or diene mixtures, and vinyl monomers such as styrene, acrylonitrile or isobutylene, or polyhydroxy-functional polybutadiene polyols, for example those which are produced by copolymerization of 1,3-butadiene and allyl alcohol and which may also be hydrogenated. Also suitable are polyhydroxy-functional acrylonitrile/butadiene copolymers, such as those that can be produced for example from epoxides or amino alcohols and carboxyl-terminated acrylonitrile/butadiene copolymers that are commercially available under the Hypro® CTBN name from Emerald Performance Materials, LLC, USA.

These likewise particularly preferred polyols may have an average molecular weight of 250 to 40 000 g/mol, especially of 1000 to 30 000 g/mol, and an average OH functionality in the range from 1.6 to 6.

Particularly suitable polyols are polyester polyols and polyether polyols, in particular polyoxyethylene polyol, polyoxypropylene polyol, and polyoxypropylene polyoxyethylene polyol, preferably polyoxyethylene diol, polyoxypropylene diol, polyoxyethylene triol, polyoxypropylene triol, polyoxypropylene polyoxyethylene diol, and polyoxypropylene polyoxyethylene triol.

In addition to these polyols mentioned, it is also possible to use small amounts of low molecular weight di- or polyhydric alcohols, for example ethane-1,2-diol, propane-1,2- and -1,3-diol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, cyclohexane-1,3- and -1,4-dimethanol, hydrogenated bisphenol A, dimeric fatty alcohols, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol, pentaerythritol, sugar alcohols such as xylitol, sorbitol or mannitol, sugars such as sucrose, other higher polyhydric alcohols, low molecular weight alkoxylation products of the aforementioned di- and polyhydric alcohols, and mixtures of the aforementioned alcohols in the use of the gel catalyst according to the invention in the production of polyurethanes, especially of unfoamed polyurethanes and/or in a two-component (2K) system according to the invention.

Isocyanate-containing compounds (Iso) have at least one NCO group (=isocyanate group). A distinction may be made between the monoisocyanates (z=1) and the di- and polyisocyanates (z=≥2). The NCO groups may react, for example, with alcohols to give urethanes or with amines to give urea derivatives. The isocyanate-containing compounds of the invention may be described by the general formula (VI)

R^xN═C═O)_z  (VI)

where

• • R^x is a carbon-containing group, preferably at least one aromatic or aliphatic group or mixtures thereof, more preferably an optionally substituted straight-chain or branched C1- to C20-alkyl group, an optionally substituted straight-chain or branched C2- to C20-alkenyl group or an optionally substituted straight-chain or branched C2- to C20-alkynyl group, an optionally substituted C4- to C14-cycloalkyl group or an optionally substituted C4- to C14-aryl group, most preferably diphenylmethane, toluene, dicyclohexylmethane, hexane or methyl-3,5,5-trimethylcyclohexyl,
  • z is at least 1, preferably at least 1, 2 or 3, more preferably 1, 2 or 3.

The term “metal-siloxane-silanol(ate)” refers to all metal-siloxane compounds that contain either one or more silanol and/or silanolate groups. In one embodiment of the invention, it is likewise possible that there are exclusively metal-siloxane-silanolates. If no specific differentiation is made between these different configurations, all combinations are included. The metal-siloxane-silanol(ate) compounds (=metal-siloxane-silanol/silanolate compounds) just described are also referred to hereinafter as oligomeric metallosilsesquioxanes, “POMS”, metal silsesquioxanes or metallized silsesquioxanes. The terms are used interchangeably hereinafter.

“Alkoxy” refers to an alkyl group joined via an oxygen atom to the main carbon chain or the main skeleton of the compound.

Unless stated otherwise, N especially denotes nitrogen. In addition, O especially denotes oxygen, unless stated otherwise. S especially denotes sulfur, unless stated otherwise. P especially denotes phosphorus, unless stated otherwise. C especially denotes carbon, unless stated otherwise. H especially denotes hydrogen, unless stated otherwise. Si especially denotes silicon, unless stated otherwise.

“Optionally substituted” means that hydrogen atoms in the corresponding group or in the corresponding radical may be replaced by substituents. Substituents may especially be selected from the group consisting of C1- to C4-alkyl, methyl, ethyl, propyl, butyl, phenyl, benzyl, halogen, fluorine, chlorine, bromine, iodine, hydroxy, amino, alkylamino, dialkylamino, C1- to C4-alkoxy, phenoxy, benzyloxy, cyano, nitro, and thio. If a group is referred to as optionally substituted, it is possible for 0 to 50, especially 0 to 20, hydrogen atoms of the group to be replaced by substituents. If a group is substituted, at least one hydrogen atom is replaced by a substituent.

The term “alkyl group” is to be understood as meaning a saturated hydrocarbon chain. Alkyl groups especially have the general formula —C_nH_2n+1. The term “C1- to C16-alkyl group” especially denotes a saturated hydrocarbyl chain having 1 to 16 carbon atoms in the chain. Examples of C1- to C16-alkyl groups are methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec butyl, tert-butyl, n-pentyl and ethylhexyl. Correspondingly, a “C1- to C8-alkyl group” especially denotes a saturated hydrocarbyl chain having 1 to 8 carbon atoms in the chain. Alkyl groups may especially also be substituted even if this is not stated specifically.

“Straight-chain alkyl groups” denote alkyl groups containing no branches. Examples of straight-chain alkyl groups are methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl.

“Branched alkyl groups” denote alkyl groups that are not straight-chain, i.e. in which the hydrocarbyl chain especially has a fork. Examples of branched alkyl groups are isopropyl, isobutyl, sec-butyl, tert-butyl, sec-pentyl, 3-pentyl, 2-methylbutyl, isopentyl, 3-methylbut-2-yl, 2-methylbut-2-yl, neopentyl, ethylhexyl, and 2-ethylhexyl.

“Alkenyl groups” describe hydrocarbon chains containing at least one double bond along the chain. For example an alkenyl group having a double bond in particular has the general formula —C_nH_2n−1. However, alkenyl groups may also have more than one double bond. The term “C2-to C16-alkenyl group” especially denotes a hydrocarbyl chain having 2 to 16 carbon atoms in the chain. The number of hydrogen atoms varies according to the number of double bonds in the alkenyl group. Examples of alkenyl groups are vinyl-, allyl-, 2-butenyl- and 2-hexenyl-.

“Straight-chain alkenyl groups” denote alkenyl groups containing no branches. Examples of straight-chain alkenyl groups are vinyl, allyl, n-2-butenyl and n-2-hexenyl.

“Branched alkenyl groups” denote alkenyl groups that are not straight-chain, i.e. in which the hydrocarbyl chain especially has a fork. Examples of branched alkenyl groups are 2-methyl-2-propenyl, 2-methyl-2-butenyl and 2-ethyl-2-pentenyl.

“Aryl groups” denote monocyclic (for example phenyl), bicyclic (for example indenyl, naphthalenyl, tetrahydronapthyl or tetrahydroindenyl) and tricyclic (for example fluorenyl, tetrahydrofluorenyl, anthracenyl or tetrahydroanthracenyl) ring systems in which the monocyclic ring system or at least one of the rings in a bicyclic or tricyclic ring system is aromatic. More particularly, a C4- to C14-aryl group denotes an aryl group having 4 to 14 carbon atoms. Aryl groups may especially also be substituted even if this is not stated specifically.

In one embodiment of the invention, a system according to the invention, especially a two-component (2K) system, comprises at least one metal-siloxane-silanol(ate) compound, where the metal-siloxane-silanol(ate) compound, is present with a proportion by weight in the range from 0.001% to 5%, preferably in the range from 0.002% to 1%, more preferably in the range from 0.003% to 0.5%, based in each case on the total weight of the reaction mixture. The two-component (2K) systems according to the invention contain metal-siloxane-silanol(ate) compounds in molar concentrations in the range from 0.00001 to 0.06 mol/kg, preferably in the range from 0.00002 to 0.01 mol/kg, more preferably in the range from 0.00003 to 0.06 mol/kg, based in each case on the total weight of the reaction mixture.

According to the invention, “reaction mixture” is understood to mean the overall composition of a system, especially of a two-component (2K) system, i.e. the sum total of components A and B, and also gel catalyst and optionally further catalysts, auxiliaries and constituents. The result of a reaction mixture on completion of reaction is a polyurethane.

In one embodiment of the present invention, the metal-siloxane-silanol(ate) compound may take the form of a monomer, oligomer and/or polymer for production of polyurethanes, the transition from oligomers to polymers being fluid according to the general definition.

The metal(s) is/are preferably present terminally and/or within the chain in the oligomeric and/or polymeric metal-siloxane-silanol(ate) compound.

In the use according to the invention for production of polyurethanes, preferably of unfoamed polyurethanes, flexible foams or rigid foams and/or in the two-component (2K) system according to the invention, the catenated metal-siloxane-silanol(ate) compound is linear, branched and/or a cage.

In a preferred use according to the invention for production of polyurethanes, preferably of unfoamed polyurethanes, flexible foams or rigid foams and/or in the two-component (2K) system according to the invention, the catenated metal-siloxane-silanol(ate) compound has a cage structure.

A “cage” or an oligomeric or polymeric “cage structure” for the purposes of the present invention is a three-dimensional arrangement of the catenated metal-siloxane-silanol(ate) compound, wherein individual atoms in the chain form the vertices of a multifaceted base structure of the compound. In this case, the mutually linked atoms form at least two surfaces, giving rise to a common intersection. In one embodiment of the invention, for example, a cubic base structure of the compound is formed. A one-cage structure or else a cage structure in singular form, i.e. a compound that has an isolated cage, is the structure (IVc). Compounds having multiple cages within the compound may be described by the compounds (I) and (Ia) to (Id). According to the invention, a cage may be “open” or else “closed”, depending on whether all vertices are bonded, joined or coordinated so as to form a closed cage structure. One example of a closed cage is the structures (II), (IV), (IVb), (IVc).

According to the invention, the term “-nuclear” gives the nuclearity of a compound, how many metal atoms are present therein. A mononuclear compound has one metal atom, whereas a dinuclear compound has two metal atoms within a compound. The metals may be bonded directly to one another or linked via their substituents. One example of a mononuclear compound according to the invention is, for example, the structures (IV), (IVb), (IVc), (Ia), (Ib) or (Ic); a dinuclear compound is represented by structure (Id).

A mononuclear one-cage structure is represented by the metal-siloxane-silanol(ate) compounds (IV), (IVb) and (IVc). Mononuclear two-cage structures are, for example, the structures (Ia), (Ib) or (Ic).

The metal-siloxane-silanol(ate) compound in the use according to the invention for selective catalysis of the gel reaction for the production of polyurethanes, preferably of unfoamed polyurethanes, flexible foams or rigid foams and/or in the two-component (2K) system according to the invention, preferably comprises an oligomeric metal silsesquioxane.

More particularly, the metal-siloxane-silanol(ate) compound in the use according to the invention for selective catalysis of the gel reaction for the production of polyurethanes, preferably of unfoamed polyurethanes, flexible foams or rigid foams and/or in the two-component (2K) system according to the invention, comprises a polyhedral metal silsesquioxane.

In one embodiment, the metal-siloxane-silanol(ate) compound in the use according to the invention for selective catalysis of the gel reaction for the production of polyurethanes, preferably of unfoamed polyurethanes, flexible foams or rigid foams and/or in the two-component (2K) system according to the invention has the general formula R*_qSi_rO_sM_t where each R* is independently selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl, optionally substituted C5- to C10-aryl, —OH and —O—(C1- to C10-alkyl), each M is independently selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,

q is an integer from 4 to 19,
r is an integer from 4 to 10,
s is an integer from 8 to 30, and
t is an integer from 1 to 8.

In a further embodiment, the metal-siloxane-silanol(ate) compound in the use according to the invention for selective catalysis of the gel reaction for the production of polyurethanes, preferably of unfoamed polyurethanes, flexible foams or rigid foams and/or in the two-component (2K) system according to the invention has the general formula R^#₄Si₄O₁₁Y₂Q₂X₄Z₃ where each X is independently selected from the group consisting of Si, M¹, -M³L¹_Δ, M³, or —Si(R⁶)—O-M³L¹_Δ, where M¹ and M³ are independently selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and

where L¹ is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L¹ is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and where R⁸ is selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C5- to C10-aryl;
each Z is independently selected from the group consisting of L², R⁵, R⁶ and R⁷, where L² is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L² is selected from the group consisting of —OH, —O— methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl;
each R^#, R⁵, R⁶ and R⁷ is independently selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C5- to C10-aryl; each Y is independently —O-M²-L³_Δ, or two Y are associated and together are —O-M²(L³_Δ)-O— or —O—, where L³ is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L³ is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and each M² is independently selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,
each Q is independently H, M⁴L⁴_Δ, —SiR⁸, -M³L¹_Δ, a single bond joined to M³ of X or a single bond joined to the Si atom of the —Si(R⁸)—O-M³L¹_Δ radical, where M³, R⁸ and L¹ are as defined for X, where M⁴ is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and where L⁴ is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L⁴ is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl,
with the proviso that at least one X is M³, -M³L¹_Δ or —Si(R⁸)—O-M³L¹_Δ.

It is known to the person skilled in the art that the number (A) of possible ligands for L¹_Δ, L²_Δ, L³_Δ, L⁴_Δ results directly from the number of free valences of the metal atom used, where the valence number describes the valency of the metal.

In a further embodiment, the metal-siloxane-silanol(ate) compound in the use according to the invention for selective catalysis of the gel reaction for the production of polyurethanes, preferably of unfoamed polyurethanes, flexible foams or rigid foams and/or in the two-component (2K) system according to the invention has the general formula (Y_0.25R^#SiO_1.25)₄(Z_0.75Y_0.25XO)₄(OQ)₂ where each X is independently selected from the group consisting of Si, M¹, -M³L¹_Δ, M³, or —Si(R⁸)—O-M³L¹_Δ, where M¹ and M³ are independently selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and where L¹ is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1-to C8-alkyl) or —O—(C1- to C6-alkyl), or where L¹ is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and where R⁸ is selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C6-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C6- to C10-aryl;

each Z is independently selected from the group consisting of L², R⁵, R⁶ and R⁷, where L² is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L² is selected from the group consisting of —OH, —O— methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl;
each R^#, R⁵, R⁶ and R⁷ is independently selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C6-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C6- to C10-aryl;
each Y is independently —O-M²-L³_Δ, or two Y are associated and together are —O-M²(L³_Δ)-O— or —O—, where L³ is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L³ is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and each M² is independently selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,
each Q is independently H, M⁴L⁴_Δ, —SiR⁸, -M³L¹_Δ, a single bond joined to M³ of X or a single bond joined to the Si atom of the —Si(R⁸)—O-M³L¹_Δ radical, where M³, R⁸ and L¹ are as defined for X, where M⁴ is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and where L⁴ is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L⁴ is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl,
with the proviso that at least one X is M³, -M³L¹_Δ or —Si(R⁸)—O-M³L¹_Δ.

The metal-siloxane-silanol(ate) compound in the use according to the invention for selective catalysis of the gel reaction for the production of polyurethanes, preferably of unfoamed polyurethanes, flexible foams or rigid foams and/or in the two-component (2K) system according to the invention preferably has the general formula Si₄O₉R¹R²R³R⁴X¹X²X³X⁴OQ¹OQ²Y¹Y²Z¹Z²Z³ where X¹, X² and X³ are independently selected from Si and M¹, where M¹ is selected from the group consisting of s- and p-block metals, B- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,

Z¹, Z² and Z³ are independently selected from the group consisting of L², R⁵, R⁶ and R⁷, where L² is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1-to C8-alkyl) or —O—(C1- to C6-alkyl), or where L2 is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl;
R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are independently selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C5- to C10-aryl;
Y¹ and Y² are independently —O-M²-L³_Δ, or Y¹ and Y² are associated and together are —O-M²(L³_Δ)-O— or —O—, where L³ is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L³ is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and M² is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and
X⁴ is -M³L¹_Δ or M³ and Q¹ and Q² are each H or a single bond joined to M³, where L¹ is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L¹ is selected from the group consisting of —OH, —O-methyl, —O— ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and where M³ is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,
or
X⁴ is -M³L¹_Δ and Q² is H or a single bond joined to M³ and Q¹ is H, M⁴L⁴_Δ or —SiR⁸, where M⁴ is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 2, 3, 4, 5 and 8 and metals from main group 1, 2, 3, 4 and 5, especially from the group consisting of Zn, Sc, Ti, Zr, Hf, V, Pt, Ga, Sn and Bi, where L⁴ is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L⁴ is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and where R⁸ is selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C5- to C10-aryl,
or
X⁴, Q¹ and Q² are independently -M³L¹_Δ,
or
X⁴ is —Si(R⁸)—O-M³L¹, Q² is a single bond joined to the silicon atom of X⁴ and Q¹ is -M⁴L⁴_Δ,
or
X⁴ is —Si(R⁸)—O-M³L¹_Δ, Q² is a single bond joined to the silicon atom of X⁴ and Q¹ is a single bond joined to the M³ atom of X⁴.

In a further embodiment, the metal silsesquioxane in the use according to the invention for selective catalysis of the gel reaction for the production of polyurethanes, preferably of unfoamed polyurethanes, flexible foams or rigid foams and/or in the two-component (2K) system according to the invention, has the general formula

(X⁴)(Z¹Y¹X²O)(Z²X¹O₂)(Z³X³O₂)(R¹Y²SiO)(R³SiO)(R⁴SiO₂)(R²SiO₂)(Q¹)(Q²) where X¹, X² and X³ are independently selected from Si and M¹, where M¹ is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,
Z¹, Z² and Z³ are independently selected from the group consisting of L², R⁵, R⁶ and R⁷, where L² is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1-to C8-alkyl) or —O—(C1- to C6-alkyl), or where L² is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl;
R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are independently selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C6-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C6- to C10-aryl;
Y¹ and Y² are independently —O-M²-L³_Δ, or Y¹ and Y² are associated and together are —O-M²(L³_Δ)-O— or —O—, where L³ is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L³ is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and M² is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and
X⁴ is -M³L¹_Δ or M³ and Q¹ and Q² are each H or a single bond joined to M³, where L¹ is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L¹ is selected from the group consisting of —OH, —O-methyl, —O— ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and where M³ is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,
or
X⁴ is -M³L¹_Δ and Q² is H or a single bond joined to M³ and Q¹ is H, M⁴L⁴_Δ or —SiR⁸, where M4 is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 2, 3, 4, 5 and 8 and metals from main group 1, 2, 3, 4 and 5, especially from the group consisting of Zn, Sc, Ti, Zr, Hf, V, Pt, Ga, Sn and Bi, where L⁴ is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L⁴ is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and where R⁸ is selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C6-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C6- to C10-aryl,
or
X⁴, Q¹ and Q² are independently -M³L¹_Δ,
or
X⁴ is —Si(R⁸)—O-M³L¹_Δ, Q² is a single bond joined to the silicon atom of X⁴ and Q¹ is -M⁴L⁴_Δ,
or
X⁴ is —Si(R⁸)—O-M³L¹_Δ, Q² is a single bond joined to the silicon atom of X⁴ and Q¹ is a single bond joined to the M³ atom of X⁴.

In a further aspect of the invention, the selective catalyst used in accordance with the invention for the gel reaction in the production of polyurethanes, especially of unfoamed polyurethanes, flexible foams or rigid foams and/or in the two-component (2K) system according to the invention based on a metal-siloxane-silanol(ate) compound, may be described by the structure (I)

where
X¹, X² and X³ are independently selected from Si and M¹, where M¹ is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,
Z¹, Z² and Z³ are independently selected from the group consisting of L², R⁵, R⁶ and R⁷, where L² is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1-to C8-alkyl) or —O—(C1- to C6-alkyl), or where L² is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl;
R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are independently selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C5- to C10-aryl;
Y¹ and Y² are independently —O-M²-L³_Δ, or Y¹ and Y² are associated and together are —O-M²(L³_Δ)-O— or —O—, where L³ is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L³ is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and where M² is selected from the group consisting of s- and p-block metals, B- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, Bi,
and X⁴ is -M³L¹_Δ or M³ and Q¹ and Q² are each H or a single bond joined to M³, where L¹ is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L¹ is selected from the group consisting of —OH, —O— methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and where M³ is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, Bi,
or
X⁴ is -M³L¹ and Q² is H or a single bond joined to M³ and Q¹ is H, M⁴L⁴_Δ or —SiR⁸, where M⁴ is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, where L⁴ is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L⁴ is selected from the group consisting of —OH, —O— methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and where R⁸ is selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C6-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C6- to C10-aryl,
or
X⁴, Q¹ and Q² are independently -M³L¹_Δ,
or
X⁴ is —Si(R⁸)—O-M³L¹_Δ, Q² is a single bond joined to the silicon atom of X⁴ and Q¹ is -M⁴L⁴_Δ,
or
X⁴ is —Si(R⁸)—O-M³L¹_Δ, Q² is a single bond joined to the silicon atom of X⁴ and Q¹ is a single bond joined to the M³ atom of X4.

In a further preferred embodiment, the metal-siloxane-silanol(ate) compound in the use according to the invention for selective catalysis of the gel reaction for the production of polyurethanes, preferably of unfoamed polyurethanes, flexible foams or rigid foams and/or in the two-component (2K) system according to the invention, has the general formula (I) where X¹, X² and X³ are independently Si,

X⁴ is -M³L¹_Δ and Q¹ and Q² are each a single bond joined to M³, where L¹ is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1-to C6-alkyl), or where L¹ is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O— propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and where M³ is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,
Z¹, Z² and Z³ are each independently selected from optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C5- to C10 aryl,
R¹, R² and R³ are each independently selected from optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C5- to C10 aryl,
Y¹ and Y² are associated and together form —O—.

In one embodiment, the metal-siloxane-silanol(ate) compound of formula (I) in the inventive use for selective catalysis of the gel reaction for the production of polyurethanes, preferably of unfoamed polyurethanes, flexible foams or rigid foams and/or in the two-component (2K) system according to the invention, depending on the equivalents of metal present, may be in mononuclear form as a monomer or in polynuclear form as a dimer (dinuclear), trimer (trinuclear), multimer (multinuclear) and/or mixtures thereof, such that, for example, structures of the formulae (Ia) to (Id) are possible.

Further polynuclear metal-siloxane-silanol(ate) compounds usable in accordance with the invention are the structures (Ia), (Ib), (Ic) and (Id)

where
M is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and each R (R¹ to R⁴) is independently selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl, optionally substituted C5- to C10-aryl, —OH and —O—(C1- to C10-alkyl). The tetravalent metal M here is a shared part of multiple cages. It is known here to the person skilled in the art that the number of bonds to the metal M depends on the valency of the metal M. The structural formulae (Ia) to (Ic) should be adjusted correspondingly if necessary. In one embodiment of the use according to the invention, in the production of polyurethanes, preferably of unfoamed polyurethanes or flexible foams, a mixture of the metal-siloxane-silanol(ate) compounds of formulae (I), (Ia), (Ib) and (Ic) is used.

In addition, the polynuclear metal-siloxane-silanol(ate) compound of formula (Id) in the use according to the invention for selective catalysis of the gel reaction for the production of polyurethanes, preferably of unfoamed polyurethanes, flexible foams or rigid foams and/or in the two-component (2K) system according to the invention, can have hexacoordinated metal centres, such that structures of formula (Id) are possible,

where each M is independently selected from the group consisting of s- and p-block metals, B- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and each R is independently selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl, optionally substituted C5- to C10-aryl, —OH and —O—(C1- to C10-alkyl).

In the context of the invention, the term “one-cage” refers to the isolated cage structure, i.e. present in singular form, of the gel catalyst according to the invention based on a metal-siloxane-silanol(ate) compound. Cage structures of the gel catalyst according to the invention that are based on a metal-siloxane-silanol(ate) compound may be encompassed by the structure (IV) and likewise by the structures (I) and (II)

where
X⁴ is -M³L¹_Δ where L¹ is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L¹ is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O— isobutyl, and where M³ is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,
Z¹, Z² and Z³ are independently selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C5- to C10-aryl;
R¹, R², R³ and R⁴ are each independently selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C5- to C10-aryl.

The use according to the invention further relates to metal-siloxane-silanol(ate) compounds of the general structural formula (II) that are used for selective catalysis of the gel reaction for the production of polyurethanes, preferably of unfoamed polyurethanes, flexible foams or rigid foams and/or in the two-component (2K) system according to the invention, where X⁴ is -M³L¹_Δ where L¹ is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L¹ is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and where M³ is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,

Z¹, Z² and Z³ are independently selected from the group consisting of L², R⁵, R⁶ and R⁷, where L² is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1-to C8-alkyl) or —O—(C1- to C6-alkyl), or where L² is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and
R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are independently selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C5- to C10-aryl.

In a particularly advantageous embodiment, the polyurethanes, preferably unfoamed polyurethanes or flexible or rigid foams, may have been produced by selective catalysis of the gel reaction with heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) as one metal-siloxane-silanol(ate) compound. The abbreviation “TiPOSS” here represents the monovalent titanium-metallized silsesquioxane of the structural formula (IV) and can be used in an equivalent manner to “heptaisobutyl POSS-titanium(IV) ethoxide” for the purposes of the invention.

In the use according to the invention, the metal-siloxane-silanol(ate) compound in the production of polyurethanes, preferably of unfoamed polyurethanes, flexible foams or rigid foams, may be a mixture comprising structures (I), (Ia), (Ib), (Ic), (Id), (II), (IV), (IVb), (IVc).

In a preferred embodiment, the metal in the metal-siloxane-silanol(ate) compound is a titanium.

In a further-preferred embodiment, in the production of polyurethanes, preferably of unfoamed polyurethanes, flexible foams or rigid foams and/or in the two-component (2K) system according to the invention by use of a metal-siloxane-silanol(ate) compound, a catalyst may additionally be present that is selected from the group consisting of metal-siloxane-silanol(ate) compounds, such as heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS), tetraalkyl titanates, such as tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-sec-butyl titanate, tetraoctyl titanate, tetra(2-ethylhexyl) titanate, dialkyl titanates ((RO)₂TiO₂ in which R is, for example, isopropyl, n-butyl, isobutyl), such as isopropyl n-butyl titanate; titanium acetylacetonate chelates, such as diisopropoxybis(acetylacetonate) titanate, diisopropoxybis(ethylacetylacetonate) titanate, di-n-butylbis(acetylacetonate) titanate, di-n-butyl-bis(ethylacetoacetat) titanate, triisopropoxidebis(acetylacetonate) titanate, zirconium tetraalkoxides, such as zirconium tetraethoxide, zirconium tetrabutoxide, zirconium tetrabutyrate, zirconium tetrapropoxide, zirconium carboxylate, such as zirconium diacetate; zirconium acetylacetonate chelates, such as zirconium tetra(acetylacetonate), tributoxyzirconium acetylacetonate, dibutoxyzirconium (bisacetylacetonate), aluminium trisalkoxides, such as aluminium triisopropoxide, aluminium trisbutoxide; aluminium acetylacetonate chelates, such as aluminium tris(acetylacetonate) and aluminium tris(ethylacetylacetonate), organotin compounds such as dibutyltin dilaurate (DBTL), dibutyltin maleate, dibutyltin diacetate, tin(II) 2-ethylhexanoate (tin octoate), tin naphthenate, dimethyltin dineodecanoate, dioctyltin dineodecanoate, dimethyltin dioleate, dioctyltin dilaurate, dimethyl mercaptide, dibutyl mercaptide, dioctyl mercaptide, dibutyltin dithioglycolate, dioctyltin glycolate, dimethyltin glycolate, a solution of dibutyltin oxide, reaction products of zinc salts and organic carboxylic acids (carboxylates), such as zinc(II) 2-ethylhexanoate or zinc(II) neodecanoate, mixtures of bismuth carboxylates and zinc carboxylates, reaction products of bismuth salts and organic carboxylic acids, such as bismuth(III) tris(2-ethylhexanoate) and bismuth(III) tris(neodecanoate) and bismuth complexes, organolead compounds such as lead octoxide, organovanadium compounds, amine compounds such as butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylendiamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole and 1,8-diazabicylo(5.4.0)undecene-7 (DBU), salts of these amines with carboxylic acids or other acids or mixtures thereof, preferably metal-siloxane-silanol(ate) compounds, especially heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), dibutyltin dilaurate (DBTL), tin(II) 2-ethylhexanoate (tin octoate), zinc(II) 2-ethylhexanoate, zinc(II) neodecanoate, bismuth(III) tris(2-ethylhexanoate), bismuth(III) tris(neodecanoate) or mixtures thereof, more preferably metal-siloxane-silanol(ate) compounds, especially heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) or heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS), dibutyltin dilaurate (DBTL) or mixtures thereof, most preferably heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS), dibutyltin dilaurate (DBTL) or mixtures thereof.

In one embodiment of an inventive use of metal-siloxane-silanol(ate) compounds for selective catalysis of the gel reaction in the production of polyurethanes, preferably of unfoamed polyurethanes, flexible foams or rigid foams and/or of a two-component (2K) system according to the invention, at least one isocyanate reactive compound (component A) is selected from the group consisting of compounds having NH, OH or SH functions, and one or more compounds having at least one isocyanate group (component B) is selected from the group consisting of isocyanates (Iso) and at least one mononuclear metal-siloxane-silanol(ate) compound.

In a preferred embodiment of an inventive use of metal-siloxane-silanol(ate) compounds for selective catalysis of the gel reaction in the production of polyurethanes, preferably of unfoamed polyurethanes, flexible foams or rigid foams and/or of a two-component (2K) system according to the invention, at least one hydroxy-functionalized polymer (component A) selected from the group consisting of polyoxyalkylene polyols, styrene-acrylonitrile, grafted polyether polyols, polyester polyols, polycarbonate polyols, polyhydroxy-functional fats and/or oils, polyhydrocarbon polyols or mixtures thereof, and one or more compounds having at least one isocyanate group (component B) selected from the group of polymeric methylene diphenyl isocyanate (polyMDI or PMDI), 4,4′-methylene diphenyl isocyanate (4,4′-MDI), 2,4-methylene diphenyl isocyanate, (2,4-MDI), 2,2′-methylene diphenyl isocyanate (2,2-MDI), NCO prepolymers based on the aforementioned MDI isomers, isophorone diisocyanate (IPDI), tolylene 2,4- and/or 2,6-diisocyanate (TDI), hexamethylene 1,6-diisocyanate (HDI) or the trimer thereof (HDI trimer) or mixtures thereof, catalysed by at least one mononuclear one-cage metal-siloxane-silanol(ate) compound, is used.

In a further-preferred embodiment of an inventive use of metal-siloxane-silanol(ate) compounds for selective catalysis of the gel reaction in the production of polyurethanes, preferably of unfoamed polyurethanes, flexible foams or rigid foams and/or a two-component (2K) system according to the invention, at least one hydroxy-functionalized polymer (component A) selected from the group of polyoxyalkylene polyols, polyester polyols, polycarbonate polyols, polyhydroxy-functional fats and/or oils, or mixtures thereof, and one or more compounds having at least one isocyanate group (component B), selected from the group of polymeric methylene diphenyl isocyanate (polyMDI or PMDI), 4,4′-methylene diphenyl isocyanate (4,4′-MDI), isophorone diisocyanate (IPDI), or mixtures thereof, catalysed by at least one mononuclear titanium-siloxane-silanol(ate) compound, especially by heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), is used.

In a very particularly preferred embodiment of a two-component (2K) system according to the invention, a gel reaction catalysed by heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) of a component A selected from the group consisting of polyalkylene diols, polyester polyols, or mixtures thereof, with a component B selected from the group consisting of polymeric methylene diphenyl isocyanate (polyMDI), 4,4′-methylene diphenyl isocyanate (4,4′-MDI), isophorone diisocyanate (IPDI) or mixtures thereof is employed.

In the most preferred embodiment, all the above uses according to the invention and/or two-component (2K) systems include heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) in the selective catalysis of the gel reaction in the production of polyurethanes, preferably the unfoamed polyurethanes, flexible foams or rigid foams.

In an alternative embodiment, all the above uses according to the invention and/or two-component (2K) systems include, rather than heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), heptaisobutyl POSS tin(IV) ethoxide(SnPOSS) or a mixture thereof. In what is, however, the most preferred embodiment, solely heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) is present in the uses according to the invention and/or in the two-component (2K) system.

The inventive two-component (2K) systems and uses of all the above combinations, in a preferred embodiment, include a further catalyst selected from metal-siloxane-silanol(ate) compounds, especially heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) or heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS), dibutyltin dilaurate (DBTL) or mixtures thereof.

In an alternative preferred embodiment, all the above systems of the invention, especially two-component (2K) systems, combinations or uses, include dibutyltin dilaurate (DBTL) or heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS) as second catalyst.

In a further-preferred embodiment, the use according to the invention, as well as the metal-siloxane-silanol(ate) compounds for selective catalysis of the gel reaction in the production of polyurethanes, preferably of unfoamed polyurethanes, flexible foams or rigid foams and/or the two-component (2K) system according to the invention, also comprises additives such as one or more fillers selected from the group of inorganic and organic fillers, especially natural, ground or precipitated calcium carbonates optionally coated with fatty acids, especially stearic acid, barite (heavy spar), talcs, quartz flours, quartz sand, dolomites, wollastonites, kaolins, calcined kaolins, mica (potassium aluminium silicate), molecular sieves, aluminium oxides, aluminium hydroxides, magnesium hydroxide, silicas including finely divided silicas from pyrolysis processes, industrially produced carbon blacks, graphite, metal powders such as aluminium, copper, iron, silver or steel, PVC powders or hollow beads, one or more adhesion promoters from the group of the silanes, especially aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-N′-[3-(trimethoxysilyl)propyl]ethylenediamine and analogues thereof having methoxy or isopropoxy in place of the methoxy groups on the silicon, aminosilanes having secondary amino groups, such as, in particular, N-phenyl-, N-cyclohexyl- and N-alkylaminosilanes, and also mercaptosilanes, epoxysilanes, (meth)acryloylsilanes, anhydridosilanes, carbamatosilanes, alkylsilanes and iminosilanes, and oligomeric forms of these silanes, and adducts of primary aminosilanes with epoxysilanes or (meth)acryloylsilanes or anhydridosilanes. Especially suitable are 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-N′-[3-(trimethoxysilyl)propyl]ethylenediamine, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane and the corresponding silanes having ethoxy groups in places of the methoxy groups, and oligomeric forms of these silanes, one or more moisture scavengers from the group of silanes, especially tetraethoxysilane, vinyltrimethoxy- or vinyltriethoxysilane or organoalkoxysilanes having a functional group in the a position to the silane group, especially N-(methyldimethoxysilylmethyl)-O-methyl carbamate, (methacryloyloxymethyl)silanes, methoxymethylsilanes, orthoformic esters, and calcium oxide or molecular sieves, one or more plasticizers from the group of carboxylic esters, such as phthalates, especially diisononyl cyclohexane-1,2-dicarboxylate, dioctyl phthalate, diisononyl phthalate or diisodecyl phthalate, adipates, especially dioctyl adipate, azelates, sebacates, polyols, especially polyoxyalkylene polyols or polyester polyols, glycol ethers, glycol esters, citrates, especially triethyl citrate, organic phosphoric and sulfonic esters, polybutenes, or fatty acid methyl or ethyl esters derived from natural fats or oils, one or more UV stabilizers from the group of organic (benzophenones, benzotriazoles, oxalanilides, phenyltriazines) and inorganic (titanium dioxide, iron oxide, zinc oxide) UV absorbers, and antioxidants from the group of sterically hindered phenols, amines, phosphites and phosphonites, one or more thixotropic agents from the group of sheet silicates such as bentonites, derivatives of castor oil, hydrogenated castor oil, polyamides, polyurethanes, urea compounds, fumed silicas, cellulose ethers or hydrophobically modified polyoxyethylenes, one or more wetting agents selected from the group of nonionic, anionic and cationic surfactants, or combinations of these.

In a further embodiment, the inventive two-component (2K) system, especially for unfoamed polyurethanes, additionally includes a water scavenger, preferably a molecular sieve, UOP-L powder, vinylalkoxysilane or mixtures thereof, more preferably vinyltrimethoxysilane (VTMO), UOP-L powder or mixtures thereof, most preferably UOP-L powder.

In one embodiment, the system, especially the two-component (2K) system, in a use according to the invention comprises a water scavenger. The proportion here of the water scavenger is not more than 5.0% by weight, preferably not more than 3.5% by weight, more preferably not more than 2.5% by weight, even more preferably not more than 1.5% by weight, exceptionally preferably not more than 1% by weight, based on the overall composition of the system.

In a preferred embodiment, the system, especially the two-component (2K) system, in the overall composition of a use according to the invention comprises, as water scavenger, at least one molecular sieve, especially UOP-L powder, in a proportion of not more than 5.0% by weight, preferably not more than 3.5% by weight, more preferably not more than 2.5% by weight, most preferably not more than 2.0% by weight, or at least one monooxazolidine, especially Incozol®, in a proportion of not more than 4% by weight, preferably not more than 2.5% by weight, more preferably not more than 2% by weight, most preferably not more than 1.5% by weight, or at least one organoalkoxysilane, especially vinyltrimethoxysilane, or alkoxysilanes, especially tetraethoxysilane, in a proportion of not more than 3% by weight, preferably not more than 2.0% by weight, more preferably not more than 1.5% by weight, most preferably not more than 1.25% by weight, or p-tosyl isocyanate in a proportion of not more than 4% by weight, preferably not more than 3% by weight, more preferably not more than 2.5% by weight, most preferably not more than 2% by weight, or calcium oxide in a proportion of not more than 3% by weight, preferably not more than 2% by weight, more preferably not more than 1.5% by weight, most preferably not more than 1.25% by weight, or at least one orthoformic ester, especially triethyl orthoformate (TEOF), in a proportion of not more than 3% by weight, preferably not more than 2% by weight, more preferably not more than 1.5% by weight, most preferably not more than 1.25% by weight, or mixtures thereof.

In a particularly preferred embodiment, the system, especially the two-component (2K) system, especially for unfoamed polyurethanes in a use according to the invention, does not include any water scavenger.

In a further, very particularly preferred embodiment, the density of the unfoamed polyurethanes is ≥1000 kg/m³ when the total water content is ≤0.6%, preferably 0.6%, in the production thereof.

A preferred embodiment of a process according to the invention for production of unfoamed polyurethanes comprises the following steps:

• • (i) providing a component A comprising at least one hydroxy-functionalized polymer according to any of the above definitions,
  • (ii) providing a component B comprising at least one compound having one or more isocyanate groups according to any of the above definitions,
  • (iii) adding at least one metal-siloxane-silanol(ate) compound according to any of the above definitions to component A or B,
  • (iv) optionally adding a water scavenger, preferably a molecular sieve or UOP-L powder or mixtures thereof, more preferably UOP-L powder, to at least one of components A and/or B,
  • (v) optionally adding at least one additive according to any of the above definitions to at least one of components A and/or B,
  • (vi) combining component A with component B.

A particularly preferred embodiment of a process according to the invention for production of unfoamed polyurethanes comprises the following steps:

• • (i) providing a component A comprising at least one hydroxy-functionalized polymer selected from the group consisting of difunctional or higher-functionality polyoxyalkylene polyols, polyester polyols, polycarbonate polyols, polyhydroxy-functional fats and/or oils, or mixtures thereof, preferably with number-average molar masses (Mn) of 250-35 000 g/mol, more preferably of about 350 g/mol or about 19 000 g/mol, or mixtures thereof, and at least one metal-siloxane-silanol(ate) compound, especially heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS) or mixtures thereof,
  • (ii) providing a component B comprising one or more isocyanates (Iso) selected from the group consisting of polymeric methylene diphenyl isocyanate (polyMDI), 4,4′-methylene diphenyl isocyanate (4,4′-MDI), isophorone diisocyanate (IPDI) or mixtures thereof,
  • (iii) optionally adding a water scavenger, preferably a molecular sieve or UOP-L powder or mixtures thereof, more preferably UOP-L powder, to at least one of components A and/or B,
  • (iv) optionally adding at least one additive according to any of the above definitions to at least one components A and/or B,
  • (v) combining component A with component B.

An alternative preferred embodiment of a process according to the invention for production of flexible or rigid foams comprises the following steps:

• • (i) providing a component A comprising at least one hydroxy-functionalized polymer according to any of the preceding embodiments,
  • (ii) providing a component B comprising at least one compound having one or more isocyanate groups according to any of the preceding embodiments,
  • (iii) adding at least one metal-siloxane-silanol(ate) compound according to any of the preceding claims to component A and/or B,
  • (iv) optionally adding a water scavenger according to any of the preceding embodiments to at least one of components A and/or B,
  • (v) optionally adding at least one additive according to any of the preceding embodiments to at least one of components A and/or B,
  • (vi) adding a blowing agent to at least one of components A and/or B according to any of the preceding embodiments,
  • (vii) combining component A with component B.

A particularly preferred embodiment of a process according to the invention for production of flexible or rigid foams comprises the following steps:

• • (i) providing a component A comprising at least one hydroxy-functionalized polymer selected from the group consisting of EO-tipped polyether triols, difunctional or higher-functional polyoxyalkylene polyols, polyester polyols, polycarbonate polyols, polyhydroxy-functional fats and/or oils, preferably EO-tipped polyether triols, difunctional or higher-functional polyoxyalkylene polyols, polyester polyols, or mixtures thereof,
  • (ii) providing a component B comprising at least one compound having one or more isocyanate groups, selected from the group consisting of polymeric methylene diphenyl isocyanate (polyMDI), 4,4′-methylene diphenyl isocyanate (4,4′-MDI), isophorone diisocyanate (IPDI) or mixtures thereof,
  • (iii) adding at least one metal-siloxane-silanol(ate) compound, especially heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS) or mixtures thereof, to component A and/or B,
  • (iv) optionally adding a water scavenger, preferably a molecular sieve or UOP-L powder or mixtures thereof, more preferably UOP-L powder, to at least one of components A and/or B,
  • (v) optionally adding at least one additive according to any of the above definitions to at least one of components A and/or B,
  • (vi) adding a blowing agent to at least one of components A and/or B, selected from the group consisting of water, nitrogen, air, carbon dioxide, pentane, hydrofluorocarbons (HFCs) or mixtures thereof, preferably water or mixtures thereof,
  • (vii) combining component A with component B.

A preferred embodiment of a combination for production of unfoamed polyurethanes comprising at least one component A and component B, where component A comprises at least one hydroxy-functionalized polymer according to any of the preceding claims and at least one metal-siloxane-silanol(ate) compound according to any of the preceding claims, and component B comprises at least one compound having one or more isocyanate groups according to any of the preceding claims, characterized in that components A and B are each present separately and in a relative ratio of 2:1 up to 1:2, preferably in a ratio of 1.8:1 to 1:1.8, more preferably in a ratio of 1.5:1 up to 1:1.5, most preferably in a ratio of 1.2:1 up to 1:1.2.

An alternative preferred embodiment of a combination for production of rigid or flexible foams comprising at least one component A and component B, where component A comprises at least one hydroxy-functionalized polymer according to any of the preceding claims and at least one metal-siloxane-silanol(ate) compound according to any of the preceding claims, and component B comprises at least one compound having one or more isocyanate groups according to any of the preceding claims, characterized in that components A and B are each present separately and in a relative ratio of 2:1 up to 1:2, preferably in a ratio of 1.8:1 to 1:1.8, more preferably in a ratio of 1.5:1 up to 1:1.5, most preferably in a ratio of 1.2:1 up to 1:1.2.

The process according to the invention is preferably conducted at temperatures of at least 0° C., more preferably at least 20° C., and preferably at most 150° C., especially at most 80° C.

The process according to the invention can be effected continuously, by means of conventional high-pressure and low-pressure mixing systems having multiple metering sites in parallel or else in series, or batchwise, for example in a conventional reaction tank with stirrer system.

In one embodiment, unfoamed polyurethanes are producible by a process using at least one metal-siloxane-silanol(ate) compound, preferably a mononuclear one-cage structure according to any of structures (IV), (IVb) or (IVc), more preferably a titanium-containing one-cage structure according to one of structures (IV), (IVb) or (IVc), most preferably TiPOSS.

In one embodiment of the unfoamed polyurethanes according to the invention, these are elastomers.

In a further embodiment of the unfoamed polyurethanes according to the invention, these are thermosets.

In an alternative embodiment, foamed polyurethanes, especially flexible or rigid foams, are producible by a process using at least one metal-siloxane-silanol(ate) compound, preferably a mononuclear one-cage structure according to any of structures (IV), (IVb) or (IVc), more preferably a titanium-containing one-cage structure according to one of structures (IV), (IVb) or (IVc), most preferably TiPOSS.

In an advantageous embodiment of the use of at least one metal-siloxane-silanol(ate) compound, preferably a mononuclear one-cage structure according to any of structures (IV), (IVb) or (IVc), more preferably a titanium-containing one-cage structure according to any of structures (IV), (IVb) or (IVc), most preferably TiPOSS, in the production of polyurethanes, these polyurethanes are particularly suitable for use in CASE applications (coatings, adhesives, sealants and elastomers) and/or elastomer materials.

In a further advantageous embodiment of the use of at least one metal-siloxane-silanol(ate) compound, preferably a mononuclear one-cage structure according to any of structures (IV), (IVb) or (IVc), more preferably a titanium-containing one-cage structure according to any of structures (IV), (IVb) or (IVc), most preferably TiPOSS, in the production of flexible foams, these flexible foams are particularly suitable for use in furniture, mattresses, car seats, gasket materials or acoustic materials.

In a further advantageous embodiment of the use of at least one metal-siloxane-silanol(ate) compound, preferably a mononuclear one-cage structure according to any of structures (IV), (IVb) or (IVc), more preferably a titanium-containing one-cage structure according to any of structures (IV), (IVb) or (IVc), most preferably TiPOSS, in the production of rigid foams, these rigid foams are particularly suitable for use in sound insulations, heat insulations and/or cold insulations.

In a further advantageous embodiment of the use of at least one metal-siloxane-silanol(ate) compound, preferably a mononuclear one-cage structure according to any of structures (IV), (IVb) or (IVc), more preferably a titanium-containing one-cage structure according to any of structures (IV), (IVb) or (IVc), most preferably TiPOSS, in the production of rigid foams, these rigid foams are particularly suitable for use in district heating pipes, tanks and pipelines, and for production of all kinds of refrigeration units.

In a further advantageous embodiment of the use of at least one metal-siloxane-silanol(ate) compound, preferably a mononuclear one-cage structure according to any of structures (IV), (IVb) or (IVc), more preferably a titanium-containing one-cage structure according to any of structures (IV), (IVb) or (IVc), most preferably TiPOSS, in the production of rigid foams, these rigid foams are particularly suitable for use in insulation panels for the fields of use of roofs, walls, floors and/or ceilings, in window frame insulations or as assembly foam.

PARTICULARLY PREFERRED EMBODIMENTS OF THE INVENTION

• 1. Use of at least one metal-siloxane-silanol(ate) catalyst for selective catalysis of the gel reaction in a system for the production of polyurethanes.
• 2. Use of at least one metal-siloxane-silanol(ate) compound for the production of unfoamed polyurethanes, especially of elastomers and/or encapsulating compounds.
• 3. Use of at least one metal-siloxane-silanol(ate) compound for production of flexible foams, especially flexible polyurethane foams.
• 4. Use of at least one metal-siloxane-silanol(ate) compound for production of rigid foams, especially rigid polyurethane foams.
• 5. Use according to any of the preceding claims, wherein the system is a two-component (2K) system.
• 6. Use according to Embodiment 5, characterized in that the two-component (2K) system comprises a component A and a component B, where the metal-siloxane-silanol(ate) compound(s) is/are formulated preferably together with component A comprising at least one hydroxy-functionalized polymer or with component B comprising at least one compound having one or more isocyanate groups.
• 7. Use according to Embodiment 2, 5 or 6, wherein the unfoamed polyurethane has a density in the range according to DIN EN ISO 845:2009-10 of 800 to 1950 kg/m³, preferably in the range from 950 to 1750 kg/m³, more preferably in the range from 980 to 1650 kg/m³, most preferably in the range from 990 to 1600 kg/m³.
• 8. Use according to Embodiment 2 or 5 to 7, wherein the unfoamed polyurethane has a Shore 00 hardness according to ASTM D2240-15 in the range of 40-100, preferably in the range from 45 to 95, preferably in the range from 50 to 90, especially preferably in the range from 55 to 85.
• 9. Use according to Embodiment 2, 5 or 6 to 8, wherein the unfoamed polyurethane has a Shore A hardness according to ASTM D2240-15 in the range of 0-100, preferably in the range from 5 to 95, preferably in the range from 10 to 90, especially preferably in the range from 15 to 85.
• 10. Use according to Embodiment 2, 5 or 6 to 9, wherein the unfoamed polyurethane has a Shore D hardness according to ASTM D2240-15 in the range of 0-100, preferably in the range from 5 to 95, preferably in the range from 10 to 90, especially preferably in the range from 15 to 85.
• 11. Use according to Embodiment 3, wherein the flexible foam has a density according to DIN EN ISO 845:2009-10 in the range from 50 to 900 kg/m³, preferably in the range from 100 to 850 kg/m³, more preferably in the range from 200 to 750 kg/m³, most preferably in the range from 200 to 700 kg/m³.
• 12. Use according to Embodiment 3, 5, 6 or 11, wherein the flexible foam has a Shore 00 hardness according to ASTM D2240-15 in the range of 0-100, preferably in the range from 5 to 95, preferably in the range from 15 to 90, especially preferably in the range from 20 to 85.
• 13. Use according to Embodiment 3, 5, 6 or 11 to 12, wherein the flexible foam has a Shore A hardness according to ASTM D2240-15 in the range of 0-100, preferably in the range from 20 to 95, preferably in the range from 20 to 60, especially preferably in the range from 20 to 50.
• 14. Use according to Embodiment 3, 5, 6 or 11 to 13, wherein the flexible foam has a tensile strength according to DIN EN ISO 1798:2008-04 of between 180 and 400 kPa, preferably between 200 and 380 kPa, more preferably between 200 and 350 kPa.
• 15. Use according to Embodiment 4, wherein the rigid foam has a density according to DIN EN ISO 845:2009-10 in the range from 50 to 900 kg/m³, preferably in the range from 150 to 850 kg/m³, more preferably in the range from 200 to 750 kg/m³, most preferably in the range from 200 to 700 kg/m³
• 16. Use according to Embodiment 5 to 6 to 15, wherein the rigid foam has a Shore D hardness according to ASTM D2240-15 in the range from 0 to 100, preferably in the range from 15 to 100, preferably in the range from 20 to 95, especially preferably in the range from 25 to 90.
• 17. Use according to Embodiment 5 to 6 or 15 to 16, wherein the flexible foam has a tensile strength according to ISO 1926:2009-12 of between 100 and 2500 kPa, preferably between 150 and 2250 kPa, more preferably between 200 and 2000 kPa.
• 18. Use according to any of the preceding embodiments, characterized in that the system comprises a water scavenger and the proportion of the water scavenger is not more than 5.0% by weight, preferably not more than 3.5% by weight, more preferably not more than 2.5% by weight, very preferably not more than 1.5% by weight, extremely preferably not more than 1% by weight, of the total composition of the system.
• 19. Use according to Embodiment 18, characterized in that the system does not include any water scavenger.
• 20. Use according to any of the preceding embodiments, characterized in that the metal-siloxane-silanol(ate) compound is in the form of a monomer, oligomer and/or polymer, where the metal(s) are present terminally and/or within the chain.
• 21. Use according to any of the preceding embodiments, characterized in that the metal-siloxane-silanol(ate) compound has the general formula R*_qSi_rO_sM_t where each R* is independently selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C6-cycloalkyl, optionally substituted C2- to C20-alkenyl, optionally substituted C6- to C10-aryl, —OH and —O—(C1- to C10-alkyl), each M is independently selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals of transition groups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,
  • q is an integer from 4 to 19,
  • r is an integer from 4 to 10,
  • s is an integer from 8 to 30, and
  • t is an integer from 1 to 8.
• 22. Use according to any of the preceding embodiments, characterized in that the metal-siloxane-silanol(ate) compound has a general structure (I)

where
X¹, X² and X³ are independently selected from Si and M¹, where M¹ is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals of transition groups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,
Z¹, Z² and Z³ are independently selected from the group consisting of L², R⁵, R⁶ and R⁷, where L² is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L² is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O— isobutyl;
R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are independently selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C5- to C10-aryl; Y¹ and Y² are independently —O-M²-L³_Δ, or Y¹ and Y² are associated and together are —O-M²(L³_Δ)-O— or —O—, where L³ is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L³ is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O— isopropyl, and —O-isobutyl, and where M² is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals,
especially from the group consisting of metals of transition groups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,
and
X⁴ is -M³L¹_Δ or M³ and Q¹ and Q² are H or each is a single bond joined to M³, where L¹ is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L¹ is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and where M³ is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals,
especially from the group consisting of metals of transition groups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,
or
X⁴ is -M³L¹_Δ and Q² is H or a single bond joined to M³ and Q¹ is H, M⁴L⁴_Δ or —SiR⁸, where M⁴ is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals of transition groups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,
and where L⁴ is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L⁴ is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and where R⁸ is selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C5- to C10-aryl,
or
X⁴, Q¹ and Q² are independently -M³L¹_Δ,
or
X⁴ is —Si(R⁸)—O-M³L¹_Δ, Q² is a single bond joined to the silicon atom of X⁴ and Q¹ is -M⁴L⁴_Δ,
or
X⁴ is —Si(R⁸)—O-M³L¹_Δ, Q² is a single bond joined to the silicon atom of X⁴ and Q¹ is a single bond joined to the M³ atom of X⁴.

• 23. Use according to any of the preceding embodiments, characterized in that the metal-siloxane-silanol(ate) compound has the structural formula (II)

• • where X⁴, R¹, R², R³, R⁴, Z¹, Z² and Z³ are defined according to Embodiment 22.
• 24. Use according to Embodiment 23, characterized in that the metal-siloxane-silanol(ate) compound of the structure (IV) is a metal silsesquioxane

• • where
    • X⁴ is selected from the group consisting of metals of transition groups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, most preferably from the group consisting of Ti and Sn, and is most preferably Ti, and
    • X⁴ is joined to OR where R is selected from the group consisting of —H, -methyl, -ethyl, -propyl, -butyl, -octyl, -isopropyl, and -isobutyl, Z¹, Z² and Z³ are each independently C1- to C20-alkyl, C3- to C8-cycloalkyl, C2- to C20-alkenyl and C5- to C10-aryl, especially selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, heptyl, octyl, vinyl, allyl, butenyl and phenyl, and benzyl, and R¹, R², R³ and R⁴ are each independently C1- to C20-alkyl, C3- to C8-cycloalkyl, C2- to C20-alkenyl, and C5- to C10-aryl, especially selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, heptyl, octyl, vinyl, allyl, butenyl and phenyl, and benzyl.
• 25. Use according to Embodiment 25, characterized in that the metal-siloxane-silanol(ate) compound is a metal silsesquioxane of the structure (IVb)

• • where
    • X⁴ is selected from the group consisting of metals of transition groups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, most preferably from the group consisting of Ti (and therefore is heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS)) and Sn (and therefore is heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS)), and is most preferably Ti (and therefore is heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS)).
• 26. Use according to any of the preceding embodiments, characterized in that the hydroxy-functionalized polymer in component A is selected from the group consisting of polyoxyalkylene diols or polyoxyalkylene triols, especially polyoxyethylene di- and triols and polyoxypropylene di- and triols, higher-functionality polyols such as sorbitol, pentaerythritol-started polyols, ethylene oxide-terminated polyoxypropylene polyols, polyester polyols, styrene-acrylonitrile, acryloyl-methacrylate, (poly)urea-grafted or -containing polyether polyols, polycarbonate polyols, CO₂ polyols, polyhydroxy-functional fats and oils, especially castor oil, polyhydrocarbon polyols such as dihydroxypolybutadiene, polytetrahydrofuran-based polyethers (PTMEG), OH-terminated prepolymers based on the reaction of a polyetherol or polyesterol with a diisocyanate, polyalkylene diols, polyester polyols or mixtures thereof, preferably polyalkylene diols, polyester polyols, or mixtures thereof.
• 27. Use according to Embodiment 26, characterized in that the hydroxy-functionalized polymer in component A is selected from the group consisting of polyoxyalkylene diols, polyoxyalkylene triols, higher-functionality polyoxyalkylene polyols, especially polyoxyethylene di- and/or triols and/or polyoxypropylene di- and/or triols, KOH-catalysed hydroxy-functionalized polyethers or double metal cyanide complex-catalysed (DMC-catalysed) hydroxy-functionalized polyethers or mixtures thereof.
• 28. Use according to any of the preceding embodiments, characterized in that the compound having one or more isocyanate groups in component B is selected from the group consisting of aromatic and/or aliphatic isocyanates (Iso) of the general structure (VI) or mixtures thereof

R^x—(N═C═O)_z  (VI)

• • where
    • R^x is a hydrocarbon-containing group, preferably at least one aromatic or aliphatic group or mixtures thereof, more preferably an optionally substituted straight-chain or branched C1- to C16-alkyl group, an optionally substituted straight-chain or branched C2- to C16-alkenyl group or an optionally substituted straight-chain or branched C2- to C16-alkynyl group, an optionally substituted C4- to C14-cycloalkyl group or an optionally substituted C4- to C14-aryl group, most preferably diphenylmethane, toluene, dicyclohexylmethane, hexane or methyl-3,5,5-trimethylcyclohexyl,
    • z is at least 1, preferably at least 2 or 3.
• 29. Use according to any of the preceding embodiments, characterized in that the compound having one or more isocyanate groups in component B is selected from the group consisting of aromatic and/or aliphatic isocyanates (Iso) of the general structure (VI) or mixtures thereof

R^xN═C═O)_z  (VI)

• • where
    • R^x is diphenylmethane, toluene, dicyclohexylmethane, hexane or methyl-3,5,5-trimethylcyclohexyl, preferably diphenylmethane or hexane or methyl-3,5,5-trimethylcyclohexyl, most preferably diphenylmethane or methyl-3,5,5-trimethylcyclohexyl, and
    • z is at least 2, preferably 2 or 3
• 30. Use according to Embodiment 29, characterized in that at least one isocyanate (Iso) of the general structure (VI) is selected from the group consisting of polymeric, oligomeric and monomeric methylene diphenyl isocyanate (MDI), especially of polymeric methylene diphenyl isocyanate (poly-MDI), 4,4′-methylene diphenyl isocyanate (4,4′-MDI), 2,4′-methylene diphenyl isocyanate (2,4′-MDI), 2,2′-methylene diphenyl isocyanate (2,2′-MDI), 4,4′-diisocyanatodicyclohexylmethane (H₁₂MDI), 2-methylpentamethylene 1,5-diisocyanate, dodecamethylene 1,12-diisocyanate, lysine and lysine ester diisocyanate, cyclohexane 1,3-diisocyanate, cyclohexane 1,4-diisocyanate, perhydro(diphenylmethane 2,4′-diisocyanate), perhydro(diphenylmethane 4,4′-diisocyanate), 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (=isophorone diisocyanate or IPDI), hexamethylene 1,6-diisocyanate (HDI) or the trimer thereof (HDI trimer), 2,2,4- and/or 2,4,4-trimethylhexamethylene 1,6-diisocyanate, 1,4-bis(isocyanato)cyclohexane, 1,4-bis(isocyanato)benzene (PPDI), 1,3- and/or 1,4-bis(isocyanatomethyl)cyclohexane, m- and/or p-xylylene diisocyanate (m- and/or p-XDI), m- and/or p-tetramethylxylylene 1,3-diisocyanate, m- and/or p-tetramethylxylylene 1,4-diisocyanate, bis(1-isocyanato-1-methylethyl)naphthalene, 1,3-bis(isocyanato-4-methylphenyl)-2,4-dioxo-1,3-diazetidine, naphthalene 1,5-diisocyanate (NDI), 3,3′-dimethyl-4,4′-diisocyanatodiphenyl (TODD, tolylene 2,4- and/or 2,6-diisocyanate (TDI), 1,3-bis(isocyanatomethyl)benzene or mixtures thereof, preferably polymeric methylene diphenyl isocyanate (poly-MDI), 4,4′-methylene diphenyl isocyanate (4,4′-MDI) or isophorone diisocyanate (IPDI), hexamethylene 1,6-diisocyanate (HDI) or the trimer thereof (HDI trimer) or mixtures thereof, most preferably polymeric methylene diphenyl isocyanate (poly-MDI), 4,4′-methylene diphenyl isocyanate (4,4′-MDI) or isophorone diisocyanate (IPDI) or mixtures thereof.
• 31. Use according to any of the preceding embodiments, characterized in that the metal-siloxane-silanol(ate) compound has a gel/blow reaction selectivity of >1, preferably >5, more preferably >10, further preferably >30, most preferably >40.
• 32. Use according to any of the preceding embodiments, characterized in that the metal-siloxane-silanol(ate) compound has a gel/blow reaction selectivity of ≥30.
• 33. Use according to any of the preceding embodiments, characterized in that the metal-siloxane-silanol(ate) compound is present in a molar concentration in the range from 0.00001 to 0.06 mol/kg, preferably in the range from 0.0002 to 0.01 mol/kg, more preferably in the range from 0.0003% to 0.01 mol/kg, based in each case on the total weight of the system.
• 34. Use according to any of the preceding embodiments, characterized in that the metal-siloxane-silanol(ate) compound is present with a proportion by weight of 0.001% to 5%, preferably in the range from 0.002% to 1%, more preferably in the range from 0.003% to 0.5%, based in each case on the total weight of the system.
• 35. Use according to any of the preceding embodiments, characterized in that the system cures after combination of components A and B to give a reaction product, especially to give a polyurethane.
• 36. Use according to any of the preceding embodiments, characterized in that the resulting reaction product has a higher density by >3% compared to a dibutyltin dilaurate (DBTL)- or triethylenediamine (DABCO)-catalysed resulting reaction product when the water content of component A or component B is >0.2%.
• 37. Use according to any of the preceding embodiments, characterized in that the system additionally comprises a catalyst selected from the group consisting of metal-siloxane-silanol(ate) compounds, such as heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS), tetraalkyl titanates, such as tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-sec-butyl titanate, tetraoctyl titanate, tetra(2-ethylhexyl) titanate, dialkyl titanates ((RO)₂TiO₂ in which R is, for example, isopropyl, n-butyl, isobutyl), such as isopropyl n-butyl titanate; titanium acetylacetonate chelates, such as diisopropoxybis(acetylacetonate) titanate, diisopropoxybis(ethylacetylacetonate) titanate, di-n-butylbis(acetylacetonate) titanate, di-n-butyl-bis(ethylacetoacetat) titanate, triisopropoxidebis(acetylacetonate) titanate, zirconium tetraalkoxides, such as zirconium tetraethoxide, zirconium tetrabutoxide, zirconium tetrabutyrate, zirconium tetrapropoxide, zirconium carboxylate, such as zirconium diacetate; zirconium acetylacetonate chelates, such as zirconium tetra(acetylacetonate), tributoxyzirconium acetylacetonate, dibutoxyzirconium (bisacetylacetonate), aluminium trisalkoxides, such as aluminium triisopropoxide, aluminium trisbutoxide; aluminium acetylacetonate chelates, such as aluminium tris(acetylacetonate) and aluminium tris(ethylacetylacetonate), organotin compounds such as dibutyltin dilaurate (DBTL), dibutyltin maleate, dibutyltin diacetate, tin(II) 2-ethylhexanoate (tin octoate), tin naphthenate, dimethyltin dineodecanoate, dioctyltin dineodecanoate, dimethyltin dioleate, dioctyltin dilaurate, dimethyl mercaptide, dibutyl mercaptide, dioctyl mercaptide, dibutyltin dithioglycolate, dioctyltin glycolate, dimethyltin glycolate, a solution of dibutyltin oxide, reaction products of zinc salts and organic carboxylic acids (carboxylates), such as zinc(II) 2-ethylhexanoate or zinc(II) neodecanoate, mixtures of bismuth carboxylates and zinc carboxylates, reaction products of bismuth salts and organic carboxylic acids, such as bismuth(III) tris(2-ethylhexanoate) and bismuth(III) tris(neodecanoate) and bismuth complexes, organolead compounds such as lead octoxide, organovanadium compounds, amine compounds such as butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylendiamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole and 1,8-diazabicylo(5.4.0)undecene-7 (DBU), salts of these amines with carboxylic acids or other acids or mixtures thereof, preferably metal-siloxane-silanol(ate) compounds, especially heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), dibutyltin dilaurate (DBTL), tin(II) 2-ethylhexanoate (tin octoate), zinc(II) 2-ethylhexanoate, zinc(II) neodecanoate, bismuth(III) tris(2-ethylhexanoate), bismuth(III) tris(neodecanoate) or mixtures thereof, more preferably metal-siloxane-silanol(ate) compounds, especially heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) or heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS), dibutyltin dilaurate (DBTL) or mixtures thereof, most preferably heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS), dibutyltin dilaurate (DBTL) or mixtures thereof.
• 38. Use according to any of the preceding embodiments, wherein the blowing agent is selected from the group consisting of water, air, nitrogen, carbon dioxide, pentane, cyclopentane, hydrofluorocarbons and mixtures thereof.
• 39. Use according to any of the preceding embodiments, wherein the system further comprises one or more additives selected from the group comprising filler, an adhesion promoter, plasticizers, UV stabilizers, thixotropic agents, wetting agents or combinations thereof.
• 40. Two-component (2K) system defined according to any of the preceding embodiments.
• 41. Process for producing unfoamed polyurethane, comprising the following steps:
  • (i) providing a component A comprising at least one hydroxy-functionalized polymer according to any of the preceding embodiments,
  • (ii) providing a component B comprising at least one compound having one or more isocyanate groups according to any of the preceding embodiments,
  • (iii) adding at least one metal-siloxane-silanol(ate) compound according to any of the preceding embodiments to component A or B,
  • (iv) optionally adding a water scavenger according to any of the preceding embodiments to at least one of components A and/or B,
  • (v) optionally adding at least one additive according to any of the preceding embodiments to at least one of components A and/or B,
  • (vi) combining component A with component B.
• 42. Process for producing flexible foams, comprising the following steps:
  • (i) providing a component A comprising at least one hydroxy-functionalized polymer according to any of the preceding embodiments,
  • (ii) providing a component B comprising at least one compound having one or more isocyanate groups according to any of the preceding embodiments,
  • (iii) adding at least one metal-siloxane-silanol(ate) compound according to any of the preceding embodiments to component A and/or B,
  • (iv) optionally adding a water scavenger according to any of the preceding embodiments to at least one of components A and/or B,
  • (v) optionally adding at least one additive according to any of the preceding embodiments to at least one of components A and/or B,
  • (vi) adding a blowing agent to at least one of components A and B according to any of the preceding embodiments,
  • (vii) combining component A with component B.
• 43. Process for producing rigid foams, comprising the following steps:
  • (i) providing a component A comprising at least one hydroxy-functionalized polymer according to any of the preceding embodiments,
  • (ii) providing a component B comprising at least one compound having one or more isocyanate groups according to any of the preceding embodiments,
  • (iii) adding at least one metal-siloxane-silanol(ate) compound according to any of the preceding embodiments to component A and/or B,
  • (iv) optionally adding a water scavenger according to any of the preceding embodiments to at least one of components A and/or B,
  • (v) optionally adding at least one additive according to any of the preceding embodiments to at least one of components A and/or B,
  • (vi) adding a blowing agent to at least one of components A and B according to any of the preceding embodiments,
  • (vii) combining component A with component B.
• 44. Combination for production of unfoamed polyurethanes, comprising at least one component A and component B, where component A comprises at least one hydroxy-functionalized polymer according to any of the preceding embodiments and at least one metal-siloxane-silanol(ate) compound according to any of the preceding embodiments, and component B comprises at least one compound having one or more isocyanate groups according to any of the preceding embodiments, characterized in that components A and B are each present separately and in a relative NCO:OH ratio of 2:1 up to 1:2, preferably in a ratio of 1.8:1 to 1:1.8, more preferably in a ratio of 1.5:1 up to 1:1.5, most preferably in a ratio of 1.2:1 up to 1:1.2.
• 45. Combination for production of rigid or flexible foams, comprising at least one component A and component B, where component A comprises at least one hydroxy-functionalized polymer according to any of the preceding embodiments and at least one metal-siloxane-silanol(ate) compound according to any of the preceding embodiments, and component B comprises at least one compound having one or more isocyanate groups according to any of the preceding embodiments, characterized in that components A and B are each present separately and in a relative ratio of 2:1 up to 1:2, preferably in a ratio of 1.8:1 to 1:1.8, more preferably in a ratio of 1.5:1 up to 1:1.5, most preferably in a ratio of 1.2:1 up to 1:1.2.
• 46. Unfoamed polyurethanes producible by a process using at least one metal-siloxane-silanol(ate) compound according to one or more of Embodiments 20 to 25.
• 47. Unfoamed polyurethanes according to Embodiment 46, characterized in that they are elastomers.
• 48. Unfoamed polyurethanes according to Embodiment 47, characterized in that they are thermosets.
• 49. Unfoamed polyurethanes according to Embodiments 46 to 48, characterized in that they have a density in the range according to DIN EN ISO 845:2009-10 of 800 to 1950 kg/m³, preferably in the range from 950 to 1750 kg/m³, more preferably in the range from 980 to 1650 kg/m³, most preferably in the range from 990 to 1600 kg/m³.
• 50. Unfoamed polyurethanes according to Embodiments 46 to 49, characterized in that they have a Shore 00 hardness according to ASTM D2240-15 in the range of 40-100, preferably in the range from 45 to 95, preferably in the range from 50 to 90, especially preferably in the range from 55 to 85.
• 51. Unfoamed polyurethanes according to Embodiments 46 to 50, characterized in that they have a Shore A hardness according to ASTM D2240-15 in the range of 0-100, preferably in the range from 5 to 95, preferably in the range from 10 to 90, especially preferably in the range from 15 to 85.
• 52. Unfoamed polyurethanes according to Embodiments 46 to 51, characterized in that they have a Shore D hardness according to ASTM D2240-15 in the range of 0-100, preferably in the range from 5 to 95, preferably in the range from 10 to 90, especially preferably in the range from 15 to 85.
• 53. Flexible foams producible by a process using at least one metal-siloxane-silanol(ate) compound according to one or more of Embodiments 20 to 25.
• 54. Flexible foams according to Embodiment 53, characterized in that they have a Shore A hardness according to ASTM D2240-15 of ≥20.
• 55. Flexible foams according to Embodiment 53 or 54, characterized in that they have a Shore A hardness according to ASTM D2240-15 between 20 and 100, preferably between 20 and 60, more preferably between 20 and 50.
• 56. Flexible foams according to embodiment 53, 54 or 55, characterized in that they have a tensile strength according to DIN EN ISO 1798:2008-04 of ≥200 kPa.
• 57. Flexible foams according to embodiment 53, 54 or 55, characterized in that they have a tensile strength according to DIN EN ISO 1798:2008-04 between 200 and 350 kPa.
• 58. Rigid foams producible by a process using at least one metal-siloxane-silanol(ate) compound according to one or more of Embodiments 20 to 25.
• 59. Rigid foams according to Embodiment 58, characterized in that the rigid foams are produced by the process according to Embodiment 43.
• 60. Rigid foams according to embodiment 58 or 59, characterized in that they have a tensile strength according to ISO 1926:2009-12 of ≥100 kPa.
• 61. Rigid foams according to embodiment 51, 52 or 53, characterized in that they have a tensile strength according to ISO 1926:2009-12 between 200 and 2000 kPa.
• 62. Use of at least one metal-siloxane-silanol(ate) compound for production of flexible foams for use in CASE applications (coatings, adhesives, sealants and elastomers) and/or elastomer materials.
• 63. Use of at least one metal-siloxane-silanol(ate) compound for production of flexible foams in furniture, mattresses, car seats, seal materials or acoustic materials.
• 64. Use of at least one metal-siloxane-silanol(ate) compound for production of rigid foams in sound insulations, heat insulations and/or cold insulations, or in CASE applications (coatings, adhesives, sealants and elastomers).
• 65. Use of at least one metal-siloxane-silanol(ate) compound for production of rigid foams for insulation of district heating pipes, tanks and pipelines, and for production of all kinds of refrigeration units.
• 66. Use of at least one metal-siloxane-silanol(ate) for production of rigid foams in insulation panels for the fields of use of roofs, walls, floors and/or ceilings, in window frame insulations or as assembly foam.

EXAMPLES

Example I)—Unfoamed Polyurethanes

The comparative examples (EP1-EP18) show the influence of the gel catalyst according to the invention. In spite of the influence of a certain water content, it is possible to produce even unfoamed polyurethanes at a high technical level. The known blowing catalysts DBTL and DABCO that are utilized in the specialist field show much poorer performance in direct comparison. It has thus been found that, surprisingly, metal-siloxane-silanol(ate) compounds catalyse the gel reaction particularly selectively.

In the course of the studies, it has been found that, surprisingly, the use of TiPOSS as catalyst for the construction of unfoamed polyurethane systems catalyses the gel reaction particularly selectively, with considerable differences from the DBTL and TEDA reference gel catalysts tested by comparison. In the context of this study, polyol mixtures (components A) each having equal proportions of catalyst and rising water contents were produced. Components A obtained by comparison were reacted with polymer MDI (component B) in a stoichiometric ratio to give polyurethane compounds. The assessment of the reactions involved in the curing process (gel and blowing reaction) was made with reference to the density and hardness values obtained, and the foaming characteristics.

The following materials were used for the production of component A, of component B and of the elastomer products (EP):

• • Voranate M230, BASF
  • PolyU-Pol M5020 (OH number 35 mg KOH/g, viscosity 850 mPa*s), PolyU GmbH
  • BNT-Cat 422, dibutyltin dilaurate (DBTL), 20% and 1% strength, dissolved in Hexamoll® DINCH, BASF
  • Heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS)
  • TiPOSS, 20% and 1% strength, dissolved in Hexamoll® DINCH, BASF
  • Dabco® 33 LV, 1,4-diazabicyclo[2.2.2]octane, also triethylenediamine (DABCO or TEDA), 33% strength in dipropylene glycol, Evonik

A-I) Production of Components A—Comparative Examples to Study the Influence of Different Water Contents:

In one reaction vessel each, the comparative examples of component A were produced by adding 0.1% (A4-A6), 0.2% (A7-A9), 0.4% (A10-A12), 0.6% (A13-A15) and 0.8% (A16-A18) of water to an initial charge of 200 g of PolyU-Pol M5020 and mixing with a propeller stirrer at 2500 min⁻¹. For each mixture of different water content, after being left to stand for 1 h, the batches were divided into 3×60 g batches, and 1% of a 20% TiPOSS solution in DINCH, 1% of a 20% DBTL solution in DINCH and 0.66% of a 33% TEDA solution in dipropylene glycol were added, and they were mixed once again at 2500 min⁻¹ for 1 min. In addition, as reference materials, mixtures (A1-A3) were produced without additional introduction of water.

TABLE 3
Composition of components B B1-B18 for the study
	A1	A2	A3	A4	A5	A6	A7	A8	A9
PolyU-	100	100	100	100	100	100	100	100	100
Pol
M5020
TiPOSS	1	—	—	1	—	—	1	—	—
20% in
DINCH
DBTL	—	1	—	—	1	—	—	1	—
20% in
DINCH
TEDA	—	—	0.66	—	—	0.66	—	—	0.66
33% in
DPG
Water	0	0	0	0.1	0.1	0.1	0.2	0.2	0.2
	B10	B11	B12	B13	B14	B15	B16	B17	B18
PolyU-	100	100	100	100	100	100	100	100	100
Pol
M5020
TiPOSS	1	—	—	1	—	—	1	—	—
20% in
DINCH
DBTL	—	1	—	—	1	—	—	1	—
20% in
DINCH
TEDA	—	—	0.66	—	—	0.66	—	—	0.66
33% in
DPG
Water	0.4	0.4	0.4	0.6	0.6	0.6	0.8	0.8	0.8

B-I) Reaction of Components A A1 to A18 with Polymer MDI, Voranate M230 (Component B)

In a disposable beaker, Voranate M230 (component B) was added to 20 g in each case of the mixtures A1-A18 produced in 1) in a stoichiometric ratio (100% isocyanate conversion based on the resulting overall OH number of the polyol mixture), and the mixture was mixed with a propeller stirrer at 1500 min⁻¹ for 10 s. 15 g of the mixture was then transferred to a 100 ml PP beaker, and the curing characteristics were determined with reference to foaming characteristics, density and Shore A hardness of the resultant elastomer products EP1-EP18 (numbering as in the table above). The results can be found in Table 4 below.

C-I) Results of the Syntheses of the Elastomer Products (EP)

The visual assessment of the foaming characteristics of the various elastomer products EP1-EP18 shows that the TiPOSS-catalysed combinations (comprising components A and B) (marked area of the table, EP1, EP4, EP7, EP10, EP13 and EP16) foam only at a greater water content (EP16, water content about 0.8%) than the correspondingly DBTL- or TEDA-catalysed mixtures (EP11 and EP12, water content about 0.4%). FIGS. 1-5 show the foaming characteristics with increasing water content and the surprising effect of TiPOSS catalysis in the reaction of component A with component B.

Example II)—Foamed Polyurethanes

Example IIa)—Flexible Foams

It has been found that, surprisingly, the use of TiPOSS as catalyst for the production of foamed polyurethane systems leads to products having a considerable improvement in the level of strength compared to foamed polyurethane systems that are obtained via conventional catalysis. The increase in strength is advantageous since the polyurethane foams produced with TiPOSS can withstand greater mechanical loads.

The study of the catalytic properties of TiPOSS in foamed polyurethane systems was conducted on 2-component polyurethane reaction mixtures (A component=multicomponent system with base polyol, B component=isocyanate) that find use, for example, for production of gaskets foamed in situ in a component (formed-in-place foam gasket, FIPFG). In this process, the 2-component reaction mixture is applied directly to the component in as yet unreacted form with the aid of a CNC machine or a robot.

For the study, significantly simplified base formulations were used, which are guided in their raw material setup by the above-described 2-component reaction systems for the FIPFG process. The raw materials used are listed in Table 5 below. The assessment of TiPOSS as catalyst for the foam-forming process was made by producing the foams

• • either with just one catalyst (TiPOSS or DBTL or TEDA/DABCO)
  • or with a catalyst mixture (TiPOSS and TEDA or DBTL and TEDA/DABCO).

TABLE 5
Base constituents of the A component for the production of foamed polyurethane systems
PolyU-Pol M5020      Base polyol, EO-tipped polyether triol, M~4850 g/mol
Glycerol, Alfa Aesar Crosslinker
Water                Blowing agent
Catalyst 1           Metal catalyst, TiPOSS
Catalyst 2           Metal catalyst, DBTL
Catalyst 3           Amine catalyst, TEDA

The reactions were conducted at various indices (index 100 means complete conversion of the A component (OH) with the B component (NCO); index 75 and index 50 mean 25% and 50% NCO deficiency respectively), since the production of industrially produced gasket foams in this index range is common practice and is used for adjusting foam properties such as hardness, density, strength properties and compression characteristics.

A-IIa) Production of Gasket Foams (GF) GF1-GF15:

Production of the A Component:

For the production of the A components, 5×500 g batches were produced with the percentage ratios specified in Table 6 below. For this purpose, an initial charge of PolyU-Pol M5020, glycerol and water was admixed with the amounts, specified in Table 6, of a 20% TiPOSS solution in DINCH (for GF1, GF6 and GF11), a 20% DBTL solution in DINCH (for GF2, GF7 and GF12), a 33% TEDA solution in dipropylene glycol (for GF3, GF8 and GF13), a mixture of a 20% TiPOSS solution in DINCH with a 33% TEDA solution in dipropylene glycol (for GF4, GF9 and GF14), a mixture of a 20% DBTL solution in DINCH and 0.66% of a 33% TEDA solution in dipropylene glycol (for GF5, GF10 and GF15) and mixed with a propeller stirrer at 2500 rpm.

BIIa) Reaction of the A Component with the B Component Polymer MDI, Voranate M230

In a 300 ml disposable beaker, 80-140 g of the A component in each case was prepared with the appropriate amount of the B component (PMDI isocyanate, Voranate M230) apparent from the mixing ratio in the MR line in Table 6 below, and mixed with a propeller stirrer at 2500 rpm for 15 s. The different mixing ratios MR represent the degree of conversion of the A component with the B component (index 100, index 75 and index 50).

Columns GF1-GF5, MR 3.8:1 to MR 3.9:1 correspond to 100% conversion of the A component with the B component (stoichiometric conversion NCO:OH)

Columns GF6-GF10, MR 5.2:1 to MR 5.1:1 correspond to 75% conversion of the A component with the B component (B component is present in deficiency)

Columns GF11-GF15, MR 7.7:1 to MR 7.6:1 correspond to 50% conversion of the A component with the B component (B component is present in deficiency) The mixtures of A and B components (about 90-150 g) were poured into an open plastic mould (Ø 20 cm, t=1 cm), demoulded and cured at 23° C. for 72 h.

C-IIa) Results of Gasket Foam Investigations GF1-GF15

The resultant foam slabs (h˜1 cm) GF1-GF15 were used to ascertain the technical properties such as density, Shore A hardness, tensile strength, elongation at break and compression set. The results can be found in Table 6 below.

D-IIa) Conclusion

The mixture experiments GF1-GF15 gave foams having a smooth surface and fine cell structure. Comparison of the technical parameters of the gasket foams GF1 to GF5 for index 100 (stoichiometric conversion, marked area) makes it clear that tensile strength TS is significantly elevated for TiPOSS-catalysed systems in particular (GF1 compared to GF2 and GF3, and GF4 compared to GF5). This observation is reflected analogously in the systems that were produced with a deficiency of isocyanate (for index 75 GF6 compared to GF7 and GF8, and GF9 compared to GF10, and index 50 GF11 compared to GF12 and GF13, and GF14 compared to GF15).

The essential outcome of the experiments can be summarized in that the use of TiPOSS as catalyst leads to more selective formation of polyurethane linkages and hence to improved strength properties in the foam systems examined.

Example IIb)—Rigid Foams

The study of the catalytic properties of TiPOSS in rigid polyurethane systems was conducted on 2-component polyurethane reaction mixtures (A component=multicomponent system with polyols of low molecular weight and relatively high functionality, B component=isocyanate), which find use, for example, in the production of seals, fillings and insulations of gaps/cavities in housing components of electronic devices (e.g. white goods).

The study took place—in analogy to the above studies—using a greatly simplified base formulation that was guided in its raw material selection by the above-described 2-component reaction systems for the filling of cavities with foam. The raw materials used are listed in Table 7 below.

TABLE 7
Base constituents of the A component for the production of a rigid polyurethane foam system
PolyU-Pol G500 Polyether polyol, MW = 560 g/mol, OH functionality ~3, PolyU GmbH
PolyU-Pol      Polyether polyol, MW = 600 g/mol, OH functionality ~4.5, PolyU GmbH
RF551
Water          Blowing agent
Catalyst 1     Metal catalyst, TiPOSS
Catalyst 2     Amine catalyst, Dabco 33 LV, TEDA (triethylenediamine 33% in DPG),
               Evonik
Catalyst 3     Blowing catalyst, Dabco DMDEE (2,2′-dimorpholinediethyl ester), Evonik
Stabilizer     Tegostab B 8863z, Evonik

The assessment of TiPOSS as catalyst for the rigid foam-forming process was made by producing

• • rigid foam 1 (RF1) with a catalyst mixture of Dabco DMDEE (blowing catalyst) and TiPOSS (gel catalyst) and
  • rigid foam 2 (RF2) with a catalyst mixture of Dabco DMDEE (blowing catalyst) and Dabco 33 LV (gel catalyst).

The reactions were conducted at index 100, i.e. full conversion of the A component (OH) with the B component (NCO).

A-IIb) Production of the Rigid Foams (RF) RF1 and RF2:

Density

Production of the A Component:

For the production of the A components, 2×500 g batches were produced with the percentage ratios specified in the table below. For this purpose, PolyU-Pol G500, PolyU-Pol RF551, DMDEE, water and Tegostab B 8863z were initially charged and admixed with the amounts, specified in the table, of a 20% TiPOSS solution in DINCH (RF1) and a 33% TEDA solution in dipropylene glycol (RF2), and mixed with a propeller stirrer at 2500 rpm for 2 min.

Reaction of the A Component with the B Component Polymer MDI, Voranate M230

In an 800 ml disposable beaker, 300 g of the A component in each case was prepared with the appropriate amount (˜275 g) of the B component (PMDI isocyanate, Voranate M230, BASF) apparent from the mixing ratio in the MR line in Table 8 below, and mixed with a propeller stirrer at 2500 rpm for 15 s.

The mixtures of A and B components (about 550 g) were poured into a plastic-lined wooden box (20 cm×20 cm×23 cm), cured at 23° C. for 72 h and demoulded.

B-IIb) Results of the Rigid Foam Studies RF1 and RF2

The requisite test specimens were sawn out of the rigid foam cubes obtained (20 cm×20 cmט14 cm, RF1 and RF2) by means of a bandsaw, and these were used to ascertain the technical properties such as density, Shore D hardness (surface measurement), tensile strength and elongation at break. The results of the studies can be found in Table 8 below.

C-IIb) Conclusion

In both cases, mixture experiments RF1 and RF2 gave rigid foams having a very smooth surface. The foam structure in the foams RF1 and RF2 examined is a fine-cell structure overall, and tends to have finer cells than the foam obtained with TiPOSS. Comparison of the technical parameters of the gasket foams RF1 and RF2 makes it clear that tensile strength TS is improved for the TiPOSS-catalysed system (RF1 compared to RF2, marked area). By contrast, the other parameters (density and hardness) remain constant.

The essential outcome of the experiments can be summarized in that the use of TiPOSS as catalyst can be utilized in rigid foam systems as well for selective formation of polyurethane linkages and hence for improved strength properties in the foam systems examined.

Example III)—Procedure for Ascertaining Selectivity (According to Farkas)

For determination of the selectivity (“gel/blow reaction selectivity”) of catalysts in the production of polyurethanes by means of the titration method according to Farkas, an aliquot of 50 ml of a tolylene 2,4-diisocyanate (TDI)-benzene solution (0.1533 mol/l) and an aliquot of 50 ml of a diethylene glycol- (DEG, 0.1533 mol/l) or water-benzene solution (0.0752 mol/l) was reacted with 5 ml of a catalyst-containing benzene solution (0.0735 mol/l) at 30-70° C. At various time intervals, a sample was taken from the reaction flask, and the unreacted isocyanate was quenched with the n-butylamine-benzene solution. The NCO content of the respective sample was determined by back-titration with a standardized HCl solution.

In the titration method, it is assumed that the reaction of isocyanate with diol (or with water) in the presence of a catalyst is a first-order reaction in relation to the isocyanate or alcohol concentration.

$\begin{array}{cc}\frac{\mathrm{dx}}{\mathrm{dt}}={K\left(a-x\right)}^2& \left(A\right)\end{array}$

in which
x is the concentration of NCO groups converted,
a is the initial concentration of the NCO groups,
K is the reaction rate constant (I/mol/h), and
t is the reaction time (h).

The integration of equation (A), introducing the initial state (x=0 when t=0), gives the following expression:

$\begin{array}{cc}\frac{1}{a-x}=\mathrm{Kt}+\frac{1}{a}& \left(B\right)\end{array}$

The catalysis reaction constant Kc can be obtained for any catalyst assuming equation (C):

K=K₀+Kc×C  (C)

in which
K₀ is the reaction rate constant (I/mol h, no catalyst),
Kc is the catalysis reaction constant (I²/eq mol h), and
C is the concentration of the catalyst (mol/l).

The activities of the gel and blow reactions, ascertained by the titration method in the model reaction of TDI/DEG (or water), is shown in Table A for a selection of prior art catalysts.

TABLE A
Activities of the gel and blow reactions, and selectivity of the catalysts ascertained
via titration method
		Activity of	Activity of
		the gel	the blow
		reaction	reaction	Selectivity
		k1w	k2w	(gel reaction/
Abbreviation	Chemical name	(×10)	(×10)	blow reaction)
TEA	Triethylamine	1.16	0.60	1.93
DMCHA	Dimethylcyclohexylamine	2.22	0.83	2.67
TE	Tetramethylethylenediamine	4.19	1.14	3.68
MR	Tetramethylhexamethylenediamine	2.95	0.84	3.51
DT	Pentamethyldiethylenetriamine	4.26	15.9	0.27
PMA	Pentamethyldipropylenetriamine	3.80	1.16	3.28
TEDA or	Triethylenediamine	10.9	1.45	7.52
DABCO
DMP	Dimethylpiperazine	1.3	0.28	4.64
NP	Dimethylaminoethylmethylpiperazine	1.71	0.78	2.19
NEM	N-Ethylmorpholine	0.22	0.01	22.00
TRC	Tri(dimethylaminopropyl)hexahydro-	3.00	1.12	2.68
	1,3,5-triazine
ETS	Bis(2-Dimethylaminoethyl) ether	2.99	11.7	0.26
DMEA	Dimethylaminoethanol	2.91	0.36	8.08
HP	Hydroxyethylmethylpiperazine	0.61	0.11	5.55
RX3	Dimethylaminoethoxyethanol	1.84	2.55	0.72
RX5	Trimethylaminoethylethanolamine	2.89	4.33	0.67
F22	Special catalyst for CASE	26.1	0.83	31.45
	applications
DBTL	Dibutyltin dilaurate	14.4	0.48	30.00

Example IV

The present invention also relates to a composition and to a process for producing polyurethane prepolymers and polyurethane systems based on polyols, di- or polyisocyanates and a TiPOSS-based catalyst.

TiPOSS-based catalysts that are preferred in accordance with the invention are those disclosed in EP 2 989 155 B1 and EP 2 796 493 A1. The disclosure of these documents is fully incorporated with regard to the catalysts. Particular preference is given to the catalysts (metallosilsesquioxane) according to claim 5 of EP 2 989 155 B1.

The study of the activity of heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) for the formation of polyurethane compounds was conducted by way of example in comparison with dibutyltin dilaurate (DBTDL) and tin(II) 2-ethylhexanoate (tin octoate) in various unfoamed and foamed polyurethane systems. Particular attention was paid to the effect on the preparation of the silylated polyurethanes (SPUR) by the IPDI route. The model formulations from the CASE application sectors, soft foam and flexible foam (slabstock foam), were examined here with regard to their curing characteristics at room temperature (23° C./50% RH) using various polyols and isocyanates with the same catalyst content of TiPOSS and DBTDL or tin octoate. For simplification, the studies have been conducted under the assumption that a complete stoichiometric reaction (index 100) can take place between isocyanate and polyol. In principle, the studies are also applicable to the preparation of prepolymers. The catalytic activity of the catalysts examined was determined by the determination and comparison of cream time, fibre time and tack-free time.

1.) Study of TiPOSS/DBTDL in Unfoamed Polyurethane Formulations

a) Propylene Glycol Polyols

The polyol A component consisted of a polypropylene diol and the TiPOSS catalyst in the form of a 20% solution in diisononyl phthalate (DINP). For comparison of catalytic activity, a corresponding identical polyol A component was prepared using DBTDL. The amount of catalyst was 0.2 per cent by weight in each case (neglecting the amount of solvent). In order to study the influence of molecular weight, the molecular weight was additionally varied from low (MW ˜2000) to high (MW ˜18 000), since it can be assumed that the reactivity of polypropylene polyols that are of limited reactivity in any case will decrease further with rising molecular weight, and hence differences in reactivity will be particularly readily observable.

The polypropylene polyols tested were accordingly those with MW˜2000 (Rokopol D2002, PCC Rokita), MW ˜8000 (Rokopol LDB 8000), MW ˜12 000 (Rokopol LDB 12 000) and MW ˜18 000 (Rokopol LDB 18 000).

The crosslinker components used were the isocyanates P-MDI (Voranate M230, Dow), IPDI (Wanate IPDI, DKSH) and HDI trimer isocyanurates (Vestanat HT2500/100). The reaction between polyol A and isocyanate B component was effected by stirring the two components at 1000 rpm with a conventional propeller stirrer for 10 s. After the stirring process had ended, the resultant reaction mixture was cast into slabs of thickness ˜6 mm (10 g). The curing characteristics were determined from the cream time, fibre time and tack-free time.

It was found that the TiPOSS-catalysed curing of polyurethane at room temperature is significantly accelerated using the polypropylene polyols described compared to the corresponding DBTDL-catalysed crosslinking. The acceleration of the reaction, according to the combination of polyol and isocyanate examined, is between a factor of 2 and a factor of 100. Viewed overall, the factor of reaction acceleration when TiPOSS is used particularly surprisingly increases for the HDI trimer of isocyanurate used, and to a lesser degree for IPDI.

Conclusion for SPUR Methodology:

Since the reaction between the DMC polyols and IPDI isocyanate is the crucial reaction for the commercial preparation of SPUR (hybrid polymers), this finding is of great significance. Since we are already able to establish a considerable increase in reaction at room temperature and with 1:1 stoichiometry, it can be expected that, under the customary conditions of SPUR prepolymer preparation, it is possible to work with considerably smaller amounts of catalyst (1/5 to 1/10) and/or a lower temperature (<80° C.) and/or shortening of the reaction time. Since the formation of by-products in this preparation leads to an unwanted increase in viscosity, a distinct improvement in the reaction regime and product quality is thus to be expected.

With regard to the ever-increasing economic significance of the SPUR products, the use of the TiPOSS catalyst is expected to lead both to a cost benefit over tin catalysts and to a product benefit.

a) Propylene Glycol Polyols, Ethylene Glycol-Tipped

In order to assess whether these observations are also applicable to more reactive polyether polyols, by way of example, polyether polyols with MW ˜4000 and f=2 and MW ˜4850 and f=3 tipped with ethoxy groups at the termini were examined. It has been found that the differences in reactivity of the polyol systems catalysed with TiPOSS and DBTDL are smaller in the case of use of reactive polyether triol. Here too, it is again observed that the acceleration in reactivity of the crosslinking by TiPOSS is particularly effective for the HDI trimer.

2.) Study of the Activity of TiPOSS/DBTL in Silane-Terminated Polyurethanes

The speed of fibre formation and curing in silane-terminated polyurethanes was determined on 6 mm SPUR slabs that had been produced by mixing the silane-terminated polyurethanes with 0.2 per cent by weight each of TiPOSS and DBTL (each in solution, 20% in DINP). The mixing was effected with exclusion of air in an argon inert gas atmosphere with a conventional propeller stirrer. The mixed material was cured at 23° C./50% RH.

3.) Study of the Activity of TiPOSS/DBTDL in Flexible Polyurethane Foam Formulations

The polyol A component consisted of a reactive, ethoxy group-tipped polyether triol (Rokopol M 5020, f=3), water and the TiPOSS catalyst, in the form of a 20% solution in diisononyl phthalate (DINP). For comparison of catalytic activity, a corresponding identical polyol A component was prepared using DBTDL. The amount of catalyst was 0.2 per cent by weight in each case (neglecting the DINP solvent). By way of comparison, the reaction was conducted using a less reactive polypropylene polyol (Rokopol D 2002, f=2).

The crosslinking component used was the isocyanate P-MDI (Voranate M230). The reaction between polyol A and isocyanate B component was effected by stirring the two components at 2500 rpm with a conventional propeller stirrer for 10 s. The reaction was stoichiometric. After the stirring process had ended, the reaction mass obtained (20 g) was poured into cups. The curing characteristics were determined from the cream time and tack-free time.

It was found that the activity of TiPOSS when using ethoxylated polyols is comparable to that of DBTDL. By contrast, the curing process in the case of the formulation made from a pure polypropylene polyol is more significantly accelerated by TiPOSS.

4.) Study of the Activity of TiPOSS/Tin Octoate in a Slabstock Polyurethane Foam Formulation

The polyol A component consisted of a standard polyester polyol based on Desmophen 2200 B, an amine catalyst (N,N-dimethylpiperazine and N,N-dimethylhexadecylamine), cell stabilizers, water and the TiPOSS catalyst, in the form of a 20% solution in DINP. For comparison of catalytic activity, a corresponding identical polyol A component was prepared using tin octoate. The amount of TiPOSS and tin octoate catalyst was 0.03 per cent by weight in each case.

The crosslinking component used was the isocyanate Desmodur T65 and a prepolymer having an NCO content of about 12%. The reaction was effected in a stoichiometric ratio (index 100). The reaction between polyol A and isocyanate B components was effected by stirring the two components at 1000 rpm with a Visco Jet stirrer unit for 10 s. After the stirring process had ended, the resultant reaction mass (˜400 g) was poured into a 2 L wooden box, and the curing characteristics were determined from the cream time and tack-free time.

It was found that the activity of TiPOSS is comparable to that of tin octoate. The resultant foams from the reaction with TiPOSS have lower density; strength properties and indentation hardness are correspondingly lower.

5.) Overall Conclusion/Applications

a) Use of TiPOSS in the Preparation of SPUR Prepolymers

The significant increase in reaction described in the reaction between the DMC polyols and IPDI can be used for the commercial production of SPUR (hybrid polymers). It can be expected here that it will be possible to use considerably smaller amounts of catalyst (1/5 to 1/10) and/or a lower temperature (<80° C.) and/or a shortened reaction time. Since, in general, the formation of by-products in this preparation leads to an unwanted increase in viscosity, a distinct improvement in the reaction regime and product quality, including lower product viscosity (very important for the formulator), is thus possible.

b) Preparation of KOH-Based PU Prepolymers with TiPOSS

The formation of prepolymers obtained from the reaction of KOH-based polyols and aliphatic and aromatic isocyanates can be brought about with considerably smaller amounts of TiPOSS catalyst (1/5 to 1/10) and/or a lower temperature (<80° C.) and/or a shortened reaction time. Since the formation of by-products in this preparation leads to an unwanted increase in viscosity, a distinct improvement in the reaction regime and product quality can thus be assumed.

c) Use of TiPOSS in 2-Component Clear Encapsulating Systems and PU Varnishes Based on HDI and Other Aliphatic Isocyanates

Use of TiPOSS as catalyst increases the curing rate in 2-component polyurethane clear encapsulation systems and PU varnishes. The increase in molecular weight distinctly improve the mechanical properties of the varnishes and encapsulating compounds.

d) TDI Foams/Use of TiPOSS in the Production of Slabstock Foams

In the production of TDI-based slabstock foams, through use of TiPOSS as catalyst, it is possible to dispense with the use of tin compounds that are harmful to health—as in all other applications mentioned in 5.). There is no loss here in product quality.

e) FIPFG (Foamed in Place Foam Gaskets)—Sealant Foams

The production of 2-component polyurethane systems for the FIPFG process based on TiPOSS-catalysed curing is particularly advantageous since the curing process is accelerated by the higher reactivity of TiPOSS compared to DBTL. Polyurethane products can additionally be produced without tin compounds that are harmful to health, which is particularly important for the production of sealant materials in the medical sector, kitchen applications, etc.

f) Use of TiPOSS in Moisture-Curing 1-Component Isocyanate-Terminated Prepolymers

The curing of 1-component isocyanate-terminated prepolymers can be accelerated by the use of TiPOSS. It is possible to dispense with the use of tin compounds that are harmful to health. This is of particular relevance when these prepolymers are used as adhesives for customary floor coverings, since it is thus possible to avoid possible contamination, even if only by small amounts of tin, via the skin of the foot.

6.) Specific Embodiments

Studies on the activity of heptaisobutyl-POSS-titanium(IV) ethoxide TiPOSS in comparison to DBTL

TABLE 1
		Polyols from the KOH-catalyzed reaction
		f = 2, MW = 2000, PO
		f = 2, MW = 4000, PO, EO tipped
Isocyanate	Catalyst	f = 3, MW = 4800, PO, EO tipped
P-MDI*	TiPOSS 0.2% vs.	+
	DTBL 0.2 %
P-MDI	TiPOSS 0.2% vs.	++
	DTBL 0.2 %

	TABLE 2
	SPUR	Catalyst	activity
	Silylated	TiPOSS 0.2% vs.	+
	Polyurethane	DTBL 0.2 %
	(nonaromatic)

LIST OF ABBREVIATIONS

Coatings, Adhesives, Sealants, Elastomers (CASE)

Diisononyl phthalate (DINP)

Dibutyltin dilaurate (DBTDL or DBTL)

Tin(II) 2-ethylhexanoate (tin octoate)

Silylated polyurethanes/silylated polyurethane resins (SPUR)

Heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS)

Dimethylcyclosiloxane (DMC)

Polyurethane (PU)

Potassium hydroxide (KOH)

FIPFG (foamed in place foam gaskets—gasket foams)

Titanium (Ti)

Polyhedral oligomeric silsesquioxane (POSS)

EMBODIMENTS, ESPECIALLY FOR EXAMPLES IV

• 1. Process for preparing prepolymers by reacting a component A with a component B in the presence of a catalyst in a liquid medium, where component A is a polyol and component B a crosslinking component (crosslinker), characterized in that component A is in deficiency relative to component B, and component A and component B are especially used in a ratio of at least 1:1.05, preferably of 1:2.2, and the catalyst is selected from the group of the tin-free polyhedral oligomeric metallosilsesquioxanes, preferably from the group of the titanium(IV) polyoctahedral silsesquioxanes.
• 2. Process for preparing polyurethanes by combining a two-component system having a component A and a components B in the presence of a catalyst in a liquid medium, where component A is a polyol and component B a crosslinking component (crosslinker), characterized in that components A and B are present separately, and the catalyst has preferably been formulated with component A, and components A and B are present in a ratio of 1.2:1.0 up to 1.0:1.2.
• 3. Process for producing polyurethane systems, characterized in that the prepolymers are prepared or preparable according to either of Embodiments 1 and 2 using a catalyst selected from the group of the tin-free polyhedral oligomeric metallosilsesquioxanes, preferably from the group of the titanium(IV) polyoctahedral silsesquioxanes.
• 4. Process according to Embodiment 3, characterized in that the prepolymers are functionalized before the reaction with aminosilanes.
• 5. Process according to any of the preceding embodiments, characterized in that auxiliaries are added.
• 6. Process according to Embodiment 5, characterized in that the auxiliaries are selected from the group consisting of water, cell stabilizers, amine catalysts, fillers, adhesion promoters, moisture scavengers, plasticizers, UV stabilizers, thixotropic agents, or combinations thereof, preferably with one or more additives being one or more silanes.
• 7. Process according to Embodiment 6, characterized in that the amine catalyst may be N,N-dimethylpiperazine and/or N,N-dimethylhexadecylamine or a mixture thereof.
• 8. Process according to any of the preceding embodiments, characterized in that the catalyst is R¹—POSS-titanium(IV) ethoxide (TiPOSS) where R¹ is an alkyl, allyl or aryl radical or mixtures thereof, and R¹ is preferably a heptaisobutyl radical.
• 9. Process according to any of the preceding embodiments, characterized in that the catalyst content is between 0.0001% and 5% by weight, preferably between 0.001% and 2% by weight, further preferably between 0.01% and 0.3% by weight, especially preferably 0.2, more especially preferably 0.03.
• 10. Process according to any of the preceding embodiments, characterized in that the crosslinker is an isocyanate.
• 11. Process according to Embodiment 10, characterized in that the isocyanate is aromatic and/or aliphatic, preferably methylene diphenyl isocyanates (MDI) and/or isophorone diisocyanate (IPDI) and/or a hexamethylene diisocyanate trimer (HDI trimer) or a mixture thereof.
• 12. Process according to any of the preceding embodiments, characterized in that the polyol is a polyoxypropylene diol, preferably having a molar mass between 2000 g/mol and 18 000 g/mol, more preferably having a molar mass between 12 000 g/mol and 18 000 g/mol.
• 13. Process according to any of the preceding Embodiments 1 to 11, characterized in that the polyol is an ethoxylated polyol, preferably a polyether triol tipped with ethoxy groups, and more preferably has a molar mass between 2000 g/mol and 4850 g/mol.
• 14. Process according to any of Embodiments 1 to 11, characterized in that the polyol is a polyester polyol, preferably Desmophen 2200 B.
• 15. Process according to any of the preceding embodiments, characterized in that the polyol comes from a KOH— and/or DMC-catalysed reaction.
• 16. Process according to any of the preceding embodiments, characterized in that the liquid medium is an organic solvent, preferably diisononyl phthalate (DINP).
• 17. Process according to any of the preceding embodiments, characterized in that it is tin-free.

Claims

1. A composition comprising at least one silylated polymer (SiP) and at least two catalysts A and B, wherein catalyst A is a metal-siloxane-silanol(ate) compound.

2. The composition according to claim 1, wherein catalyst A is heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), and catalyst B is a metal-siloxane-silanol(ate) compound.

3. The composition according to claim 2, wherein catalyst A is heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), and catalyst B is heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS).

4. The composition according to claim 1, wherein catalyst B is not a metal-siloxane-silanol(ate) compound.

5. The composition according to claim 4, wherein catalyst B is an organometallic compound.

6. The composition according to claim 4, wherein catalyst B is selected from the group consisting of tetraalkyl titanates, such as tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-sec-butyl titanate, tetraoctyl titanate, tetra(2-ethylhexyl) titanate, dialkyl titanates ((RO)2TiO2 in which R is, for example, isopropyl, n-butyl, isobutyl), such as isopropyl n-butyl titanate; titanium acetylacetonate chelates, such as diisopropoxybis(acetylacetonate) titanate, diisopropoxybis(ethylacetylacetonate) titanate, di-n-butylbis(acetylacetonate) titanate, di-n-butylbis(ethylacetoacetate) titanate, triisopropoxidebis(acetylacetonate) titanate, zirconium tetraalkoxides, such as zirconium tetraethoxide, zirconium tetrabutoxide, zirconium tetrabutyrate, zirconium tetrapropoxide, zirconium carboxylates, such as zirconium diacetate; zirconium acetylacetonate chelates, such as zirconium tetra(acetylacetonate), tributoxyzirconium acetylacetonate, dibutoxyzirconium bisacetylacetonate, aluminium trisalkoxides, such as aluminium triisopropoxide, aluminium trisbutoxide; aluminium acetylacetonate chelates, such as aluminium tris(acetylacetonate) and aluminium tris(ethylacetylacetonate), organotin compounds such as dibutyltin dilaurate (DBTL), dibutyltin maleate, dibutyltin diacetate, tin(II) 2-ethylhexanoate (tin octoate), tin naphthenate, dimethyltin dineodecanoate, dioctyltin dineodecanoate, dimethyltin dioleate, dioctyltin dilaurate, dimethyl mercaptides, dibutyl mercaptides, dioctyl mercaptides, dibutyltin dithioglycolate, dioctyltin glycolate, dimethyltin glycolates, a solution of dibutyltin oxide, reaction products of zinc salts and organic carboxylic acids (carboxylates) such as zinc(II) 2-ethylhexanoate or zinc(II) neodecanoate, mixtures of bismuth carboxylates and zinc carboxylates, reaction products of bismuth salts and organic carboxylic acids, such as bismuth(III) tris(2-ethylhexanoate) and bismuth(III) tris(neodecanoate) and bismuth complexes, organolead compounds such as lead octoxide, organovanadium compounds, amine compounds such as butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole and 1,8-diazabicyclo(5.4.0)undecene-7 (DBU), salts of these amines with carboxylic acids or other acids or mixtures thereof.

7. The composition according to claim 6, wherein catalyst B is selected from the group consisting of dibutyltin dilaurate (DBTL), tin(II) 2-ethylhexanoate (tin octoate), zinc(II) 2-ethylhexanoate, zinc(II) neodecanoate, bismuth(III) tris(2-ethylhexanoate), bismuth(III) tris(neodecanoate) or mixtures thereof.

8. The composition according to claim 6, wherein catalyst B is dibutyltin dilaurate (DBTL).

9. The composition according to claim 3, wherein catalyst A is selected from the group consisting of heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) and heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS), preferably in that the catalyst is heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS).

10. The composition according to claim 9, wherein said composition includes more than one catalyst A metal-siloxane-silanol(ate) compound.

11. The composition according to claim 1, wherein the metal-siloxane-silanol(ate) compound has the general formula R*qSirOsMt where each R* is independently selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C6-cycloalkyl, optionally substituted C2- to C20-alkenyl, optionally substituted C6- to C10-aryl, —OH and —O—(C1- to C10-alkyl), each M is independently selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals of transition groups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,

q is an integer from 4 to 19,

r is an integer from 4 to 10,

s is an integer from 8 to 30, and

t is an integer from 1 to 8.

12. The composition according to claim 1, wherein the metal-siloxane-silanol(ate) compound has a general structure (I)

where

X1, X2 and X3 are independently selected from Si and M1, where M1 is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals,

especially from the group consisting of metals of transition groups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,

Z1, Z2 and Z3 are independently selected from the group consisting of L2, R5, R6 and R7, where L2 is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L2 is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl;

R1, R2, R3, R4, R5, R6 and R7 are independently selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C5- to C10-aryl;

Y1 and Y2 are independently —O-M2-L3Δ, or Y1 and Y2 are associated and together are —O-M2(L3Δ)-O— or —O—, where L3 is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L3 is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and where M2 is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals,

especially from the group consisting of metals of transition groups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,

and

X4 is -M3L1Δ or M3 and Q1 and Q2 are H or each is a single bond joined to M3, where L1 is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L1 is selected from the group consisting of —OH, —O— methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and where M3 is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals,

especially from the group consisting of metals of transition groups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,

or

X4 is -M3L1Δ and Q2 is H or a single bond joined to M3 and Q1 is H, M4L4Δ or where M4 is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals,

especially from the group consisting of metals of transition groups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,

and where L4 is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L4 is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O— isobutyl, and where R8 is selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C5- to C10-aryl,

or

X4, Q1 and Q2 are independently -M3L1Δ,

or

X4 is —Si(R8)—O-M3L1Δ, Q2 is a single bond joined to the silicon atom of X4 and Q1 is -M4L4Δ,

or

X4 is —Si(R8)—O-M3L1Δ, Q2 is a single bond joined to the silicon atom of X4 and Q1 is a single bond joined to the M3 atom of X4.

13. The composition according to claim 1, wherein the metal-siloxane-silanol(ate) compound has the structural formula (II)

where

Z1, Z2 and Z3 are independently selected from the group consisting of L2, R5, R6 and R7, where L2 is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L2 is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl;

R1, R2, R3 and R4 are independently selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C5- to C10-aryl;

and

X4 is -M3L1Δ or M3 and Q1 and Q2 are H or each is a single bond joined to M3, where L1 is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L1 is selected from the group consisting of —OH, —O— methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and where M3 is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals,

especially from the group consisting of metals of transition groups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,

or

X4 is -M3L1Δ and Q2 is H or a single bond joined to M3 and Q1 is H, M4L4Δ or where M4 is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals,

especially from the group consisting of metals of transition groups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,

and where L4 is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L4 is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O— isobutyl, and where R8 is selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C5- to C10-aryl,

or

X4, Q1 and Q2 are independently -M3L1Δ,

or

X4 is —Si(R8)—O-M3L1Δ, Q2 is a single bond joined to the silicon atom of X4 and Q1 is -M1L4Δ,

or

X4 is —Si(R8)—O-M3L1Δ, Q2 is a single bond joined to the silicon atom of X4 and Q1 is a single bond joined to the M3 atom of X4.

14. The composition according to claim 13, wherein the metal-siloxane-silanol(ate) compound is a metal silsesquioxane of the structure (IV)

where X4 is selected from the group consisting of metals of transition groups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, most preferably from the group consisting of Ti and Sn, and is most preferably Ti, and X4 is joined to OR where R is selected from the group consisting of —H, -methyl, -ethyl, -propyl, -butyl, -octyl, -isopropyl, and -isobutyl, Z1, Z2 and Z3 are each independently C1- to C20-alkyl, C3- to C8-cycloalkyl, C2- to C20-alkenyl and C5- to C10-aryl, especially selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, heptyl, octyl, vinyl, allyl, butenyl and phenyl, and benzyl, and R1, R2, R3 and R4 are each independently C1- to C20-alkyl, C3- to C8-cycloalkyl, C2- to C20-alkenyl, and C5- to C10-aryl, especially selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, heptyl, octyl, vinyl, allyl, butenyl and phenyl, and benzyl.

15. The composition according to claim 14, wherein the metal-siloxane-silanol(ate) compound is a metal silsesquioxane of the structure (IVb)

where X4 is selected from the group consisting of metals of transition groups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, most preferably from the group consisting of Ti (and therefore is heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS)) and Sn (and therefore is heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS)), and is most preferably Ti (and therefore is heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS)).

16. The composition according to claim 1, wherein the silylated polymer (SiP) is obtainable by a synthesis, catalysed by a metal-siloxane-silanol(ate) compound, of at least one isocyanate-reactive compound, especially at least one hydroxy-functionalized polymer (component A), and one or more compounds having at least one isocyanate group (component B).

17. The composition according to claim 16, wherein the metal-siloxane-silanol(ate) compound for catalysed synthesis of component A and component B is heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) and/or heptaisobutyl POS S-tin(IV) ethoxide (SnPOSS), preferably heptaisobutyl POS S-titanium(IV) ethoxide (TiPOSS).

18. The composition according to claim 1, wherein the polymer backbone (P) of the silylated polymer (SiP) has constituents selected from the group consisting of polyurethanes, polyureas, polyethers, polyesters, phenolic resins, polyalkylenes, poly(meth)acrylates, polyamides, polycaprolactones, polybutadienes or polyisoprenes, and polycarbonates or mixtures thereof, preferably from the group consisting of polyurethanes, polyureas, poly(meth)acrylates or polyethers or mixtures thereof, most preferably polyethers.

19. The composition according to claim 1, wherein the silylated polymer (SiP) has at least two end groups of the general formula (V)

where X is C, Si or a heteroatom and these, according to their valency, optionally have one or more R8 radicals, preferably C, N, O, P, S, more preferably C, N or O, most preferably N or O, and each is bonded to a carbon in the polymer backbone, R* is O or an optionally substituted straight-chain or branched C1- to C25-alkyl group or an optionally substituted C4- to C18-cycloalkyl group or an optionally substituted C4- to C18-aryl group and, when R*=0, the silicon atom is bonded directly to the nitrogen atom, each Y is independently either O or a direct bond of the silicon atom to the respective R9, R10 or R11 radical, and preferably at least one Y is O, R8 is H, an optionally substituted straight-chain or branched C1- to C16-alkyl group, an optionally substituted straight-chain or branched C2- to C16-alkenyl group or an optionally substituted straight-chain or branched C2- to C16-alkynyl group, an optionally substituted C4- to C14-cycloalkyl group or an optionally substituted C4- to C14-aryl group, or a radical of the general structure (Vb), R12 and R14 are each independently H or a radical from the group consisting of —R15, —COOR15 and —CN, R13 is H or a radical from the group consisting of —CH2—COOR15, —COOR15, —CONHR15, —CON(R15), —CN, —NO2, —PO(OR15)2, —SOR15 and —SO2OR15, R15 is a hydrocarbyl radical having 1 to 20 carbon atoms and optionally having at least one heteroatom, R9, R10 and R11 are independently H, an optionally substituted straight-chain or branched C1- to C5-alkyl group, an optionally substituted straight-chain or branched C2- to C10-alkenyl group or an optionally substituted C4- to C14-cycloalkyl group or an optionally substituted C4- to C14-aryl group, m is 0 or 1 and, when m=0, the silicon atom is bonded directly to a carbon in the polymer backbone (P).

20. The composition according to claim 19, wherein the silylated polymer (SiP) has a polyether polymer backbone having at least two end groups of the general formula (V)

where X is N or O and N optionally has an R8 radical, R* is 0 or an optionally substituted straight-chain or branched C1- to C20-alkyl group or an optionally substituted C4- to C12-cycloalkyl group or an optionally substituted C4- to C12-aryl group, preferably an optionally substituted straight-chain or branched C1- to C15-alkyl group, and, when R*=0, the silicon atom is bonded directly to the nitrogen atom, Y in Y—R9 and Y—R10 are O and the Y in Y—R11 is either O or a direct bond of the silicon atom to the respective R11 radical, R8 is H, an optionally substituted straight-chain or branched C1- to C10-alkyl group, an optionally substituted straight-chain or branched C2- to C10-alkenyl group or an optionally substituted straight-chain or branched C2- to C10-alkynyl group, an optionally substituted C4- to C10-cycloalkyl group or an optionally substituted C4- to C10-aryl group or a succinic acid derivative of the general structure (Vb), R9, R10 and R11 are independently H, an optionally substituted straight-chain or branched C1- to C4-alkyl group, an optionally substituted straight-chain or branched C2- to C5-alkenyl group or an optionally substituted C4- to C10-cycloalkyl group or an optionally substituted C4- to C10-aryl group, preferably independently H or a C1- to C2-alkyl group, and m is 0 or 1 and, when m=0, the silicon atom is bonded directly to a carbon in the polymer backbone (P), preferably m=1.

21. The composition according to claim 20, wherein the silylated polymer (SiP) has a polyether polymer backbone having at least two end groups of the general formula (V)

where R* is 0 or an optionally substituted straight-chain or branched C1- to C15-alkyl group or an optionally substituted C4- to C6-cycloalkyl group or an optionally substituted C4- to C6-aryl group, preferably an optionally substituted straight-chain or branched C1- to C10-alkyl group, more preferably a C1-alkyl group (=alpha-silane) or a C3-alkyl group (=gamma-silane), and, when R*=0, the silicon atom is bonded directly to the nitrogen atom, R8 is H, an optionally substituted straight-chain or branched C1- to C8-alkyl group, an optionally substituted straight-chain or branched C2- to C8-alkenyl group or an optionally substituted straight-chain or branched C2- to C8-alkynyl group, an optionally substituted C4- to C6-cycloalkyl group or an optionally substituted C4- to C6-aryl group, R9, R10 and R11 are independently H, an optionally substituted straight-chain or branched C1- to C4-alkyl group, an optionally substituted straight-chain or branched C2- to C5-alkenyl group or an optionally substituted C4- to C6-cycloalkyl group or an optionally substituted C4- to C6-aryl group, preferably independently H or a C1- to C2-alkyl group, and m is 0 or 1 and, when m=0, the silicon atom is bonded directly to a carbon in the polymer backbone (P), preferably m=1.

22. The composition according to claim 16, wherein the hydroxy-functionalized polymer is selected from the group consisting of polyoxyalkylene diols or polyoxyalkylene triols, especially polyoxyethylene di- and triols and polyoxypropylene di- and triols, higher-functionality polyols such as sorbitol, pentaerythritol-started polyols, ethylene oxide-terminated polyoxypropylene polyols, polyester polyols, styrene-acrylonitrile, acryloyl-methacrylate, (poly)urea-grafted or -containing polyether polyols, polycarbonate polyols, CO2 polyols, polyhydroxy-functional fats and oils, especially castor oil, polyhydrocarbon polyols such as dihydroxypolybutadiene, polytetrahydrofuran-based polyethers (PTMEG), OH-terminated prepolymers based on the reaction of a polyetherol or polyesterol with a diisocyanate, polypropylene diols, polyester polyols or mixtures thereof, preferably polypropylene diols, polyester polyols, or mixtures thereof.

23. The composition according to claim 22, wherein the hydroxy-functionalized polymer is selected from the group consisting of polyoxyalkylene diols, polyoxyalkylene triols, especially polyoxyethylene di- and/or triols and/or polyoxypropylene di- and/or triols, KOH-catalysed hydroxy-functionalized polyethers or double metal cyanide complex-catalysed (DMC-catalysed) hydroxy-functionalized polyethers or mixtures thereof.

24. The composition according to claim 16, wherein component B is selected from the group consisting of aromatic and/or aliphatic isocyanates (Iso) of the general structure (VI) or mixtures thereof or isocyanatosilanes (Iso-Si) of the general structure (VII) or mixtures thereof

where Rx is a carbon-containing group, preferably at least one aromatic or aliphatic group or mixtures thereof, more preferably an optionally substituted straight-chain or branched C1- to C16-alkyl group, an optionally substituted straight-chain or branched C2- to C16-alkenyl group or an optionally substituted straight-chain or branched C2- to C16-alkynyl group, an optionally substituted C4- to C14-cycloalkyl group or an optionally substituted C4- to C14-aryl group, most preferably diphenylmethane, toluene, dicyclohexylmethane, hexane or methyl-3,5,5-trimethylcyclohexyl, each Y is independently either O or a direct bond of the silicon atom to the respective R9, R10 or R11 radical, and preferably at least one Y is O, z is at least 1, preferably at least 2, R9, R10 and R11 are independently H, an optionally substituted straight-chain or branched C1- to C5-alkyl group, an optionally substituted straight-chain or branched C2- to C10-alkenyl group or an optionally substituted C4- to C8-cycloalkyl group or an optionally substituted C4- to C8-aryl group and R* is 0 or an optionally substituted straight-chain or branched C1- to C25-alkyl group or an optionally substituted C4- to C18-cycloalkyl group or an optionally substituted C4- to C18-aryl group and, when R*=0, the silicon atom is bonded directly to the nitrogen atom.

25. The composition according to claim 16, wherein component B is selected from the group consisting of aromatic and/or aliphatic isocyanates (Iso) of the general structure (VI) or mixtures thereof or isocyanatosilanes (Iso-Si) of the general structure (VII) or mixtures thereof

where Rx is diphenylmethane, toluene, dicyclohexylmethane, hexane or methyl-3,5,5-trimethylcyclohexyl, preferably diphenylmethane or hexane or methyl-3,5,5-trimethylcyclohexyl, most preferably diphenylmethane or methyl-3,5,5-trimethylcyclohexyl, and z is at least 2, preferably 2, Y in Y—R9 and Y—R10 are O and the Y in Y—R11 is either O or a direct bond of the silicon atom to the respective R11 radical, R9, R10 and R11 are independently H, an optionally substituted straight-chain or branched C1- to C3-alkyl group and R* is 0 or an optionally substituted straight-chain or branched C1- to C15-alkyl group or an optionally substituted C4- to C6-cycloalkyl group or an optionally substituted C4- to C6-aryl group, preferably an optionally substituted straight-chain or branched C1- to C10-alkyl group, more preferably a C1-alkyl group (=alpha-silane) or a C3-alkyl group (=gamma-silane), and, when R*=0, the silicon atom is bonded directly to the nitrogen atom.

26. The composition according to claim 25, wherein Component B is at least one isocyanate (Iso) of the general structure (VI) selected from the group consisting of polymeric, oligomeric and monomeric methylene diphenyl isocyanate (MDI), especially from 4,4′-methylene diphenyl isocyanate (4,4′-MDI), 2,4′-methylene diphenyl isocyanate (2,4′-MDI), 2,2′-methylene diphenyl isocyanate (2,2′-MDI), 4,4′-diisocyanatodicyclohexylmethane (H12MDI), 2-methylpentamethylene 1,5-diisocyanate, dodecamethylene 1,12-diisocyanate, lysine and lysine ester diisocyanate, cyclohexane 1,3-diisocyanate, cyclohexane 1,4-diisocyanate, perhydro(diphenylmethane 2,4′-diisocyanate), perhydro(diphenylmethane 4,4′-diisocyanate), 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (=isophorone diisocyanate or IPDI), hexamethylene 1,6-diisocyanate (HDI) or the trimer thereof (HDI trimer), 2,2,4- and/or 2,4,4-trimethylhexamethylene 1,6-diisocyanate, 1,4-bis(isocyanato)cyclohexane, 1,4-bis(isocyanato)benzene (PPDI), 1,3- and/or 1,4-bis(isocyanatomethyl)cyclohexane, m- and/or p-xylylene diisocyanate (m- and/or p-XDI), m- and/or p-tetramethylxylylene 1,3-diisocyanate, m- and/or p-tetramethylxylylene 1,4-diisocyanate, bis(1-isocyanato-1-methylethyl)naphthalene, 1,3-bis(isocyanato-4-methylphenyl)-2,4-dioxo-1,3-diazetidine, naphthalene 1,5-diisocyanate (NDI), 3,3′-dimethyl-4,4′-diisocyanatodiphenyl (TODI), tolylene 2,4- and/or 2,6-diisocyanate (TDI), 1,3-bis(isocyanatomethyl)benzene or mixtures thereof, preferably 4,4′-methylene diphenyl isocyanate (4,4′-MDI) or isophorone diisocyanate (IPDI), hexamethylene 1,6-diisocyanate (HDI) or the trimer thereof (HDI trimer) or mixtures thereof, most preferably 4,4′-methylene diphenyl isocyanate (4,4′-MDI) or isophorone diisocyanate (IPDI) or mixtures thereof.

27. The composition according to claim 26, wherein Component B is at least one isocyanatosilane (Iso-Si) of the general structure (VII), or mixtures thereof,

where R9, R10, and R11 a methyl or ethyl group or mixtures thereof, preferably selected from the group consisting of 3-(triethoxy silyl)methyl isocyanate, 3-(trimethoxysilyl)methyl isocyanate, 3-(triethoxy silyl)ethyl isocyanate, 3-(trimethoxysilyl)ethyl isocyanate, 3-(triethoxysilyl)propyl isocyanate, 3-(trimethoxysilyl)propyl isocyanate, 3-(triethoxy silyl)butyl isocyanate, 3-(trimethoxysilyl)butyl isocyanate, 3-(triethoxysilyl)pentyl isocyanate, 3-(trimethoxysilyl)pentyl isocyanate, 3-(triethoxysilyl)hexyl isocyanate, 3-(trimethoxysilyl)hexyl isocyanate or mixtures thereof, preferably 3-(trimethoxysilyl)methyl isocyanate, 3-(triethoxysilyl)methyl isocyanate, 3-(trimethoxysilyl)propyl isocyanate, 3-(triethoxysilyl)propyl isocyanate or mixtures thereof, more preferably 3-(trimethoxysilyl)propyl isocyanate, 3-(triethoxysilyl)propyl isocyanate, or mixtures thereof.

28. The composition according to claim 1, wherein the silylated polymer (SiP) has been prepared by reaction with an aminosilane (AmSi).

29. The composition according to claim 28, wherein the aminosilane (AmSi) is at least one aminosilane (AmSi) of the general structure (VIII), or is a mixture thereof,

where R7 is H, R8 is H, an optionally substituted straight-chain or branched C1- to C25-alkyl group, an optionally substituted straight-chain or branched C2- to C25-alkenyl group or an optionally substituted C4- to C18-cycloalkyl group or an optionally substituted C4- to C18-aryl group, or a radical of the general structure (Vb), R* is 0 or an optionally substituted straight-chain or branched C1- to C25-alkyl group or an optionally substituted C4- to C18-cycloalkyl group or an optionally substituted C4- to C18-aryl group and, when R*=0, the silicon atom is bonded directly to the nitrogen atom, R12 and R14 are each independently H or a radical from the group consisting of —R15, —COOR15 and —CN, R13 is H or a radical from the group consisting of —CH2—COOR15, —COOR15, —CONHR15, —CON(R15), —CN, —NO2, —PO(OR15)2, —SOR15 and —SO2OR15, R15 is a hydrocarbyl radical having 1 to 20 carbon atoms and optionally having at least one heteroatom, R9, R10 and R11 are independently H, an optionally substituted straight-chain or branched C1- to C4-alkyl group, an optionally substituted straight-chain or branched C2- to C5-alkenyl group or an optionally substituted C4- to C10-cycloalkyl group or an optionally substituted C4- to C10-aryl group, preferably independently H or a C1-to C2-alkyl group, and each Y is independently either O or a direct bond of the silicon atom to the respective R9, R10 or R11 radical, and preferably at least one Y is O.

30. The composition according to claim 29, wherein the aminosilane (AmSi) of the general structure (VIII) is selected from the group of N-[3-(trimethoxysilyl)methyl]butylamine, N-[3-(triethoxysilyl)methyl]butylamine, N-[3-(trimethoxysilyl)ethyl]butylamine, N-[3-(triethoxysilyl)ethyl]butylamine, N-[3-(trimethoxysilyl)propyl]butylamine, N-[3-(triethoxysilyl)propyl]butylamine, N-[3-(trimethoxysilyl)butyl]butylamine, N-[3-(triethoxysilyl)butyl]butylamine, N-[3-(trimethoxysilyl)pentyl]butylamine, N-[3-(triethoxysilyl)pentyl]butylamine, N-[3-(trimethoxysilyl)hexyl]butylamine, N-[3-(triethoxysilyl)hexyl]butylamine, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-cyclohexyl-3-aminopropyltrimethoxysilane, N-cyclohexyl-3-aminopropyltriethoxysilane, N-(3-trimethoxysilylpropyl)aminosuccinic acid diethyl ester, N-(3-triethoxysilylpropyl)aminosuccinic acid diethyl ester or a mixture thereof, preferably N-[3-(trimethoxysilyl)methyl]butylamine, N-[3-(triethoxysilyl)methyl]butylamine, N-[3-(trimethoxysilyl)propyl]butylamine, N-[3-(triethoxysilyl)propyl]butylamine, N-(3-trimethoxysilylpropyl)aminosuccinic acid diethyl ester, N-(3-triethoxysilylpropyl)aminosuccinic acid diethyl ester, more preferably N-[3-(trimethoxysilyl)propyl]butylamine, N-[3-(triethoxysilyl)propyl]butylamine, N-[3-(trimethoxysilyl)methyl]butylamine, N-[3-(triethoxysilyl)methyl]butylamine, N-(3-triethoxysilylpropyl)aminosuccinic acid diethyl ester, N-(3-trimethoxysilylpropyl)aminosuccinic acid diethyl ester or a mixture thereof, most preferably N-(3-triethoxysilylpropyl)aminosuccinic acid diethyl ester, N-[3-(triethoxysilyl)propyl]butylamine, N-[3-(triethoxysilyl)methyl]butylamine or a mixture thereof.

31. (canceled)