Selective polyurethane prepolymer synthesis

Abstract

The present invention relates to a selective process for producing polyurethane prepolymers, to the polyurethane prepolymers obtainable from this process, and also to a process for producing moisture-crosslinked silylated polymers, more particularly silane-functional hybrid polymers, and also to their use in the CASE field (coatings, adhesives, sealants, and elastomers). The molecular weight profile of the polyurethane prepolymers of the present invention is determined by the area integral F in the range from 2000 Da to 200,000 Da along the x-axis. I The first section and area integral of F II This indicates that the second section has a

Description

[Technical Field]

[0001] The present invention relates to a selective process for producing polyurethane prepolymers, to polyurethane prepolymers obtainable from this process, and also to a process for producing water-crosslinked polymers, more specifically to a process for producing silane-functionalized hybrid polymers, and also to their use in the CASE field (coatings, adhesives, sealants, and elastomers). [Background technology]

[0002] Polymers and oligomers produced from isocyanate-holding compounds by reaction with hydroxyl or amine-functionalized compounds have long been known to be highly chemically diverse. Depending on the stoichiometric amounts of the reaction and the properties of the starting compounds, the products are correspondingly prepolymers containing urethane and / or urea groups and holding reactive isocyanate, hydroxyl, or amine groups at their ends, which can be further reacted in downstream steps during synthesis or used as crosslinkable base materials for adhesives and sealants, or otherwise as coating materials.

[0003] Particularly widespread and economically important are urethane prepolymers that retain isocyanate groups (NCO prepolymers). Urethane prepolymers containing curable functional groups such as silane groups are also known.

[0004] A common method for obtaining polyurethanes having terminal NCO groups is to react a polyfunctional alcohol with an excess isocyanate-containing compound, generally a polyisocyanate. These NCO-terminated polyurethane prepolymers may then act as initiators for producing silylated polymers, in which case the NCO prepolymer reacts with the corresponding aminosilane.

[0005] Silylated polyurethanes that undergo condensation ("crosslinking") upon contact with water or moisture in the air at room temperature have been known for a considerable period. They are also called moisture-crosslinked polymers. Factors such as silane group content and silane group structure determine whether long-chain polymers, wide-mesh three-dimensional network structures, or highly crosslinked systems are formed.

[0006] Water-crosslinked polymers, particularly silylated polyurethanes, have long been used in a wide variety of applications as adhesives and sealants. Accordingly, the fields of traditional silicone adhesives and sealants based on dimethylpolysiloxane, as well as polyurethane adhesives and sealants with free isocyanate groups, have been developed, extending to silane-terminated adhesives and sealants.

[0007] The conversion of long-chain polyols to NCO prepolymers and the subsequent silylation with alkoxysilanes containing NCO reactive groups are described, for example, in EP1093482A1. However, the high viscosity of silane-modified polymers means that plasticizers and reactive diluents are required.

[0008] High-viscosity silane-modified polymers (SMPs), when used in sealant and adhesive systems, typically require 30–50% by weight of inorganic fillers such as calcium carbonate or silicates, resulting in poor processing properties. The addition of plasticizers and diluents necessary for effective processing introduces problems caused by potential plasticizer migration. The addition of viscosity-reducing reactive diluents or monomeric alkoxysilanes results in undesirable costs and higher methanol release from the adhesive system.

[0009] EP1924623A1 describes, for example, alkoxysilyl groups and allophanate-modified urethane prepolymers, whose allophanate structures contain water-curable silane-functionalized radicals. Through controlled allophanation, the prior art has attempted to counteract the high viscosity resulting from the strong intermolecular hydrogen bonding and dipole interactions between urethane units and, if necessary, urea units. Example 1 describes how PPG (Acclaim 8200) conversion using a secondary aminosilane results in a polymer with a molecular weight of about 8000 g / mol and an initial viscosity of about 3000 mPas in the most preferred case, resulting in a viscosity of 20500 mPas.

[0010] EP2468759A1 describes urethane prepolymers similarly containing alkoxysilyl groups and modified with substituted aminosilanes. Examples 8-14 convert PPG (Acclaim 12200) with an IPDI of approximately 12,000 g / mol and a molar ratio of 1:2.4 into a PU prepolymer with a viscosity of 40,000 mPas. Subsequent reactions with various aminosilanes demonstrate the advantages of secondary aminosilanes as end-cappers compared to primary aminosilanes. Nevertheless, the lowest viscosity achieved (Example 13) was very high at 81,000 mPas, similarly suggesting a high proportion of oligomer components.

[0011] Processes described in the prior art for producing NCO-terminated polyurethane prepolymers often involve relatively large excess polyisocyanates, which must be fractionated through costly and inconvenient distillation processes, or lead to increased viscosity because they contain a high proportion of higher-grade oligomers. In particular, with long-chain polyols, oligomerization results in a considerable increase in viscosity and significant drawbacks that affect the processing properties of such NCO prepolymers.

[0012] At the same time, the processes described in the prior art for producing silylated polyurethanes often produce products with very high viscosity, making it more difficult to further process and compound the polymer. In this case, the viscosity of the silylated polymer is already considerably influenced by the viscosity of the previously produced NCO-terminated polyurethane prepolymer. Insufficient selectivity in the reaction regime here results in an NCO-terminated prepolymer with high viscosity and therefore poor processability.

[0013] Accordingly, an object of the present invention was to provide an NCO polyurethane prepolymer and a silylated polyurethane polymer containing urethane groups and prepared from the prepolymer, characterized in that the proportion of higher oligomers is reduced. The product shall, as far as possible, have an appropriate viscosity from the viewpoint of advantageous further processing and retain better processing characteristics. Despite prior art, there is still a need for polyurethanes that retain NCO-terminated groups, and silylated polyurethanes that can be prepared from them, which have low viscosity, are therefore suitable for a wide range of applications, and are particularly easy to process at room temperature. [Prior art documents] [Patent Documents]

[0014] [Patent Document 1] European Patent Application Publication No. 1093482 [Patent Document 2] European Patent Application Publication No. 1924623 [Patent Document 3] European Patent Application Publication No. 2468759 [Overview of the project] [Means for solving the problem]

[0015] The objective is achieved by the present invention through the provision of polyurethane prepolymers obtainable according to claim 1. Advantageous developments are the subject matter of the dependent or concurrent independent claims. Further subject matter of the present invention is compositions comprising mixtures of two or more polyurethane prepolymers of the present invention. The same can be said for silylated polyurethanes obtainable from these polyurethane prepolymers.

[0016] It was unexpectedly discovered that it is possible to produce NCO-terminated polyurethane prepolymers (hereinafter also simply referred to as "polyurethane prepolymers") having a narrow molar mass distribution through a kinetically controlled regime in the reaction of isocyanate-containing compounds and hydroxy-functionalized polymers. These prepolymers have low viscosity. The reaction kinetics according to this specification are determined, in particular, through parameters such as reaction temperature, catalyst properties and quantity, and reaction time.

[0017] In principle, NCO-terminated polyurethane prepolymers can be selectively produced by controlling the process regime using methods known to those skilled in the art. The selectivity of the reaction can be expressed by analyzing the molecular weight distribution. Therefore, the polyurethane prepolymers of the present invention can be characterized using their molecular weight distribution.

[0018] Therefore, selectivity can be verified and represented, for example, using gel permeation chromatography (GPC). An elugram obtained from the analysis of polyurethane prepolymers by GPC allows plotting the elution volume progressing with the continuous flow of eluent against the relevant signal intensity from the detector. The elugram shows, in its profile, "when" the components of the sample are detected by the detector, i.e., the elution volume (V, mL). Here, components with high molar weights are detected first, and components with low molar weights are detected later. According to the continuous measurement profile, the result is a curved profile with rising and falling regions (i.e., the intensity of the rise or fall in signal). The height of the intensity and the area integral below it indicate, among other things, the amount of each component present in the sample depending on the concentration of the injected sample.

[0019] It is possible to determine the relevant molar mass by comparing the elution volume of components of a sample with an unknown molar mass with the elution volume of molecules with a known molar mass (co-migration standard), by comparing it with the resulting graph, or mathematically using standardized regression analysis. From this, it is possible to obtain the corresponding molar mass distribution as a reciprocal plot of molar weight against the relevant signal intensity of the eluted sample. This plot is currently called the molecular weight profile. Here, the profile starts on the x-axis of the diagram of components of the sample with lower molecular weights, and therefore, as the profile on the x-axis progresses, it shows intensity signals of higher molecular weights.

[0020] The molecular weight profile of the polyurethane prepolymer of the present invention is, in the range of 2000 Da (x1) to 200000 Da (x3) along the x-axis, the area integral F I The first section and area integral F II It is shown that it has a second section, and its ratio F II / F Iis between 0 and 0.4 (including 0.4), preferably between 0.05 and 0.39, more preferably between 0.1 and 0.38. The first section extends from x1 to x2, the second section extends from x2 to x3, and x2 defines an extreme point between the (last) maximum intensity value (M1a) (see Figure 1) in the first section, which is within the molecular weight range of the hydroxy-functionalized polymer, and the first subsequent maximum intensity value (M2) in the second section.

[0021] In the context of the present invention, an "extreme point" is preferably a minimum point or, if not, an intensity minimum value.

[0022] "Molecular weight" can be used synonymously with the terms "molar weight" or "molar mass". It may be expressed in daltons (Da) or, if not, equivalently in grams per mole (g / mol).

Brief Description of the Drawings

[0023] [Figure 1] Figure 1 shows a molecular weight profile for calculating the ratio of area integrals (FII / FI). This shows the curve profile of such a molecular weight profile in the range from 2000 to 200000 Da (Da is also synonymous with g / mol).

Embodiments for Carrying out the Invention

[0024] In the first section, there may be one or more other maximum intensity values (e.g., M1b). The area integral of all these maximum values in the first section forms the area integral F I (F I = F(M1a) + F(M1b) + ···).

[0025] In the second section, there may similarly be one or more further maximum intensity values (e.g., M2a). The area integral of each maximum intensity value (M2) present in the second section is the sum of the area integrals F II of F IIforms part of = F(M2a) + F(M2b) + ···). In the present invention, F II The ratio of F I to is in the range from 0 to 0.4 (including 0.4), preferably from 0.05 to 0.39 (including 0.39), more preferably from 0.1 to 0.38 (including 0.38).

[0026] The position of the maximum strength M1a is within the range of the molecular weight of the specific hydroxy-functionalized polymer used. From this, the position of x2 similarly depends on the molecular weight of the hydroxy-functionalized polymer used.

[0027] Therefore, the maximum strength M1a is given by the following formula A

Chemical formula

[0028] Here, the area F I corresponds to the molecular weight range of the polyurethane prepolymer of the present invention obtained by the reaction of the NCO groups of the polyisocyanate. F II corresponds to the molecular weight range of the higher oligomers, and the higher oligomers are reaction products obtained in the production of the NCO-terminated prepolymer, and for this purpose the polyisocyanate used reacts with more than one NCO group, for example allophanate reaction products, biuret reaction products, isocyanurates, and oligomer blocks longer than isocyanate-polymer-isocyanate, etc.

[0029] For computer-controlled software, it is preferable to use the PSS WinGPC UniChrom V 8.31, Build 8417, manufactured by PSS GmbH, DE. The polyurethane prepolymer of the present invention, in the presence of a catalyst, I. A compound containing at least one isocyanate having a molecular weight of 120 g / mol to 1000 g / mol, II. Number average molecular weight M of 3500 to 100000 g / mol, preferably 3800 to 90000, more preferably 4000 to 80000 g / mol n Hydroxy-functionalized polymer having It can be obtained through a reaction with [this].

[0030] As a result of converting the polyurethane prepolymer of the present invention to silylated polyurethane, there is no significant change in the molecular weight distribution. Consequently, assuming that there is no water-induced condensation of the silylated polyurethane, the calculation of the area quotient of the present invention based on silylated polyurethane is permissible.

[0031] In this invention, the molecular weight is measured by the molecular weight distribution obtained by GPC (gel permeation chromatography) under the following conditions:

[0032] The column is prepared in a furnace heated to 70 degrees Celsius. The solvent guided into the column, which is maintained at this temperature, is tetrahydrofuran (THF) at a flow rate of 1 ml per minute, and 50 to 200 μl of a THF sample solution of polyurethane prepolymer, at a sample concentration of 0.5 to 1.5 g / L, is injected for measurement.

[0033] For measurement, the molecular weight distribution attributable to the sample is calculated from the relationship between the logarithm of a calibration curve created using multiple types of monodisperse polystyrene standard samples and the count at elution time.

[0034] Examples of standard polystyrene samples suitable for creating calibration curves are samples having the following molecular weights Mp [Da]: 66000; 42400; 25500; 15700; 8680; 6540; 4920; 3470; 2280; 1306; 370; 266, which are available from PSS Polymer-Standards-Service GmbH, Mainz, Germany. The detector used is a refractive index detector (RI detector).

[0035] The GPC columns can preferably be used in combination with a number of commercially available polystyrene gel columns. For example, such columns may preferably consist of a combination of an Agilent PLGEL 5μm MIXED-D, 7.5×300mm column and a PLGEL 3μm MIXED-E, 7.5×300mm column. In a combination consisting of three columns, the first two columns are PLGEL 5μm MIXED-D columns and the third column is a PLGEL 3μm MIXED-E, 7.5×300mm column.

[0036] In the examples described later, the molecular weight distribution of the polyurethane prepolymer is measured under the conditions shown there.

[0037] In the reaction for producing the polyurethane prepolymer of the present invention, the selected molar ratio of NCO groups to hydroxyl groups in the reaction of I. and II. is preferably from 5.0:1 to 1.05:1, more preferably from 4:1 to 1.5:1, and very preferably from 3.0:1 to 1.8:1.

[0038] The isocyanate-containing compound contains at least one NCO group (= isocyanate group). A distinction can be made between monoisocyanates (z = 1) and polyisocyanates (z ≧ 2). The NCO group can react with, for example, an alcohol to give a urethane or with an amine to give a urea derivative. The isocyanate-containing compound of the present invention can be described by the general formula (VI).

Chemical formula

[0039] The polyisocyanate used to produce the polyurethane prepolymer of the present invention may be a commercially conventional isocyanate, more specifically, one of the general formulas (VI) [ka] (In the formula, - R x is a carbon-containing group, preferably at least one aromatic or aliphatic group, or a mixture thereof, more preferably optionally substituted linear or branched C1 to C20 alkyl group, optionally substituted linear or branched C2 to C20 alkenyl group, optionally substituted linear or branched C2 to C20 alkynyl group, optionally substituted C4 to C14 cycloalkyl group, optionally substituted C4 to C14 aryl group, very preferably diphenylmethane, toluene, dicyclohexylmethane, hexane, or methyl-3,5,5-trimethylcyclohexyl, and (z is at least 2) It is a polyisocyanate.

[0040] Examples of suitable polyisocyanates include diphenylmethane diisocyanate (MDI), particularly diphenylmethane 4,4'-diisocyanate (4,4'-MDI), diphenylmethane 2,4'-diisocyanate (2,4'-MDI), diphenylmethane 2,2'-diisocyanate (2,2'-MDI), 4,4'-diisocyanatodicyclohexylmethane (H12MDI), 2-methylpentamethylene 1,5-diisocyanate, 2,2,4- and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate (TMDI), 1,12 Dodecamethylene diisocyanate, lysine diisocyanate and lysine ester diisocyanate, cyclohexane 1,3-diisocyanate, cyclohexane 1,4-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (=isophorone diisocyanate or IPDI), perhydro-2,4'-diphenylmethane diisocyanate and perhydro-4,4'-diphenylmethane diisocyanate, 1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), 1,6 Hexamethylene diisocyanate (HDI) or its trimer (HDI trimer), 1,4-bis(isocyanato)cyclohexane, 1,4-bis(isocyanate)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-tetramethyl-1,3-xylylene diisocyanate, bis(1-isocyanato-1-methylethyl)naphthalene, 2,4- and 2,6-toluene diisocyanate Diisocyanate (TDI), 1,3- and 1,4-phenylenediisocyanate, 2,4-dioxo-1,3-diazethidine-1,3-bis(methyl-m-phenylene)diisocyanate, 2,3,5,6-tetramethyl-1,4-diisocyanatobenzene, naphthalene 1,5-diisocyanate (NDI), 3,3'3'-dimethyl-4,4',4'-diisocyanatobiphenyl (TODI), or mixtures thereof, preferably diphenylmethane 4,4'-diisocyanate (4,4'-MDI), diphenylmethane-2,4'-diisocyanate (2,Examples include 4'-MDI), or isophorone diisocyanate (IPDI), 1,6-hexamethylene diisocyanate (HDI), or their trimers (HDI trimers), or mixtures thereof, very preferably diphenylmethane 4,4'-diisocyanate (4,4'-MDI), diphenylmethane 2,4'-diisocyanate (2,4'-MD), or isophorone diisocyanate (IPDI), oligomers and polymers of the aforementioned isocyanates, and any desired mixtures of the aforementioned isocyanates.

[0041] Preferred are aromatic, aliphatic, or alicyclic polyisocyanates having a molecular weight of 120 g / mol to 1000 g / mol and possessing NCO groups with different reactivity to diols. The different reactivity of the NCO groups of the polyisocyanates is caused by various substituents adjacent to the NCO groups on the molecule, which, by steric shielding, reduces the reactivity of, for example, one NCO group compared to other NCO groups, and / or takes the form of, for example, primary or secondary NCO groups through different bonding of the NCO groups with the rest of the molecule.

[0042] Preferred aromatic polyisocyanates include toluene diisocyanate (TDI), naphthalene 1,5-diisocyanate (NDI), naphthalene 1,4-diisocyanate (NDI), diphenylmethane diisocyanate (4,4'-MDI), diphenylmethane 2,4'-diisocyanate (2,4'-MDI), as well as mixtures of 4,4'-diphenylmethane diisocyanate (4,4'-MDI) and the 2,4'-MDI isomer, and all isomers of 1,3-phenylenediisocyanate.

[0043] Examples of preferred alicyclic polyisocyanates include, for example, 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethylcyclohexane (isophorone diisocyanate, IPDI), 1-methyl-2,4-diisocyanatocyclohexane, or hydrogenation products of the aforementioned aromatic polyisocyanates, particularly hydrogenated MDI in its pure form as an isomer, preferably hydrogenated 2,4'-MDI.

[0044] Examples of preferred aliphatic polyisocyanates include 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, and lysine diisocyanates.

[0045] Particularly preferred are isophorone diisocyanate (IPDI), and similarly diphenylmethane-2,4'-diisocyanate (2,4'-MDI), and similarly diphenylmethane-4,4'-diisocyanate (4,4'-MDI), as well as mixtures thereof. Particularly preferred are IPDI and mixtures with the aforementioned polyisocyanates.

[0046] Similarly, isophorone diisocyanate (IPDI), diphenylmethane 2,4'-diisocyanate (2,4'-MDI), and diphenylmethane 4,4'-diisocyanate (4,4'-MDI), as well as mixtures thereof, can be used in combination with other isocyanate-containing compounds.

[0047] It is understood that hydroxy-functional compounds refer to hydroxy-functional polymers. Suitable polyols for producing polyurethane polymers are, in particular, polyether polyols, polyester polyols, and polycarbonate polyols, as well as mixtures of these polyols. The number average molecular weight M of the hydroxy-functional compounds is preferably 3,500 to 100,000 g / mol, preferably 3,800 to 90,000, and more preferably 4,000 to 80,000 g / mol. n It holds.

[0048] The hydroxy-functionalized polymer is preferably selected from the group consisting of polyoxyalkylenediol or polyoxyalkylentriol, more specifically polyoxyethylene and polyoxypropylenediol and triol, higher functional polyols such as sorbitol, pentaerythritol-starting polyol, ethylene oxide-terminated polyoxypropylene polyol, polyester polyol, styrene-acrylonitrile, acrylic-methacrylate, (poly)urea-grafted or containing polyether polyol, polycarbonate polyol, CO2 polyol, polytetrahydrofuran-based polyether (PTMEG), OH-terminated prepolymers based on the reaction of polyetherol or polyesterol with polyisocyanate, polypropylene diol, polyester polyol, or mixtures thereof, preferably polypropylene diol, polyester polyol, or mixtures thereof.

[0049] "Polyethers" constitute a class of polymers. They are long-chain compounds containing at least two identical or different ether groups. In this invention, the term "polyether" is also used when polymer ether groups are interposed by other groups (e.g., copolymerized / integrated isocyanates or other polymer or oligomer units having different monomer origins).

[0050] Particularly suitable polyether polyols, also called polyoxyalkylene polyols or oligoetherols, are polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, oxetane, tetrahydrofuran, or mixtures thereof, with a starter molecule having two or more active hydrogen atoms, such as water, ammonia, etc., or a compound having two or more OH or NH groups, such as 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, These compounds are polymerized as needed using diethylene glycol, triethylene glycol, isomers dipropylene glycol and tripropylene glycol, isomers butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, 1,3- and 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol, aniline, and mixtures of the compounds described.

[0051] One particular embodiment uses polyether polyols having a block copolymer structure. These may be used by reacting the above-mentioned cyclic ethers having oligomer initiation blocks, such as polyoxytetramethylene-, polyoxyethylene-, polybutadiene-, polyisoprene-, polyamide-, polycaprolactone-, polyurethane-, etc., with hydroxyalkyl-substituted polydimethylsiloxanes, hydroxyl-containing polyacrylates and / or polymethacrylates, or polyesters, as described in, for example, EP 2 546 278 A1, EP 2 271 691 A1, EP 2 493 957 A1, and WO 09 / 133061 A1, with hydroxyalkyl-substituted polydimethylsiloxanes, hydroxyl-containing polyacrylates and / or polymethacrylates, or polyesters.

[0052] Another embodiment uses copolymers of carbon dioxide with cyclic ethers, particularly propylene oxide. These types of copolymers can be obtained using organometallic catalysts such as DMC and cobalt and chromium complexes, by a variety of processes, e.g., WO 2015 / 032717 A1, WO 2012 / 136657 A1, EP 2 321 364 A1, and WO 2018 / 158389 A1, etc. The high viscosity of these copolymers compared to pure polyethers makes the process of polyurethane prepolymer synthesis according to the present invention particularly advantageous. These types of copolymers may also be produced by the reaction of alcohols with dialkyl carbonates, e.g., dimethyl carbonate, diaryl carbonates, e.g., diphenyl carbonate, or phosgene. Particularly suitable are polycarbonate diols, especially amorphous polycarbonate diols.

[0053] Monools can also be used in the process of the present invention. In this case, the starter molecule used for polymerization with cyclic ethers includes monofunctional alcohols, such as methanol, undecyl alcohol, and isopropanol. The use of oligomeric monofunctional alcohols such as ethoxylated fatty alcohols is also possible.

[0054] Not only polyoxyalkylene polyols with a low degree of unsaturation (measured by ASTM D-2849-69 and expressed as milliequivalents of unsaturation per gram of polyol (meq / g)) and produced using, for example, a bimetallic cyanide complex catalyst (DMC catalyst), but also polyoxyalkylene polyols with a higher degree of unsaturation produced using, for example, anionic catalysts such as NaOH, KOH, CsOH, or alkali metal alkoxides can be used. Particularly suitable are polyoxyethylene polyols and polyoxypropylene polyols, more specifically polyoxyethylene diols, polyoxypropylene diols, polyoxyethylene triols, and polyoxypropylene triols.

[0055] Particularly suitable are polyoxyalkylenediols or polyoxyalkylentriols having a degree of unsaturation of less than 0.02 meq / g, as well as polyoxyethylenediols, polyoxyethylenetriols, polyoxypropylenediols, and polyoxypropylenetriols having molecular weights of 3,500 to 100,000 g / mol, preferably 3,800 to 90,000 g / mol, and more preferably 4,000 to 80,000 g / mol.

[0056] Similarly, particularly suitable are what are called ethylene oxide-terminated ("EO-end cap") polyoxypropylene polyols. The latter are specific polyoxypropylene-polyoxyethylene polyols obtained, for example, by subjecting pure polyoxypropylene polyols, especially polyoxypropylene diols and triols, to further alkoxylation with ethylene oxide after the polypropoxylation reaction, which consequently contain primary hydroxyl groups. In this case, polyoxypropylene-polyoxyethylenediols and polyoxypropylene-polyoxyethylenetriols are preferred. Even more suitable are polybutadiene polyols with hydroxyl groups at the terminus, such as those produced by polymerization of 1,3-butadiene and allyl alcohol, or by oxidation of polybutadiene, and their hydrogenation products are also suitable. Even more suitable are styrene-acrylonitrile grafted polyether polyols of the type commercially available under the trademark name LupranoL® from Elastogran GmbH, Germany.

[0057] Particularly suitable as polyester polyols are polyesters that retain at least two hydroxyl groups and are produced by known processes, particularly by polycondensation of hydroxycarboxylic acids or polycondensation of aliphatic and / or aromatic polycarboxylic acids with dihydric or polyhydric alcohols.

[0058] Particularly suitable polyester polyols are those produced from dihydric to trihydric alcohols, such as 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, glycerol, 1,1,1-trimethylolpropane, or mixtures of the aforementioned alcohols, and organic dicarboxylic acids or their anhydrides or esters, such as succinic acid, glutaric acid, adipic acid, trimethyladipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, dimer fatty acids, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, dimethyl terephthalate, hexahydrophthalic acid, trimellitic acid and trimellitic anhydride, or mixtures of the aforementioned acids, as well as polyester polyols derived from lactones, such as ε-caprolactone. Particularly suitable are those produced from polyester diols, especially dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, dimer fatty acids, phthalic acid, isophthalic acid, and terephthalic acid, or from lactones such as ε-caprolactone, as well as from dihydric alcohols such as ethylene glycol, diethylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, dimer fatty acid diol, and 1,4-cyclohexanedimethanol.

[0059] Particularly suitable polyols are polyester polyols and polyether polyols, more specifically polyoxyethylene polyols, polyoxypropylene polyols, and polyoxypropylene-polyoxyethylene polyols, preferably polyoxyethylene diols, polyoxypropylene diols, polyoxyethylene triols, polyoxypropylene triols, polyoxypropylene-polyoxyethylene diols, and polyoxypropylene-polyoxyethylene triols.

[0060] Molecular weight M nA polyol-based prepolymer having a molecular weight of 12,000 g / mol, and the viscosity of these prepolymers, which can be produced by the process of the present invention, is preferably in the range of 10,000 to 20,000 mPas. Molecular weight M n At 18,000 g / mol, the viscosity is in the range of 40,000 to 50,000 mPas (determined at 25°C by a Brookfield Rheometer DV-3T Extra, with spindle size and spindle speed selected so that the torque is >90%). Therefore, it can be at least 30% lower than the viscosity of a prepolymer that would not be produced by the process of the present invention.

[0061] The process of the present invention is preferably carried out at a temperature of at least 0°C, preferably at least 20°C, preferably 150°C or lower, and more specifically 80°C or lower.

[0062] The temperature at which the polyurethane prepolymer of the present invention is produced is very preferably between 10°C and 120°C, preferably between 15°C and 100°C, more preferably between 20°C and 90°C, and very preferably between 25°C and 85°C.

[0063] Suitable catalysts for producing the polyurethane prepolymer of the present invention are selected from the group including metal-siloxane-silanol (silanolate) compounds and organometallic compounds of elemental aluminum, tin, zinc, titanium, manganese, iron, bismuth, and zirconium, such as dibutyltin laurate, zinc octanoate, or titanium tetraisopropoxide, or otherwise tertiary amines, such as 1,4-diazabicyclo[2.2.2]octane.

[0064] The term "catalyst" refers to a substance that lowers the activation energy for a particular reaction and therefore increases the reaction rate.

[0065] The term “metal-siloxane-silanol(silanolate)” refers to all metal-siloxane compounds containing one, two, or more silanol and / or silanolate groups. In one embodiment of the present invention, it is also possible to exclusively include metal-siloxane-silanolate in the catalyst present. All combinations are included unless a distinction is made between these various scenarios in a particular case. In the following text, the metal-siloxane-silanol(silanolate) compounds (=metal-siloxane-silanol / silanolate compounds) just described are also called oligomeric metallo-silsesquioxanes, “POMS”, metal-silsesquioxanes, or metallated silsesquioxanes. The terms are used synonymously below.

[0066] In one embodiment of the present invention, the metal-siloxane-silanol (silanolate) compound may take the form of a monomer, oligomer, and / or polymer for generating the polyurethane prepolymer of the present invention, and the transition from oligomer to polymer is fluid according to a general definition.

[0067] In the oligomer and / or polymer metal-siloxane-silanol (silanolate) compounds, one or more metals were preferably present at the ends and / or within the chain.

[0068] In the production of polyurethane prepolymers according to the present invention, the catenary (chain-like) metal-siloxane-silanol(ate) compound is linear, branched, and / or cage-type.

[0069] The "cage" or oligomer or polymer "cage structure" of the present invention is a three-dimensional arrangement of a catenary metal-siloxane-silanol (silanolate) compound, where individual atoms in the chain form vertices of the compound's polyhedral base structure. In this case, interconnected atoms form at least two surfaces, resulting in common intersection lines. For example, in one embodiment of the present invention, a cubic base structure of the compound is formed. A compound defined by a single cage structure or, if otherwise, a singular cage structure, i.e., an isolated cage, represents structure (IVc). Compounds having multiple cages in the compound may also be described by compounds (I) and (Ia) through (Id). The cages in the present invention may be "open" or, if not, "closed." This depends on whether all the vertices are connected, joined, or coordinated so that a closed cage structure is formed. Examples of closed cages are structures (II), (IV), (IVb), and (IVc).

[0070] In this invention, the term "nuclear" refers to the nucleality of a compound, the number of metal atoms it contains. A mononuclear compound has one metal atom, while a polynuclear or dinuclear compound has two metal atoms in the compound. Here, the metals may be directly linked to each other or linked via their substituents. Examples of mononuclear compounds in this invention are represented, for example, by structures (IV), (IVb), (IVc), (Ia), (Ib), or (Ic); a dinuclear compound is represented by structure (Id).

[0071] Mononuclear single-cage structures are represented by metal-siloxane-silanol (silanolate) compounds (IV), (IVb), and (IVc). Mononuclear double-cage structures are, for example, structures (Ia), (Ib), or (Ic).

[0072] The metal-siloxane-silanol (silanolate) compound used in the production of the polyurethane prepolymer of the present invention preferably comprises an oligomeric metal-silsesquioxane.

[0073] More specifically, the metal-siloxane-silanol (silanolate) compound in the production of the polyurethane prepolymer of the present invention includes a polyhedral metal-silsesquioxane.

[0074] In one embodiment, the metal-siloxane-silanol (silanolate) compound is of the general formula R * q Si r O s M t It has, in the formula, each R * These are independently selected from the group consisting of optionally substituted C1-C20 alkyl groups, optionally substituted C3-C8 cycloalkyl groups, optionally substituted C2-C20 alkenyl groups, optionally substituted C5-C10 aryl groups, -OH groups, and -O-(C1-C10 alkyl groups). 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 metalloids; more specifically, from the group consisting of metals from transition elements groups 1, 2, 3, 4, 5, 8, 10, and 11, and metals from main group elements groups 1, 2, 3, 4, and 5; preferably selected from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn, and Bi; particularly preferably selected from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, and Bi; q is an integer between 4 and 19. r is an integer between 4 and 10. s is an integer between 8 and 30. t is an integer between 1 and 8.

[0075] In another embodiment, the metal-siloxane-silanol (silanolate) compound is of the general formula R # 4Si4O 11 The formula Y2Q2X4Z3, where each X is independently of Si, M 1 ,-M 3 L 1 Δ M3 , or -Si(R 8 )-OM 3 L 1 Δ Selected from the group consisting of M 1 and M 3 These are independently selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and metalloids; more specifically, selected from the group consisting of metals from transition elements groups 1, 2, 3, 4, 5, 8, 10, and 11, and metals from main group elements groups 1, 2, 3, 4, and 5; preferably selected from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn, and Bi; even more preferably selected from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, and Bi;

[0076] In the formula, L 1 The group is selected from the group consisting of -OH and -O-(C1 to C10 alkyl), more specifically -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 1 R is selected from the group consisting of -OH, -O-methyl, -O-ethyl, -O-propyl, -O-butyl, -O-octyl, -O-isopropyl, and -O-isobutyl, where R 8 This is selected from the group consisting of C1 to C20 alkyls, C3 to C8 cycloalkyls, C2 to C20 alkenyls, and C5 to C10 aryls, which are optionally substituted; Each Z is independent of the others, L 2 , R 5 , R 6 , and R 7 A group consisting of is selected, where L 2 The group is selected from the group consisting of -OH and -O-(C1 to C10 alkyl), more specifically -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 2This 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 # , R 5 , R 6 , and R 7 The elements are independently selected from the group consisting of optionally substituted C1-C20 alkyls, optionally substituted C3-C8 cycloalkyls, optionally substituted C2-C20 alkenyls, and optionally substituted C5-C10 aryls; each Y is independently -OM 2 -L 3 Δ And either the two Ys are together -OM 2 (L 3 Δ )-O- or -O-, L 3 The group is selected from the group consisting of -OH and -O-(C1 to C10 alkyl), more specifically -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 3 The group 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 M 2 These are independently selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and metalloids; more specifically, selected from the group consisting of metals from transition elements groups 1, 2, 3, 4, 5, 8, 10, and 11, and metals from main group elements groups 1, 2, 3, 4, and 5; preferably selected from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn, and Bi; even more preferably selected from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, and Bi; Each Q is independent of H and M. 4 L 4 Δ , -SiR 8 ,-M 3 L 1Δ or in each case the M of X 3 a single bond or -Si(R 8 )-O-M 3 L 1 Δ is a single bond connected to the Si atom of the radical, where M 3 , R 8 , and L 1 are as defined with respect to X, M 4 is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and metalloids, more particularly, metals from transition elements Groups 1., 2., 3., 4., 5., 8., 10., and 11., and metals from main group elements Groups 1., 2., 3., 4., and 5., preferably selected from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn, and Bi; even more preferably selected from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, and Bi; and L 4 is selected from the group consisting of -OH and -O-(C1 to C10 alkyl), more particularly -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 4 is selected from the group consisting of -OH, -O-methyl, -O-ethyl, -O-propyl, -O-butyl, -O-octyl, -O-isopropyl, and -O-isobutyl, provided that at least one X is M 3 , -M 3 L 1 Δ , or -Si(R 8 )-O-M 3 L 1 Δ is a prerequisite.

[0077] One of ordinary skill in the art would recognize that L 1 Δ , L 2 Δ , L 3 Δ , L 4 ΔThe number of possible ligands (Δ) can be directly derived from the number of free valencies of the metal atoms used, and we notice that this valency number is the valency of the metal.

[0078] In further embodiments, the metal-siloxane-silanol (silanolate) compound in the production of the polyurethane prepolymer of the present invention is of the general formula (Y 0.25 R # SiO 1.25 )4(Z 0.75 Y 0.25 XO)4(OQ)2 is formed, where each X is independently Si, M 1 ,-M 3 L 1 Δ M 3 , or -Si(R 8 )-OM 3 L 1 Δ Selected from the group consisting of M 1 and M 3 These are independently selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and metalloids, more specifically from the group consisting of metals from transition elements groups 1, 2, 3, 4, 5, 8, 10, and 11, and metals from main group elements groups 1, 2, 3, 4, and 5, preferably selected from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn, and Bi; even more preferably selected from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, and Bi; and L 1 The group is selected from the group consisting of -OH and -O-(C1 to C10 alkyl), more specifically -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 1 is selected from the group consisting of -OH, -O-methyl, -O-ethyl, -O-propyl, -O-butyl, -O-octyl, -O-isopropyl, and -O-isobutyl, and R 8This is selected from the group consisting of C1 to C20 alkyls, C3 to C6 cycloalkyls, C2 to C20 alkenyls, and C6 to C10 aryls, which are optionally substituted; Each Z is independent of the others, L 2 , R 5 , R 6 , and R 7 A group consisting of is selected, where L 2 The group is selected from the group consisting of -OH and -O-(C1 to C10 alkyl), more specifically -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 2 This 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 # , R 5 , R 6 , and R 7 These are independently selected from the group consisting of optionally substituted C1-C20 alkyls, optionally substituted C3-C6 cycloalkyls, optionally substituted C2-C20 alkenyls, and optionally substituted C6-C10 aryls; Each Y is independent of the others, -OM 2 -L 3 Δ And either the two Ys are together -OM 2 (L 3 Δ )-O- or -O-, L 3 The group is selected from the group consisting of -OH and -O-(C1 to C10 alkyl), more specifically -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 3 The group 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 M 2These are independently selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and metalloids; more specifically, selected from the group consisting of metals from transition elements groups 1, 2, 3, 4, 5, 8, 10, and 11, and metals from main group elements groups 1, 2, 3, 4, and 5; preferably selected from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn, and Bi; even more preferably selected from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, and Bi; Each Q is independent of H and M. 4 L 4 Δ , -SiR 8 ,-M 3 L 1 Δ And, or in each case, M of X 3 A single bond connected to it, or in each case -Si(R 8 )-OM 3 L 1 Δ It is a single bond connected to the Si atom of the radical, where M 3 , R 8 , and L 1 This is as defined with respect to X, and M 4 The metals are selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and metalloids, more specifically from the group consisting of metals from transition elements groups 1, 2, 3, 4, 5, 8, 10, and 11, and metals from main group elements groups 1, 2, 3, 4, and 5, preferably selected from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn, and Bi; even more preferably selected from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, and Bi, and L 4 The group is selected from the group consisting of -OH and -O-(C1 to C10 alkyl), more specifically -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 4It is selected from the group consisting of -OH, -O-methyl, -O-ethyl, -O-propyl, -O-butyl, -O-octyl, -O-isopropyl, and -O-isobutyl. However, at least one X is M 3 ,-M 3 L 1 Δ , or -Si(R 8 )-OM 3 L 1 Δ This is based on the premise that...

[0079] Metal-siloxane-silanol (silanolate) compounds are preferably of the general formula Si4O9R 1 R 2 R 3 R 4 X 1 X 2 X 3 X 4 OQ 1 OQ 2 Y 1 Y 2 Z 1 Z 2 Z 3 It has, in the formula, X 1 , X 2 , and X 3 They are independent of each other, Si or M 1 Selected from, M 1 The metal is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and metalloids; more specifically, from the group consisting of metals from transition elements groups 1, 2, 3, 4, 5, 8, 10, and 11, and metals from main group elements groups 1, 2, 3, 4, and 5; preferably selected from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn, and Bi; even more preferably selected from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, and Bi; Z 1 , Z 2 , and Z 3 They are independent of each other, L 2 , R 5 , R 6, and R 7 Selected from the group consisting of L 2 The group is selected from the group consisting of -OH and -O-(C1 to C10 alkyl), more specifically -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 2 This is selected from the group consisting of -OH, -O-methyl, -O-ethyl, -O-propyl, -O-butyl, -O-octyl, -O-isopropyl, and -O-isobutyl; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 These are independently selected from the group consisting of optionally substituted C1-C20 alkyls, optionally substituted C3-C8 cycloalkyls, optionally substituted C2-C20 alkenyls, and optionally substituted C5-C10 aryls; Y 1 and Y 2 They are independent of each other -OM 2 -L 3 Δ is, or Y 1 and Y 2 combine -OM 2 (L 3 Δ )-O- or -O-, L 3 The group is selected from the group consisting of -OH and -O-(C1 to C10 alkyl), more specifically -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 3 is selected from the group consisting of -OH, -O-methyl, -O-ethyl, -O-propyl, -O-butyl, -O-octyl, -O-isopropyl, and -O-isobutyl, and M 2The metals are selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and metalloids, more specifically from the group consisting of metals from transition elements groups 1, 2, 3, 4, 5, 8, 10, and 11, and metals from main group elements groups 1, 2, 3, 4, and 5, preferably selected from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn, and Bi; and more preferably selected from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, and Bi; and X 4 is, -M 3 L 1 Δ or M 3 Q 1 and Q 2 These are H or M respectively. 3 It is a single bond connected to L 1 The group is selected from the group consisting of -OH and -O-(C1 to C10 alkyl), more specifically -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 1 is selected from the group consisting of -OH, -O-methyl, -O-ethyl, -O-propyl, -O-butyl, -O-octyl, -O-isopropyl, and -O-isobutyl, and M 3 The metal is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and metalloids; more specifically, from the group consisting of metals from transition elements groups 1, 2, 3, 4, 5, 8, 10, and 11, and metals from main group elements groups 1, 2, 3, 4, and 5; preferably selected from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn, and Bi; even more preferably selected from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, and Bi; or X 4 is, -M 3 L 1 Δ Q 2 is H, or M3 It is a single bond connected to Q 1 H, M 4 L 4 Δ , or -SiR 8 And M 4 The metal is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and semimetals, more specifically from the group consisting of metals from transition elements groups 2, 3, 4, 5, and 8, and metals from main group elements groups 1, 2, 3, 4, and 5, more preferably from the group consisting of Zn, Sc, Ti, Zr, Hf, V, Pt, Ga, Sn, and Bi, and L 4 The group is selected from the group consisting of -OH and -O-(C1 to C10 alkyl), more specifically -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 4 is selected from the group consisting of -OH, -O-methyl, -O-ethyl, -O-propyl, -O-butyl, -O-octyl, -O-isopropyl, and -O-isobutyl, and R 8 This is selected from the group consisting of C1 to C20 alkyls which are substituted as needed, C3 to C8 cycloalkyls which are substituted as needed, C2 to C20 alkenyls which are substituted as needed, and C5 to C10 aryls which are substituted as needed. or X 4 Q 1 , and Q 2 They are independent of each other, -M 3 L 1 Δ And, or X 4 is -Si(R 8 )-OM 3 L 1 Q 2 X 4 It is a single bond connected to the Si atom, Q 1 is, -M 4 L 4 Δ And, or X 4 is -Si(R 8 )-OM 3 L 1 Δ Q 2 X 4 It is a single bond connected to the Si atom, Q 1 X 4 M 3 It is a single bond connecting atoms.

[0080] In further embodiments, the metal-silsesquioxane in the production of the polyurethane prepolymer of the present invention is a general formula (X 4 )(Z 1 Y 1 X 2 O)(Z 2 X 1 O2)(Z 3 X 3 O2)(R 1 Y 2 SiO)(R 3 SiO)(R 4 SiO2)(R 2 SiO2)(Q 1 )(Q 2 ) has, in the formula, X 1 , X 2 , and X 3 They are independent of each other, Si or M 1 Selected from, M 1 The metal is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and metalloids; more specifically, from the group consisting of metals from transition elements groups 1, 2, 3, 4, 5, 8, 10, and 11, and metals from main group elements groups 1, 2, 3, 4, and 5; preferably selected from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn, and Bi; even more preferably selected from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, and Bi; Z 1 , Z 2 , and Z 3 They are independent of each other, L 2, R 5 , R 6 , and R 7 Selected from the group consisting of L 2 The group is selected from the group consisting of -OH and -O-(C1 to C10 alkyl), more specifically -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 2 This is selected from the group consisting of -OH, -O-methyl, -O-ethyl, -O-propyl, -O-butyl, -O-octyl, -O-isopropyl, and -O-isobutyl; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 These are independently selected from the group consisting of optionally substituted C1-C20 alkyls, optionally substituted C3-C6 cycloalkyls, optionally substituted C2-C20 alkenyls, and optionally substituted C6-C10 aryls; Y 1 and Y 2 They are independent of each other, -OM 2 -L 3 Δ is, or Y 1 and Y 2 combine -OM 2 (L 3 Δ )-O- or -O-, L 3 The group is selected from the group consisting of -OH and -O-(C1 to C10 alkyl), more specifically -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 3 is selected from the group consisting of -OH, -O-methyl, -O-ethyl, -O-propyl, -O-butyl, -O-octyl, -O-isopropyl, and -O-isobutyl, and M 2The metals are selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and metalloids, more specifically from the group consisting of metals from transition elements groups 1, 2, 3, 4, 5, 8, 10, and 11, and metals from main group elements groups 1, 2, 3, 4, and 5, preferably selected from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn, and Bi; and more preferably selected from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, and Bi; and X 4 is, -M 3 L 1 Δ or M 3 Q 1 and Q 2 These are H or M respectively. 3 It is a single bond connected to L 1 The group is selected from the group consisting of -OH and -O-(C1 to C10 alkyl), more specifically -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 1 is selected from the group consisting of -OH, -O-methyl, -O-ethyl, -O-propyl, -O-butyl, -O-octyl, -O-isopropyl, and -O-isobutyl, and M 3 The metal is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and metalloids; more specifically, from the group consisting of metals from transition elements groups 1, 2, 3, 4, 5, 8, 10, and 11, and metals from main group elements groups 1, 2, 3, 4, and 5; preferably selected from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn, and Bi; even more preferably selected from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, and Bi. or X 4 is, -M 3 L 1 Δ Q 2 is H, or M3 It is a single bond connected to Q 1 H, M 4 L 4 Δ , or -SiR 8 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, more specifically from the group consisting of metals from transition elements groups 2, 3, 4, 5, and 8, and metals from main group elements groups 1, 2, 3, 4, and 5, more preferably from the group consisting of Zn, Sc, Ti, Zr, Hf, V, Pt, Ga, Sn, and Bi, and L 4 The group is selected from the group consisting of -OH and -O-(C1 to C10 alkyl), more specifically -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 4 R is selected from the group consisting of -OH, -O-methyl, -O-ethyl, -O-propyl, -O-butyl, -O-octyl, -O-isopropyl, and -O-isobutyl, 8 This is selected from the group consisting of C1 to C20 alkyls which are substituted as needed, C3 to C6 cycloalkyls which are substituted as needed, C2 to C20 alkenyls which are substituted as needed, and C6 to C10 aryls which are substituted as needed. or X 4 Q 1 , and Q 2 They are independent of each other, -M 3 L 1 Δ And, or X 4 is -Si(R 8 )-OM 3 L 1 Δ Q 2 X 4 It is a single bond connected to the Si atom, Q 1 is, -M 4 L 4 Δ And, or X 4 is -Si(R 8 )-OM 3 L 1 Δ Q 2 X 4 It is a single bond connected to the Si atom, Q 1 X 4 M 3 It is a single bond connecting atoms.

[0081] In a further sense of the present invention, a catalyst based on a metal-siloxane-silanol (silanolate) compound has structure (I) [ka] (Here, X 1 , X 2 , and X 3 They are independent of each other, Si or M 1 Selected from, M 1 The metal is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and metalloids; more specifically, from the group consisting of metals from transition elements groups 1, 2, 3, 4, 5, 8, 10, and 11, and metals from main group elements groups 1, 2, 3, 4, and 5; preferably selected from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn, and Bi; particularly preferably selected from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, and Bi; Z 1 , Z 2 , and Z 3 They are independent of each other, L 2 , R 5 , R 6 , and R 7 Selected from the group consisting of L 2 The group is selected from the group consisting of -OH and -O-(C1 to C10 alkyl), more specifically -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 2This is selected from the group consisting of -OH, -O-methyl, -O-ethyl, -O-propyl, -O-butyl, -O-octyl, -O-isopropyl, and -O-isobutyl; R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 These are independently selected from the group consisting of optionally substituted C1-C20 alkyls, optionally substituted C3-C8 cycloalkyls, optionally substituted C2-C20 alkenyls, and optionally substituted C5-C10 aryls; Y 1 and Y 2 They are independent of each other, -OM 2 -L 3 Δ is, or Y 1 and Y 2 combine -OM 2 (L 3 Δ )-O- or -O-, L 3 The group is selected from the group consisting of -OH and -O-(C1 to C10 alkyl), more specifically -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 3 is selected from the group consisting of -OH, -O-methyl, -O-ethyl, -O-propyl, -O-butyl, -O-octyl, -O-isopropyl, and -O-isobutyl, and M 2 The metal is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and metalloids; more specifically, from the group consisting of metals from transition elements groups 1, 2, 3, 4, 5, 8, 10, and 11, and metals from main group elements groups 1, 2, 3, 4, and 5; preferably selected from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn, and Bi; particularly preferably selected from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, and Bi; and X4 is, -M 3 L 1 Δ or M 3 Q 1 and Q 2 H, or M in each case. 3 It is a single bond connected to L 1 The group is selected from the group consisting of -OH and -O-(C1 to C10 alkyl), more specifically -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 1 is selected from the group consisting of -OH, -O-methyl, -O-ethyl, -O-propyl, -O-butyl, -O-octyl, -O-isopropyl, and -O-isobutyl, and M 3 The metal is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and metalloids; more specifically, from the group consisting of metals from transition elements groups 1, 2, 3, 4, 5, 8, 10, and 11, and metals from main group elements groups 1, 2, 3, 4, and 5; preferably selected from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn, and Bi; even more preferably selected from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, and Bi. or X 4 is, -M 3 L 1 Δ Q 2 is H, or M 3 It is a single bond connected to Q 1 H, M 4 L 4 Δ , or -SiR 8 And M 4The metals are selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and metalloids, more specifically from the group consisting of metals from transition elements groups 1, 2, 3, 4, 5, 8, 10, and 11, and metals from main group elements groups 1, 2, 3, 4, and 5, more preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn, and Bi; particularly preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, and Bi; and L 4 The group is selected from the group consisting of -OH and -O-(C1 to C10 alkyl), more specifically -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 4 R is selected from the group consisting of -OH, -O-methyl, -O-ethyl, -O-propyl, -O-butyl, -O-octyl, -O-isopropyl, and -O-isobutyl, 8 This is selected from the group consisting of C1 to C20 alkyls which are substituted as needed, C3 to C6 cycloalkyls which are substituted as needed, C2 to C20 alkenyls which are substituted as needed, and C5 to C10 aryls which are substituted as needed. or X 4 Q 1 , and Q 2 They are independent of each other, -M 3 L 1 Δ And, or X 4 is -Si(R 8 )-OM 3 L 1 Δ Q 2 X 4 It is a single bond connected to the Si atom, Q 1 is, -M 4 L 4 Δ And, or X 4 is -Si(R 8)-OM 3 L 1 Δ Q 2 X 4 It is a single bond connected to the Si atom, Q 1 X 4 M 3 (A single bond connecting atoms) It may also be described by [another source].

[0082] In a further preferred embodiment, the metal-siloxane-silanol (silanolate) compound in the production of the polyurethane prepolymer of the present invention has general formula (I) and X 1 , X 2 , and X 3 They are Si, independently of each other. X 4 is, -M 3 L 1 Δ Q 1 and Q 2 These are M 3 It is a single bond connected to, where L 1 The group consisting of -OH and -O-(C1 to C10 alkyl) is selected, more specifically from the group consisting of -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 1 M is selected from the group consisting of -OH, -O-methyl, -O-ethyl, -O-propyl, -O-butyl, -O-octyl, -O-isopropyl, and -O-isobutyl. 3 The metal is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and metalloids; more specifically, from the group consisting of metals from transition elements groups 1, 2, 3, 4, 5, 8, 10, and 11, and metals from main group elements groups 1, 2, 3, 4, and 5; preferably selected from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn, and Bi; particularly more preferably selected from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, and Bi; Z 1 , Z2 , and Z 3 Each of these is independently selected from optionally substituted C1-C20 alkyls, optionally substituted C3-C8 cycloalkyls, optionally substituted C2-C20 alkenyls, and optionally substituted C5-C10 aryls. R 1 , R 2 , and R 3 Each of these is independently selected from optionally substituted C1-C20 alkyls, optionally substituted C3-C8 cycloalkyls, optionally substituted C2-C20 alkenyls, and optionally substituted C5-C10 aryls. Y 1 and Y 2 They come together to form -O-.

[0083] In one embodiment, depending on the equivalent amount of metal present, the metal-siloxane-silanol (silanolate) compound of formula (I) may take the form of a mononuclear monomer or a multinuclear form of a dimer (two-nuclear), trimer (three-nuclear), multimer (multi-nuclear), and / or mixture thereof, and thus structures of formulas (Ia) to (Id) are possible, for example.

[0084] Further polynuclear metal-siloxane-silanol (silanolate) compounds that can be used in the present invention are structures (Ia), (Ib), (Ic), or (Id), [ka] Here, 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, more specifically from the group consisting of metals from transition elements groups 1, 2, 3, 4, 5, 8, 10, and 11, and metals from main group elements groups 1, 2, 3, 4, and 5, preferably selected from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn, and Bi; particularly more preferably selected from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, and Bi; each R(R 1 From R 4 The elements are independently selected from the group consisting of optionally substituted C1-C20 alkyls, optionally substituted C3-C8 cycloalkyls, optionally substituted C2-C20 alkenyls, optionally substituted C5-C10 aryls, -OH, and -O-(C1-C10 alkyls), where the tetravalent metal M is the common part of multiple cages. Those skilled in the art will notice that the number of bonds with metal M depends on the valence of metal M. Structural formulas (Ia) to (Ic) should be adapted accordingly where applicable.

[0085] In one embodiment, the polyurethane prepolymer of the present invention is produced using a mixture of metal-siloxane-silanol (silanolate) compounds of formulas (I), (Ia), (Ib), and (Ic).

[0086] Furthermore, the polynuclear metal-siloxane-silanol (silanolate) compound of formula (Id) may also have a hexa-coordinate metal center, which is formula (Id) [ka] (wherein 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 metalloids, more specifically from the group consisting of metals from transition elements groups 1, 2, 3, 4, 5, 8, 10, and 11, and metals from main group elements groups 1, 2, 3, 4, and 5, preferably Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn, and Selected from the group consisting of Bi; more preferably selected from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, and Bi; each R is independently selected from the group consisting of optionally substituted C1-C20 alkyl, optionally substituted C3-C8 cycloalkyl, optionally substituted C2-C20 alkenyl, optionally substituted C5-C10 aryl, -OH, and -O-(C1-C10 alkyl)). This creates the possibility of a specific structure.

[0087] For the purposes of the present invention, the term "mononuclear" refers to the isolated cage structure, and therefore the singular structure, of the catalysts of the present invention based on metal-siloxane-silanol (silanolate) compounds. Mononuclear catalysts based on metal-siloxane-silanol (silanolate) compounds may also be encompassed by structure (IV), as well as by structures (I) and (II). [ka] (Here, X 4 is, -M 3 L 1 Δ And L 1 The group is selected from -OH and -O-(C1 to C10 alkyl), more specifically from the group consisting of -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 1is selected from the group consisting of -OH, -O-methyl, -O-ethyl, -O-propyl, -O-butyl, -O-octyl, -O-isopropyl, and -O-isobutyl, and M 3 The metal is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and metalloids; more specifically, from the group consisting of metals from transition elements groups 1, 2, 3, 4, 5, 8, 10, and 11, and metals from main group elements groups 1, 2, 3, 4, and 5; preferably selected from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn, and Bi; particularly more preferably selected from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, and Bi; Z 1 , Z 2 , and Z 3 These are independently selected from the group consisting of optionally substituted C1-C20 alkyls, optionally substituted C3-C8 cycloalkyls, optionally substituted C2-C20 alkenyls, and optionally substituted C5-C10 aryls; R 1 , R 2 , R 3 , and R 4 Each of these is independently selected from the group consisting of optionally substituted C1-C20 alkyls, optionally substituted C3-C8 cycloalkyls, optionally substituted C2-C20 alkenyls, and optionally substituted C5-C10 aryls.

[0088] Furthermore, the metal-silsesquioxane used to produce the polyurethane prepolymer of the present invention is a metal-siloxane-silanol (silanolate) compound of general structural formula (II), where X 4 ha-M 3 L 1 Δ And L 1The group is selected from -OH and -O-(C1 to C10 alkyl), more specifically from the group consisting of -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 1 is selected from the group consisting of -OH, -O-methyl, -O-ethyl, -O-propyl, -O-butyl, -O-octyl, -O-isopropyl, and -O-isobutyl, and M 3 The metal is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and metalloids; more specifically, from the group consisting of metals from transition elements groups 1, 2, 3, 4, 5, 8, 10, and 11, and metals from main group elements groups 1, 2, 3, 4, and 5; preferably selected from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn, and Bi; particularly more preferably selected from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, and Bi; Z 1 , Z 2 , and Z 3 They are independent of each other, L 2 , R 5 , R 6 , and R 7 Selected from the group consisting of L 2 The group is selected from -OH and -O-(C1 to C10 alkyl), more specifically from the group consisting of -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or L 2 is selected from the group consisting of -OH, -O-methyl, -O-ethyl, -O-propyl, -O-butyl, -O-octyl, -O-isopropyl, and -O-isobutyl, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7These are independently selected from the group consisting of optionally substituted C1 to C20 alkyls, optionally substituted C3 to C8 cycloalkyls, optionally substituted C2 to C20 alkenyls, and optionally substituted C5 to C10 aryls.

[0089] In one particular advantageous embodiment, the polyurethane prepolymer of the present invention may be produced by a catalytic reaction with heptisobutylPOSS-titanium(IV) ethoxide (TiPOSS) as a metal-siloxane-silanol (silanolate) compound.

[0090] In this case, the abbreviation "TiPOSS" represents mononuclear titanium metallized silsesquioxane of structural formula (IV), and may be used interchangeably with "heptisobutylPOSS-titanium(IV) ethoxide" for the purposes of the present invention. [ka]

[0091] In the reaction for producing the polyurethane prepolymer of the present invention, the metal-siloxane-silanol (silanolate) compound may preferably represent a mixture comprising structures (I), (Ia), (Ib), (Ic), (Id), (II), (IV), (IVb), and (IVc).

[0092] In one preferred embodiment, the metal in the metal-siloxane-silanol (silanolate) compound is titanium.

[0093] Particularly preferred catalysts from the group of metal-siloxane-silanol (silanolate) compounds are heptisobutylPOSS-titanium(IV) ethoxide (TiPOSS) and heptisobutylPOSS-tin(IV) ethoxide (SnPOSS). HeptisobutylPOSS-titanium(IV) ethoxide (TiPOSS) is especially very preferred.

[0094] Suitable catalysts include organotin, organobismuth, organozinc, organozirconium, organoaluminum, and organotitanium compounds. Similarly, tertiary amines are also suitable catalysts.

[0095] Suitable organometallic compounds include, for example, 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, where R is, for example, isopropyl, n-butyl, or isobutyl), such as isopropyl n-butyl titanate; and titanium acetate. Triisopropyl bis(acetylacetonate) titanate, diisopropoxy-bis(ethylacetylacetonate) titanate, di-n-butyl-bis(acetylacetonate) titanate, di-n-butyl-bis(ethylacetoacetate) titanate, triisopropoxide-bis(acetylacetonate) titanate; zirconium tetraalkoxide, for example zirconium tetraethoxide, zirconium tetrabutoxide, zirconium tetrabutyrate, zirconium tetraprop Zirconium oxides, zirconium carboxylates, e.g., zirconium diacetate; zirconium acetylacetonate chelates, e.g., zirconium tetra(acetylacetonate), tributoxyzirconium acetylacetonate, dibutoxyzirconium(bisacetylacetonate); aluminum trisalkoxides, e.g., aluminum triisopropoxide, aluminum trisbutoxide; aluminum acetylacetonate chelates, e.g., aluminum tris(acetylacetonate) and aluminum tris(ethylacetate) Organotin compounds, such as dibutyltin dilaurate (DBTL), dibutyltin maleate, dibutyltin diacetate, tin(II) 2-ethylhexanoate (tin octanoate), tin naphthenate, dimethyltin dienedecanoate, dioctyltin dienedecanoate, dimethyltin dioleate, dioctyltin dilaurate, dimethyl mercaptide, dibutyl mercaptide, dioctyl mercaptide, dibutyltin dithioglycolate, dioctyltin glycolate, dimethyltin glycolate, and solutions of dibutyltin oxide;Reaction products of zinc salts with organic carboxylic acids (carboxylates), e.g., zinc(II) 2-ethylhexanoate or zinc(II) neodecanoate; mixtures of bismuth carboxylate and zinc carboxylate; reaction products of bismuth salts with organic carboxylic acids, e.g., bismuth(III) tris(2-ethylhexanoate) and bismuth(III) tris(neodecanoate); and bismuth complex compounds; as well as organic lead compounds, e.g., lead octoxide, and organic vanadium compounds.

[0096] Suitable amine compounds include, for example, 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]undeca-7-ene (DBU), salts of these amines with carboxylic acids or other acids, or mixtures thereof.

[0097] Organotin or organotitanium compounds are preferred.

[0098] Preferred organometallic compounds as catalysts are dibutyltin and dioctyltin diacetate, maleate, bis(2-ethylhexoate), dilaurate, dichloride, and bisdodecyl mercaptide, tributyltin acetate, bis(β-methoxycarbonylethyl)tin dilaurate, and bis(β-acetylethyl)tin dilaurate.

[0099] Particularly preferred organometallic compounds as catalysts are selected from the group consisting of dibutyltin dilaurate (DBTL), tin(II) 2-ethylhexanoate (tin octanoate), zinc(II) 2-ethylhexanoate, zinc(II) neodecanoate, bismuth(III) tris(2-ethylhexanoate), bismuth(III) tris(neodecanoate), or mixtures thereof.

[0100] Dibutyltin dilaurate (DBTL) is particularly very preferred.

[0101] In further embodiments, the catalyst is selected from group A and / or B, where catalyst A is selected from the group of metal-siloxane-silanol (silanolate) compounds, and catalyst B is a metal-organic catalyst or an amine catalyst.

[0102] Preferably, catalyst A and / or B are organotin or organotitanium compounds. Catalyst B is very preferably selected from the group of tin(IV) compounds.

[0103] In the production of the polyurethane prepolymer of the present invention, the total amount of catalyst is between 1.0 and 1000 ppm, preferably between 2 and 250 ppm, and more preferably between 3 and 100 ppm, relative to the total weight of the hydroxy-functionalized polymer used.

[0104] In a preferred embodiment, when a catalyst from group A is used to produce the polyurethane prepolymer of the present invention, a reaction temperature between 10°C and 120°C, preferably between 15°C and 100°C, more preferably between 20°C and 90°C, and very preferably between 25°C and 85°C is used.

[0105] In another preferred embodiment, when a catalyst from group A is used in the production of the polyurethane prepolymer of the present invention, the amount of catalyst A selected is between 1 ppm and 500 ppm, preferably between 2 ppm and 250 ppm, and more preferably between 3 ppm and 80 ppm.

[0106] In another preferred embodiment, heptisobutylPOSS-titanium(IV) ethoxide (TiPOSS) is used as catalyst A when producing the polyurethane prepolymer of the present invention.

[0107] In one particularly preferred embodiment, when a catalyst from group A is used in the production of the polyurethane prepolymer of the present invention, a reaction temperature between 10°C and 120°C, preferably between 15°C and 100°C, more preferably between 20°C and 90°C, and very preferably between 25°C and 85°C is used, and an amount of catalyst A between 1.0 ppm and 500 ppm, preferably between 2 ppm and 250 ppm, and more preferably between 3 ppm and 80 ppm is selected.

[0108] Similarly, in a particularly preferred embodiment, when heptisobutylPOSS-titanium(IV) ethoxide (TiPOSS) is used as the catalyst from group A in the production of the polyurethane prepolymer of the present invention, a reaction temperature of 10°C to 120°C, preferably 15°C to 100°C, more preferably 20°C to 90°C, and very preferably 25°C to 85°C is used.

[0109] Similarly, in a particularly preferred embodiment, when heptisobutylPOSS-titanium(IV) ethoxide (TiPOSS) is used as a catalyst from group A in the production of the polyurethane prepolymer of the present invention, the amount of selected catalyst A is between 1 ppm and 1000 ppm, preferably between 2 ppm and 250 ppm, and more preferably between 3 ppm and 100 ppm.

[0110] In a particularly preferred embodiment, when heptisobutylPOSS-titanium(IV) ethoxide (TiPOSS) is used as the catalyst from group A in the production of the polyurethane prepolymer of the present invention, a reaction temperature of 10°C to 120°C, preferably 15°C to 100°C, more preferably 20°C to 90°C, and more preferably 25°C to 85°C is used, and the amount of catalyst A is between 1 ppm and 500 ppm, preferably between 2 ppm and 250 ppm, and more preferably between 3 ppm and 80 ppm.

[0111] In a more preferred embodiment, when a catalyst from group B is used to produce the polyurethane prepolymer of the present invention, a reaction temperature of 20°C to 80°C, preferably 20°C to 70°C, and more preferably 25°C to 50°C is used.

[0112] In a more preferred embodiment, when a catalyst from group B is used in the production of the polyurethane prepolymer of the present invention, the amount of catalyst B selected is between 1 ppm and 1000 ppm, preferably between 2 ppm and 250 ppm, and more preferably between 3 ppm and 100 ppm.

[0113] In one particularly preferred embodiment, when a catalyst from group B is used to produce the polyurethane prepolymer of the present invention, a reaction temperature of 20°C to 80°C, preferably 20°C to 70°C, more preferably 25°C to 50°C is used, and the amount of selected catalyst B is between 1 ppm and 1000 ppm, preferably between 2 ppm and 250 ppm, more preferably between 3 ppm and 100 ppm.

[0114] In another preferred embodiment, dibutyltin dilaurate (DBTL) is used as a catalyst when producing the polyurethane prepolymer of the present invention.

[0115] Similarly, in a particularly preferred embodiment, when dibutyltin dilaurate (DBTL) is used as catalyst B in the production of the polyurethane prepolymer of the present invention, a reaction temperature of 20°C to 70°C, preferably 25°C to 50°C, is used.

[0116] Similarly, in a particularly preferred embodiment, when dibutyltin dilaurate (DBTL) is used as catalyst B in the production of the polyurethane prepolymer of the present invention, the amount of catalyst B selected is between 20 ppm and 100 ppm, preferably between 30 ppm and 85 ppm, and more preferably between 40 ppm and 50 ppm.

[0117] In one particularly preferred embodiment, when dibutyltin dilaurate (DBTL) is used as catalyst B in the production of the polyurethane prepolymer of the present invention, a reaction temperature of 20°C to 70°C, preferably 25°C to 50°C, is used, and the selected amount of catalyst B is between 20 ppm and 100 ppm, preferably between 30 ppm and 85 ppm, more preferably between 40 ppm and 50 ppm.

[0118] Furthermore, the polyurethane prepolymers of the present invention serve as building blocks for producing polyurethane elastomers, polyurethane ureas, one- or two-component reactive polyurethane systems, and polyurethane dispersions (these are widely used as polyurethane foams, building materials, varnishes, coatings, adhesives and sealants, grouts, films, PUR elastomers, etc.). The polyurethane prepolymers of the present invention also serve as building blocks for producing block copolymers, star polymers, or dendrimers.

[0119] The isocyanate-functional polyurethane prepolymer of the present invention may be used as a crosslinking component directly in a reactive PU composition, for example, in an aqueous 1K (one-component) or 2K (two-component) PU composition, without further reaction or post-treatment.

[0120] The aqueous 1K PU dispersion is an OH- and / or NH-functionalized dispersion combined with a raw material containing a thermoreversible blocked isocyanate group. The blocked polyisocyanate in question may be used in its unmodified form, for example, in its hydrophobic form, in which case the resin dispersion (OH- and / or NH-terminated) must have codispersive properties. Conversely, a hydrophilic modified blocked polyisocyanate forms a stable dispersion on its own and is mixed with the resin dispersion. Alternatively, the blocked isocyanate functional group may be directly bonded to the OH- and / or NH-terminated polymer scaffold. Such systems are known as self-crosslinked dispersions.

[0121] The aqueous 2K PU dispersion consists of a binder component and a crosslinking agent component, which are produced and stored separately and not combined until shortly before application. The action time or pot life (i.e., the time during which the coating composition of the present invention can be processed, preferably at room temperature (15 to 25°C, more particularly 20°C), without the corresponding crosslinking reaction that rapidly increases the viscosity at room temperature to such an extent that application is no longer possible) is known to depend on the components used.

[0122] In a preferred embodiment of the present invention, the polyurethane prepolymer of the present invention is further reacted with a silane in a further step to give a silylated polyurethane.

[0123] The subject of this invention is also a silylated polyurethane that can be obtained by reacting the polyurethane prepolymer of the present invention with an organic silane.

[0124] Silylated polyurethanes that can be obtained in this way, and compositions containing silylated polyurethanes, are also further subjects of the present invention.

[0125] The silylated polyurethane produced from at least one polyurethane prepolymer of the present invention similarly has the corresponding area ratio from the molar mass distribution (measured by GPC).

[0126] The terms "silane" or "organosilane" refer to compounds having, on the one hand, at least one, typically two or three hydrolyzable groups, preferably alkoxy or acyloxy groups, directly bonded to a silicon atom via a Si-O bond, and on the other hand, at least one organic radical directly bonded to a silicon atom via a Si-C bond. Silanes having alkoxy or acyloxy groups are also known to those skilled in the art as organic alkoxysilanes or organic siloxysilanes, respectively.

[0127] Accordingly, the term "silane group" refers to a silicon-containing group bonded to an organic radical of silane, which is bonded via a Si-C bond. Silane or its silane group has the property of hydrolyzing upon contact with moisture. The resulting compounds are organosilicon compounds containing an organosilanol, i.e., one or more silanol groups (Si-OH groups), and an organosiloxane through a subsequent condensation reaction, and these are organosilicon compounds containing one or more siloxane groups (Si-O-Si groups).

[0128] A suitable silane in the sense of the present invention includes at least one group that reacts with the isocyanate group.

[0129] This reaction is preferably carried out with isocyanate groups in a stoichiometric ratio of 1:1 to the groups reactive with the isocyanate groups, or with a slightly excess of groups reactive with the isocyanate groups, so that the resulting silane-functionalized polyurethane polymer does not contain isocyanate groups.

[0130] In the reaction between a silane containing at least one group reactive to isocyanate groups and a polyurethane polymer containing isocyanate groups, the silane is used in less than stoichiometric amounts, although this is generally undesirable, to produce a silane-functionalized polymer containing not only silane groups but also isocyanate groups. The remaining NCO groups can be quenched with compounds containing nucleophilic groups (OH, SH, NH2, NHR), such as 2-ethylhexyl alcohol, dibutylamine, benzyl alcohol, and stearylamine.

[0131] Silanes containing at least one group that is reactive to an isocyanate group are, for example, mercaptosilanes or aminosilanes.

[0132] In the context of this invention, "silylated polyurethane" refers to silane-modified, silane-functionalized, or silane-terminated polyurethanes, which are synonymous and also known as SPUR. The definition includes products of chain polymerization, polycondensation, or polyaddition.

[0133] The polymer in question is further a water-crosslinked polymer that can be cured under the influence of water by the addition of water or by mixing components with water, or by contact with moisture in the atmosphere, and preferably by the additional use of a catalyst.

[0134] A "polymer" is a compound composed of chain-like or branched-chain molecules (macromolecules), that is, several identical / similar or otherwise different units called monomers. Polymers also include oligomers. Oligomers are polymers having a relatively small number of units. Unless otherwise clearly defined, oligomers are included in the concept of polymers according to the present invention. Polymers may arise as homopolymers (= consisting of only one type of monomer unit), copolymers (= consisting of two or more types of monomer units), or polymer mixtures (= polymer alloys, polymer blends, i.e., mixtures of different polymers and copolymers).

[0135] Silane-functional polymers are also called hybrid polymers in general use and in this invention. These polymers can combine the curing chemistry of alkoxysilane groups with the chemistry of polyols and / or polyurethanes. Alkoxysilane groups are known from silicone chemistry; isocyanate-functional polymers, particularly hydroxy-functional polymers, are involved in at least part of the polymer backbone of hybrid polymers. Crosslinking ("curing") occurs via reactive silane-terminated groups, for example, through the penetration of moisture in the atmosphere. The curing mechanism of these systems is preferably neutral.

[0136] "Alkoxy" refers to an alkyl group that is connected to the main carbon chain or main skeleton of a compound via an oxygen atom.

[0137] Silane-functional polyurethanes consist of a polymer backbone (P) and the following general formula (V) [ka] (In the formula, - X is C, Si, or a heteroatom, and these can be one or more R depending on their valence. 8 It has a radical, preferably C, N, O, P, or S, more preferably C, N, or O, and very preferably N or O, and in each case is bonded to a carbon in the polymer backbone. - R * R is O, or optionally substituted linear or branched C1 to C25 alkyl groups, or optionally substituted C4 to C18 cycloalkyl groups, or optionally substituted C4 to C18 aryl groups, * In the case of =O, the Si atom is directly connected to the N atom. - Each Y is independent of the other, O, or each R 9 , R 10 , or R 11 A direct bond of Si atoms to a radical, preferably at least one Y is O. - R 8 This is H, optionally substituted linear or branched C1-C25 alkyl groups, optionally substituted linear or branched C2-C125 alkenyl groups, optionally substituted linear or branched C2-C18 alkynyl groups, optionally substituted C4-C18 cycloalkyl groups, optionally substituted C4-C18 aryl groups, or a radical of the general structure (Vb). - R 12 and R 14 These are H or -R, each independent of the other. 15 ,-COOR 15 A radical from the group consisting of , and -CN, - R 13 is H, or -CH2-COOR 15 ,-COOR 15, -CONHR 15 , -CON(R 15 ), -CN, -NO2, -PO(OR 15 )2, -SOR 15 , and -SO2OR 15 A radical from the group consisting of, - R 15 It is a hydrocarbon radical having 1 to 20 carbon atoms and optionally containing at least one heteroatom. - R 9 , R 10 , and R 11 These are, independently of each other, H, optionally substituted linear or branched C1-C20 alkyl groups, optionally substituted linear or branched C2-C20 alkenyl groups, optionally substituted C4-C14 cycloalkyl groups, or optionally substituted C4-C14 aryl groups; Preferably at least R 9 is a C2 alkyl group, more preferably at least R 9 and R 10 These are each C2 alkyl groups, - m is either 0 or 1; if m=0, the Si atom is directly bonded to the carbon in the polymer backbone (P). This also includes at least two terminal groups or functional groups or modified forms.

[0138] In an alternative embodiment, the polyurethane prepolymer of the present invention is of formula (IX) [ka] (In the formula, 2 R 16 and R 17 Each radical is independent of the others. R 16 A radical is a linear or branched monovalent hydrocarbon radical having 1 to 8 carbon atoms, more specifically a methyl or ethyl group. R 17The radical is an acyl radical, or a linear or branched monovalent hydrocarbon radical having 1 to 5 C atoms, more specifically a methyl or ethyl group, preferably a methyl group, where the subscript a is 0, 1, or 2, more specifically 0. R 18 The radical is a linear or branched divalent hydrocarbon radical having 1 to 12 carbon atoms, optionally comprising a cyclic portion and optionally one or more heteroatoms, more particularly one or more nitrogen atoms; more particularly an alkylene group having 1 to 6 carbon atoms, preferably 2 to 6 carbon atoms; and more particularly a propylene group. It may also be reacted with an organosilane.

[0139] In one silane group of formula (IX), R 16 and R 17 Each of these is a radical described independently of the others. For example, the terminal group (R) of formula (IX) is an ethoxydimethoxysilane terminal group. 16 =methyl, R 17 =methyl, R 17 Compounds containing (=ethyl) are also possible.

[0140] R 19 This is a cyclic, linear, or branched monovalent hydrocarbon radical having a hydrogen atom or 1 to 20 carbon atoms, and optionally including a cyclic portion, or the following formula: [ka] (In the formula, R 20 and R 21 In each case, the radicals are independent of each other, with respect to the hydrogen atom, or -R 23 ,-COOR 23 A radical from the group consisting of , and -CN, R 22 A radical is a hydrogen atom, or -CH2-COOR * ,-COOR 23 , -CONHR 23 , -CON(R 23)2, -CN, -NO2, -PO(OR 23 )2, -SO2R 23 , and -SO2OR 23 It is a radical from the group consisting of R 23 A radical is a hydrocarbon radical having 1 to 20 carbon atoms and optionally containing at least one heteroatom. It is radical.

[0141] R 19 This may be a hydrocarbon radical containing an alkoxysilyl group, such as a trimethoxysilylpropyl radical.

[0142] Suitable aminosilanes in the present invention include primary aminosilanes, preferably 3-aminopropyltrimethoxysilane and 3-aminopropyldimethoxymethylsilane; secondary aminosilanes, preferably N-butyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane; and Michael-like addition products of primary aminosilanes, such as products of 3-aminopropyltrimethoxysilane or 3-aminopropyldimethoxymethylsilane, with Michael acceptors such as acrylonitrile, acrylic acid esters, (meth)acrylic acid esters, (meth)acrylamide, maleic acid and fumarate diesters, citraconic acid diesters and itaconic acid diesters, preferably dimethyl and diethyl N-(3-trimethoxysilylpropyl)aminosuccinate.

[0143] A Michael acceptor is a compound that contains a double bond activated by an electron acceptor radical, and therefore can enter a nucleophilic addition reaction with a primary amino group (NH2 group) in a manner similar to Michael addition (hetero-Michael addition).

[0144] Particularly suitable aminosilanes are secondary aminosilanes, especially those with R in formula (IX). 19The aminosilane is one in which the element is not H. N-alkylaminosilanes, such as N-butyl-3-aminopropyltrimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, [(N-cyclohexylamino)methyl]methyldiethoxysilane, N-ethylaminomethylmethyldiethoxysilane, N-butyl-3-amino-2-methylpropyltrimethoxysilane, N-ethyl-4-amino-3,3-dimethylbutyldimethoxymethylsilane, and N-ethyl-4-amino-3,3-dimethylbutyltrimethoxysilane are preferred.

[0145] A suitable mercaptosilane is given by the general formula (X): HS-R 18 -(SiR 16 a (OR 17 ) 3-a ) (X) It has, in the formula, R 16 From R 18 A radical is defined as described above.

[0146] Examples include 3-mercaptopropyltrimethoxysilane and 1-mercaptomethylmethyldimethoxysilane.

[0147] It is also possible to use a mixture of the silanes of formulas (VIII) and (IX) described above, as well as mercaptosilane (X), for the end-capping reaction.

[0148] In other embodiments, suitable organosilanes include all reaction products of Michael-like additions between primary aminosilanes such as 3-aminopropyltrimethoxysilane or 3-aminopropyldimethoxymethylsilane and Michael acceptors such as acrylonitrile, acrylic acid esters, (meth)acrylic acid esters, (meth)acrylamide, maleic acid and fumarate diesters, citraconic acid diesters, itaconic acid diesters, and mixtures thereof.

[0149] Unless otherwise specified, N specifically represents nitrogen. Furthermore, unless otherwise specified, O specifically represents oxygen. S specifically represents sulfur unless otherwise specified. P specifically represents phosphorus unless otherwise specified. C specifically represents carbon unless otherwise specified. H specifically represents hydrogen unless otherwise specified. Si specifically represents silicon unless otherwise specified.

[0150] "Substituted as necessary" means that the hydrogen atoms of the corresponding group or radical may be replaced by substituents. Substituents may be selected from the group consisting of C1-C4 alkyl, methyl-, ethyl-, propyl-, butyl-, phenyl-, benzyl-, halo-, fluoro-, chloro-, bromo-, iodo-, hydroxyl-, amino-, alkylamino-, dialkylamino-, C1-C4 alkoxy-, phenoxy-, benzyloxy-, cyano-, nitro-, and thio-. When a group is said to be substituted as necessary, it is possible that 0 to 50, more specifically 0 to 20, hydrogen atoms in that group are replaced by substituents. If a group is substituted, at least one hydrogen atom is replaced by a substituent.

[0151] The term "alkyl group" refers to a saturated hydrocarbon chain. More specifically, alkyl groups are defined by the general formula -C n H 2n+1 The designation "C1 to C16 alkyl group" specifically indicates a saturated hydrocarbon 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, "C1 to C8 alkyl group" specifically indicates a saturated hydrocarbon chain having 1 to 8 carbon atoms in the chain. Alkyl groups may be substituted unless otherwise specified.

[0152] "Linear alkyl group" refers to an alkyl group that does not have branching. Examples of linear alkyl groups are methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl.

[0153] "Branched alkyl group" refers to an alkyl group that is not linear, and therefore, in particular, the hydrocarbon chain exhibits branching. Examples of branched alkyl groups include isopropyl, isobutyl, sec-butyl, tert-butyl, sec-pentyl, 3-pentyl, 2-methylbutyl, isopentyl, 3-methylbuta-2-yl, 2-methylbuta-2-yl, neopentyl, ethylhexyl, and 2-ethylhexyl.

[0154] The term "alkenyl group" refers to a hydrocarbon chain containing at least one double bond along the chain. For example, an alkenyl group with one double bond has the general formula -CnH2n-1. However, an alkenyl group may also have more than one double bond. The designation "C2 to C16 alkenyl group" specifically refers to a hydrocarbon chain having 2 to 16 carbon atoms in the chain. The number of hydrogen atoms varies depending on the number of double bonds in the alkenyl group. Examples of alkenyl groups include vinyl, allyl, 2-butenyl, and 2-hexenyl.

[0155] A "linear alkenyl group" refers to an alkenyl group that does not have branching. Examples of linear alkenyl groups are vinyl, allyl, n-2-butenyl, and n-2-hexenyl.

[0156] A "branched alkenyl group" refers to an alkenyl group that is not linear, and therefore the hydrocarbon chain is particularly branched. Examples of branched alkenyl groups are 2-methyl-2-propenyl, 2-methyl-2-butenyl, and 2-ethyl-2-pentenyl.

[0157] "Aryl group" refers to monocyclic (e.g., phenyl), bicyclic (e.g., indenyl, naphthalenyl, tetrahydronaphthyl, or tetrahydroindenyl), and tricyclic (e.g., fluorenyl, tetrahydrofluorenyl, anthracenyl, or tetrahydroanthracenyl) ring systems in which at least one ring in the monocyclic, bicyclic, or tricyclic ring system is aromatic. C4 to C14 aryl groups specifically refer to aryl groups having 4 to 14 carbon atoms. Unless otherwise specified, aryl groups may be substituted.

[0158] In the sense of the present invention, "silanol" is an organosilicon compound having at least one hydroxyl group (OH) bonded to a silicon atom (-Si-OH).

[0159] In the sense of the present invention, "silanolate" is an organosilicon compound having at least one deprotonated hydroxyl functional group (RO-) bonded to a silicon atom (-Si-O-), and this negatively charged oxygen atom may coordinate and / or covalently bond to other compounds, such as metals, and / or chemically bond to them.

[0160] In the present invention, silylated polyurethane is produced by catalytic synthesis of at least one isocyanate-reactive compound, more specifically a hydroxy-functionalized polymer, and a compound containing at least one isocyanate group.

[0161] In the present invention, the synthesis is carried out using catalytic synthesis of an isocyanate-reactive compound, more specifically a hydroxy-functionalized polymer, and a polyisocyanate compound. Preferably, a polyisocyanate is used.

[0162] Subsequently, the prepolymer of the present invention containing the isocyanate group obtained in this manner is reacted with an organosilane to obtain the silylated polyurethane of the present invention.

[0163] The polyurethane prepolymer of the present invention and formula (VIII) [ka] (In the formula, - R 7 H is H, - R 8 This is H, optionally substituted linear or branched C1-C25 alkyl groups, optionally substituted linear or branched C2-C25 alkenyl groups, optionally substituted C4-C18 cycloalkyl groups, optionally substituted C4-C18 aryl groups, or a radical of the general structure (Vb). - R * R is O, or optionally substituted linear or branched C1-C25 alkyl groups, or optionally substituted C4-C18 cycloalkyl groups, or optionally substituted C4-C18 aryl groups, * If =O, then the Si atom is directly connected to the N atom. - R 12 and R 14 These are H or -R, each independent of the other. 15 ,-COOR 15 A radical from the group consisting of , and -CN, - R 13 is H, or -CH2-COOR 15 ,-COOR 15 , -CONHR 15 , -CON(R 15 ), -CN, -NO2, -PO(OR 15 )2, -SOR 15 , and -SO2OR 15 A radical from the group consisting of, - R 15 This is a hydrocarbon radical having 1 to 20 carbon atoms and optionally containing at least one heteroatom. - R 9 , R 10 , and R 11These are independently H, optionally substituted linear or branched C1-C25 alkyl groups, optionally substituted linear or branched C2-C25 alkenyl groups, optionally substituted C4-C18 cycloalkyl groups, or optionally substituted C4-C18 aryl groups; preferably, at least one R 9 is a C2 alkyl group, moreover, R 9 and R 10 These are each C2 alkyl groups, - Each Y is independent of the other, O, or each R 9 , R 10 , or R 11 (Any of the direct bonds between Si atoms and radicals; preferably at least one Y is O) Subsequent reaction with an organosilane provides a silylated polyurethane.

[0164] The terminal group of the present invention in silylated polyurethane is of general formula (V) [ka] (In the formula, - X is C, Si, or a heteroatom, and these are one or more R depending on their valence as needed. 8 It has a radical, preferably C, N, O, P, or S, more preferably C, N, or O, and very preferably N or O, and in each case is bonded to a carbon in the polymer backbone. - R * is O, or optionally substituted linear or branched C1 to C25 alkyl groups, or optionally substituted C4 to C18 cycloalkyl groups, or optionally substituted C4 to C18 aryl groups, preferably optionally substituted linear or branched C1 to C15 alkyl groups, and R * If =O, then the Si atom is directly connected to the N atom. - Each Y is independent of the other, O, or each R 9 , R10 , or R 11 One of the direct bonds of a Si atom to a radical, preferably at least one Y is O, - R 8 This is H, optionally substituted linear or branched C1-C25 alkyl groups, optionally substituted linear or branched C2-C25 alkenyl groups, optionally substituted linear or branched C2-C18 alkynyl groups, optionally substituted C4-C18 cycloalkyl groups, optionally substituted C4-C18 aryl groups, or a radical of the general structure (Vb). - R 12 and R 14 These are H or -R, each independent of the other. 15 ,-COOR 15 A radical from the group consisting of , and -CN, - R 13 is H, or -CH2-COOR 15 ,-COOR 15 , -CONHR 15 , -CON(R 15 ), -CN, -NO2, -PO(OR 15 )2, -SOR 15 , and -SO2OR 15 A radical from the group consisting of, - R 15 This is a hydrocarbon radical having 1 to 20 carbon atoms and optionally containing at least one heteroatom. - R 9 , R 10 , and R 11 These are independently H, or a C1 or C2 alkyl group; preferably at least R 9 is a C2 alkyl group, more preferably R9 and R 10 Each of these is a C2 alkyl group, - m is either 0 or 1; if m=0, the Si atom is directly bonded to the carbon in the polymer backbone (P). It may be described by:

[0165] In all further alternative embodiments of the above combinations, the silylated polyurethane is produced by reacting with an organosilane selected from the group consisting of N-(triethoxysilyl)methyl]butylamine, N-[3-(triethoxysilyl)propyl]butylamine, diethyl N-(3-triethoxysilylpropyl)aminosuccinate, or mixtures thereof.

[0166] In an alternative embodiment, the polyurethane prepolymer of the present invention is produced by catalytic synthesis of polypropylene glycol and isophorone diisocyanate (IPDI).

[0167] In an alternative embodiment, the polyurethane prepolymer of the present invention is produced by catalytic synthesis of polypropylene glycol and isophorone diisocyanate (IPDI) using DBTL.

[0168] In further alternative embodiments, the silylated polyurethane polymer of the present invention is produced by catalytic synthesis of polypropylene glycol and isophorone diisocyanate (IPDI), followed by silanation with N-[3-(trimethoxysilyl)propyl]butylamine.

[0169] In further alternative embodiments, the silylated polyurethane polymer of the present invention is produced by catalytic synthesis of polypropylene glycol and isophorone diisocyanate (IPDI), followed by silanization with N-[3-(trimethoxysilyl)propyl]butylamine using TiPOSS.

[0170] Alternatively, in the above-described embodiment, polypropylene glycol having a number-average molecular weight of 18,000 g / mol is used.

[0171] In further alternative embodiments, one or more fillers selected from the group of inorganic and organic fillers, in particular natural, pulverized or precipitated calcium carbonate, optionally coated with fatty acids, especially stearic acid; barite, talc, quartz powder, quartz sand, dolomite, wollastonite, kaolin, calcined kaolin, mica (potassium aluminum silicate), molecular sieves, aluminum oxide, aluminum hydroxide, magnesium hydroxide, silica, including fine-grained silica from a pyrolysis process; industrially produced carbon black, graphite, metal powders such as aluminum, copper, iron, silver, or steel; PVC powder or hollow beads; one or more adhesion promoters, from the group of silanes, in particular aminosilanes, e.g., 3-aminopropyltrimethoxysilane, 3-amino The additives include propyldimethoxymethylsilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-N'-[3-(trimethoxysilyl)propyl]ethylenediamine, and analogs thereof having ethoxy or isopropoxy instead of a methoxy group on silicon, aminosilanes having a secondary amino group, such as particularly N-phenyl-, N-cyclohexyl-, and N-alkylaminosilane, as well as mercaptosilane, epoxysilane, (meth)acrylosilane, anhydrous silane, carbamatosilane, alkylsilane, and iminosilane, as well as oligomeric forms of these silanes, and additives from the group encompassing adducts of primary aminosilanes including epoxysilane or (meth)acrylosilane or anhydrous hydridosilane. Particularly 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 instead of methoxy groups, as well as the oligomeric forms of these silanes;One or more water scavengers from the group of silanes, particularly tetraethoxysilane, vinyltrimethoxy- or vinyltriethoxysilane, or organic alkoxysilane having a functional group at the α-position relative to the silane group, particularly N-(methyldimethoxysilylmethyl)-O-methylcarbamate, (methacryloyloxymethyl)silane, methoxymethylsilane, orthoformate esters, and calcium oxide or molecular sieves; one or more plasticizers from the group of carboxylic acid esters such as phthalates, particularly diisononyl 1,2-cyclohexanedicarboxylate, dioctyl phthalate, diisononyl phthalate, or diisodecyl phthalate, adipates, particularly dioctyl adipate, azelates, sebacates, polyols, particularly polyoxyalkylene polyols or polyester polyols, glycol ethers, glycol esters, citrates, particularly The following are selected: triethyl citrate, organophosphorus and sulfonic acid esters, polybutene, or fatty acid methyl or ethyl esters derived from natural fats or oils; one or more UV stabilizers, consisting of organic (benzophenone, benzotriazole, oxalanilide, phenyltriazine) and inorganic (titanium dioxide, iron oxide, zinc oxide) UV absorbers; antioxidants, consisting of sterically hindered phenols, amines, phosphates, and phosphonites; one or more thixotropes, consisting of layered silicates such as bentonite; castor oil derivatives, hydrogenated castor oil, polyamides, polyurethanes, urea compounds, fumed silica, cellulose ethers, or hydrophobic modified polyoxyethylenes; one or more wetting agents, consisting of nonionic, anionic, and cationic surfactants, or combinations thereof.

[0172] In further alternative embodiments, the compositions of the present invention further comprise a water scavenger, preferably a vinyl alkoxysilane, more preferably a vinyl trimethoxysilane (VTMO). It is always possible herein that the alkoxy substituents (e.g., methoxy or ethoxy) of the alkoxysilane in the composition of at least one silylated polyurethane can be exchanged with at least one water scavenger.

[0173] In the production of polyurethane prepolymers and silylated polyurethanes obtainable therefrom, according to the present invention, preferably, first, an entire isocyanate-containing compound (component I) or, if not, an entire isocyanate-reactive compound, more specifically a hydroxy-functionalized polymer (component II), is obtained as an initial packing, then the other components I or II are added, and then at least one catalyst is added to react the components. The catalyst may be introduced as an initial packing before components I and II, or added to the components obtained as an initial packing, or added to a mixture of components I and II. From the obtained polyurethane prepolymer of the present invention, silylated polyurethane is then produced by reaction with an organosilane. If one or more components are used, they may, in principle, be added to the reaction mixture at any desired time.

[0174] The process of the present invention is preferably carried out in the absence of (atmospheric) moisture, at the pressure of the ambient atmosphere, in other words, at about 900 to 1100 hPa.

[0175] The process of the present invention may be carried out continuously, for example, in a tubular reactor or tube reactor having a number of metering units arranged in parallel or in series, or it may be carried out in a batch manner, for example, in a conventional reaction tank equipped with a stirring system. [Examples]

[0176] I. GPC Data Instruments and parameters for STD-GPC measurement: Chromatography system: Degassing equipment: Agilent 1260 Infinity degassing equipment Pump: Agilent 1260 Infinity IsoPump Autosampler: Agilent 1260 Infinity ALS Column furnace: Agilent 1290 Infinity II TCC RI detector: Agilent 1260 Infinity RID Software: PSS WinGPC UniChrom V 8.31, Build 8417 Chromatography conditions: DIN: DIN EN ISO 16014-1, DIN 55672-1 Column: 1. PLgel 5μ Mixed D (Agilent Technologies) 2. PLgel 5μ Mixed D (Agilent Technologies) 3. PLgel 3μm Mixed E (Agilent Technologies) Mobile phase: tetrahydrofuran Flow rate: 1mL / min Temperature: 35℃ Injection volume: 100 μL Sample concentration: 1g / L Molecular weight standards: PSS Polymer-Standards-Service GmbH, Mainz;Germany M p [Da]:66000;42400;25500;15700;8680;6540;4920;3470;2280;1306;370;266 * The calibration curve is valid between 266 Da and 66000 Da. Values ​​outside these limits are extrapolated. II. Viscosity

[0177] Viscosity was determined at 25°C using a Brookfield Rheometer DV-3T Extra. Spindle size and spindle speed were selected to achieve a torque of >90%. III. Infrared (IR) spectroscopy:

[0178] IR monitoring was performed using ThermoScientific Nicolet iS5 and iD7ATR units. Evaluation was performed using Omnic 9 software. (Example I) Chemicals used: - Acclaim 18200 (Covestro AG; low monopolyoxypropylene diol, OH value 6.0 mg KOH / g, water content approximately 0.02 wt%) - 3-Isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (Desmodur® I, Covestro AG, Leverkusen) - TiPOSS (HeptisobutylPOSS-Titanium(IV) Ethoxide), 20% solution in Hexamoll® DINCH, BASF) - DBTL (Dibutyltin Dilaurate) BNT Chemicals - DBA (di-n-butylamine) purity > 99%, TCI Chemicals - N-[3-(trimethoxysilyl)propyl]butylamine, DOG Deutsche Olfabrik - VTMO, vinyltrimethoxysilane, Acros Organics A) Production of the polyurethane prepolymer of the present invention (Example 1)

[0179] Approximate number-average molecular weight M n200 g (11 mmol) of polypropylene glycol with an OH value of 18000 g / mol (OH value = 6.0 ± 1.0 mg KOH / g) was placed in a 500 ml three-necked flask and dried under reduced pressure at 80°C for 1 hour. The reduced pressure was then released with nitrogen. The polyol was cooled to 25°C. 0.01 g (0.016 mmol) of DBTL catalyst and 5.19 g (23 mmol) of isophorone diisocyanate (IPDI) were added with stirring. As soon as the theoretical NCO content of 0.52 wt% was reached, the viscosity of the NCO prepolymer was determined [46000 mPas (25°C, Brookfield viscometer)]. For GPC analysis, the prepolymer was reacted with 3.02 g (23 mmol) of di-n-butylamine and stirred at 25°C for 20 minutes. The reaction was monitored by IR spectroscopy (disappearance of the NCO band (2270 cm)). -1 )) Area integral F in the first section (x1 to x2) of the molar weight distribution I And the area integral F in the second section of the molar weight distribution. II The ratio of F II / F I It is 0.29. (Example 2)

[0180] Approximate number-average molecular weight M n 200 g (11 mmol) of polypropylene glycol with an OH value of 18000 g / mol (OH value = 6.0 ± 1.0 mg KOH / g) was placed in a 500 ml three-necked flask and dried under reduced pressure at 80°C for 1 hour. The reduced pressure was then released with nitrogen. The polyol was cooled to 25°C. 0.01 g (0.011 mmol, pure substance) of TiPOSS catalyst and 5.19 g (23 mmol) of isophorone diisocyanate (IPDI) were added, and the reaction mixture was stirred. As soon as the theoretical NCO content of 0.52 wt% was reached, the viscosity of the NCO prepolymer was determined [44000 mPas (25°C, Brookfield viscometer)]. For GPC analysis, the prepolymer was reacted with 3.02 g (23 mmol) of di-n-butylamine and stirred at 25°C for 20 minutes. The reaction was monitored by IR spectroscopy (disappearance of the NCO band (2270 cm)). -1)) Area integral F in the first section (x1 to x2) of the molar weight distribution I And the area integral F in the second section (x2 to x3) of the molar weight distribution. II The ratio of F II / F I It is 0.27.

[0181] Examples 3 to 6 were prepared according to the procedures of Examples 1 and 2. Table 1: [Table 1] B) Production of silane-terminated polymers (STPs), also known as silylated polymers, and silane-terminated polyols, from the reaction of isocyanate prepolymers. (Example 8)

[0182] Approximate number-average molecular weight M n 150.2 g (8.3 mmol) of polypropylene glycol with an OH value of 18000 g / mol (OH value = 6.0 ± 1.0 mg KOH / g) was placed in a 500 ml three-necked flask and dried under reduced pressure at 90°C for 1 hour. The reduced pressure was then released with nitrogen. The polyol was cooled to 80°C. 1.5 mg (0.0015 mmol, pure substance) of TiPOSS catalyst and 4.01 g (18 mmol) of isophorone diisocyanate (IPDI) were added with stirring. As soon as the theoretical NCO content of 0.52 wt% was reached, 4.97 g (21 mmol) of N-[3-(trimethoxysilyl)propyl]butylamine] was added with stirring, and the system was simultaneously cooled to 25°C. The reaction was monitored by IR spectroscopy (disappearance of the NCO band (2270 cm)). -1 )). 2% by weight of VTMO was added to the completed STP. The viscosity of the product was 43,000 mPas (25°C, Brookfield viscosity). The present invention provides, for example, the following items: (Item 1) In the presence of a catalyst, I. A compound containing at least one isocyanate having a molecular weight of 120 Da to 1000 Da, II. Number average molecular weight M from 3500 to 100000 Da n A hydroxy-functionalized polymer having A polyurethane prepolymer that can be obtained by the reaction, wherein 2000 Da(x) along the x-axis 1 ) to 200000Da(x 3 The molecular weight profile of the aforementioned polyurethane prepolymer, as measured by gel permeation chromatography, is obtained by area integral F I The first section and area integral F have II It has a second section having a ratio F II / F I The value is between 0 and 0.4 (including 0.4), and the first section is x 1 from x 2 It extends to and the second section is x 2 from x 3 It extends to x 2 A polyurethane prepolymer characterized by defining an extreme point between the last maximum intensity (M1a) in the first section and the subsequent maximum intensity (M2) in the second section, which are within the molecular weight range of the hydroxy-functionalized polymer. (Item 2) The polyurethane prepolymer according to item 1, characterized in that the molar ratio of NCO groups to hydroxyl groups in the reaction between I. and II. is 5.0:1 to 1.05:1, preferably 4:1 to 1.5:1, and more preferably 3.0:1 to 1.8:1. (Item 3) The peak (M1a) is given by the following equation A

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Claims

1. The molecular weight profile of a polyurethane prepolymer from 2000 Da (x １ ) to 200000 Da (x ３ ), measured by gel permeation chromatography, has a first section with an area integral F Ｉ and a second section with an area integral F ＩＩ , and the ratio F ＩＩ / F Ｉ is between 0 and 0.4 (including 0.4), the first section extends from x １ to x ２ , the second section extends from x ２ to x ３ , x ２ defines an extreme point between the last intensity maximum (M1a) in the first section within the molecular weight region of the hydroxy-functionalized polymer and the subsequent intensity maximum (M2) in the second section. In the presence of a catalyst, I. Isophorone diisocyanate (IPDI) and, II. Number average molecular weight M of 3500 to 100000 Da ｎ A hydroxy-functionalized polymer having As a result of the reaction, A process for producing polyurethane prepolymers, In the reaction between I. and II., the molar ratio of NCO group to hydroxyl group is 3.0:1 to 1.8:

1. A process characterized in that the reaction temperature between I. and II. is between 20°C and 90°C, the catalyst is heptisobutylPOSS-titanium(IV) ethoxide (TiPOSS), and the total amount of the catalyst is between 3 ppm and 80 ppm relative to the total weight of the hydroxy-functionalized polymer used.

2. The peak (M1a) is given by the following equation A 【Chemistry 14】 (In the formula, n = x + y, where n is the number of OH groups / functional groups in the polyol.) (In the formula, R Ｉｓｏ R is a structural unit of the isocyanate-containing compound, Ｐｏｌｙ (where n is the structural unit of the hydroxy-functionalized polymer, n is x + y, and n represents the number of OH groups (functional groups) in the polyol.) The process according to claim 1, which corresponds to the molecular weight range of the polyurethane prepolymer.

3. The hydroxy-functionalized polymer has a number average molecular weight M of 3,500 to 100,000 g / mol. ｎ The process according to claim 1 or 2, characterized in that the polyols having the properties are selected from the group consisting of polyether polyols, polyester polyols, polycarbonate polyols, and further mixtures thereof.

4. The hydroxy-functionalized polymer is polyoxyalkylenediol, polyoxyalkylentriol, sorbitol, pentaerythritol-starting polyol, ethylene oxide-terminated polyoxypropylene polyol, polyester polyol, styrene-acrylonitrile, acrylic-methacrylate, (poly)urea-grafted or containing polyether polyol, polycarbonate polyol, CO ２ The process according to claim 1 or 2, characterized in that the material is selected from the group consisting of a polyol, a polytetrahydrofuran polyether (PTMEG), an OH-terminated prepolymer based on the reaction of a polyetherol or polyesterol with a polyisocyanate, a polypropylene diol, a polyester polyol, or a mixture thereof.

5. The process according to claim 1 or 2, characterized in that the hydroxy-functionalized polymer is selected from the group consisting of polyester polyols and polyether polyols.

6. A polyurethane prepolymer that can be obtained by the process described in any one of claims 1 to 5.

7. A polyurethane prepolymer as described in claim 6, which can be obtained by the process described in any one of claims 1 to 5, Primary aminosilanes; secondary aminosilanes; aminosilanes selected from products obtainable by Michael-like addition of primary aminosilanes to Michael acceptors and N-alkylaminosilanes. Silylated polyurethanes can be obtained by reacting them.

8. The silylated polyurethane according to claim 7, wherein the aminosilane is selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, N-butyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, dimethyl N-(3-trimethoxysilylpropyl)aminosuccinate, diethyl N-(3-trimethoxysilylpropyl)aminosuccinate, N-butyl-3-aminopropyltrimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, [(N-cyclohexylamino)methyl]methyldiethoxysilane, N-ethylaminomethylmethyldiethoxysilane, N-butyl-3-amino-2-methylpropyltrimethoxysilane, N-ethyl-4-amino-3,3-dimethylbutyldimethoxymethylsilane, and N-ethyl-4-amino-3,3-dimethylbutyltrimethoxysilane.

9. The silylated polyurethane comprises a polymer main chain (P) and general formula (V) 【Chemistry 16】 (In the formula, - X is N, and in each case it is bonded to the carbon in the polymer main chain, - R ＊ These are, if necessary, substituted linear or branched C1 to C25 alkyl groups, or, if necessary, substituted C4 to C18 cycloalkyl groups, or, if necessary, substituted C4 to C18 aryl groups. - Each Y is independent of the others, O, or each R ９ , R １０ , or R １１ One of the direct bonds between a Si atom and a radical, - R ８ This is H, optionally substituted linear or branched C1 to C16 alkyl groups, optionally substituted linear or branched C2 to C16 alkenyl groups, optionally substituted linear or branched C2 to C16 alkynyl groups, optionally substituted C4 to C14 cycloalkyl groups, optionally substituted C4 to C14 aryl groups, or radicals of the general structure (Vb). - R １２ and R １４ These are H or -R, each independent of the other. １５ , -COOR １５ A radical from the group consisting of , and -CN, - R １３ is H, or -CH ２ - COOR １５ , -COOR １５ , -CONHR １５ , -CON(R １５ ), -CN, -NO ２ , -PO(OR １５ ) ２ , -SOR １５ , and -SO ２ OR １５ A radical from the group consisting of, - R １５ This is a hydrocarbon radical having 1 to 20 carbon atoms and optionally containing at least one heteroatom. - R ９ , R １０ , and R １１ These are independently H, optionally substituted linear or branched C1 to C5 alkyl groups, optionally substituted linear or branched C2 to C10 alkenyl groups, optionally substituted C4 to C14 cycloalkyl groups, or optionally substituted C4 to C14 aryl groups. (m is 1) The silylated polyurethane according to claim 7 or 8, characterized by comprising at least two terminal groups.

10. General structure (VIII) 【Chemistry 17】 (Here, - R ７ H is, - R ８ This is H, optionally substituted linear or branched C1-C25 alkyl groups, optionally substituted linear or branched C2-C25 alkenyl groups, optionally substituted C4-C18 cycloalkyl groups, optionally substituted C4-C18 aryl groups, or the radical of the general structure (Vb). - R １２ and R １４ These are H or -R, each independent of the other. １５ , -COOR １５ A radical from the group consisting of , and -CN, - R １３ is H, or -CH ２ - COOR １５ , -COOR １５ , -CONHR １５ , -CON(R １５ ), -CN, -NO ２ , -PO(OR １５ ) ２ , -SOR １５ , and -SO ２ OR １５ A radical from the group consisting of, - R １５ This is a hydrocarbon radical having 1 to 20 carbon atoms and optionally containing at least one heteroatom. - R ９ , R １０ , R １１ , and R ＊ is defined in accordance with claim 9, - Each Y is independent of the others, O, or each R ９ , R １０ , or R １１ (Either of the direct bonds of the Si atom to the radical) The silylated polyurethane according to claim 9, characterized in that an aminosilane is selected or a mixture thereof.

11. The general structure (VIII) (where, - R ８ is H, optionally substituted linear or branched C1 to C10 alkyl groups, optionally substituted linear or branched C2 to C10 alkenyl groups, optionally substituted linear or branched C2 to C10 alkynyl groups, optionally substituted C4 to C10 cycloalkyl groups, optionally substituted C4 to C10 aryl groups, or succinic acid derivative of the general structure (Vb) described in claim 10. - R ＊ These are linear or branched C1 to C20 alkyl groups which are substituted as needed, or C4 to C12 cycloalkyl groups which are substituted as needed, or C4 to C12 aryl groups which are substituted as needed. - R ９ , R １０ , and R １１ This is defined by claim 9, - Y-R ９ and Y-R １０ The Y inside is O, and Y-R １１ The Y inside is O, or each R １１ (Either of the direct bonds of the Si atom to the radical) The silylated polyurethane according to claim 10, characterized in that at least one aminosilane is selected, or a mixture thereof.

12. The above aminosilane is of formula (IX) 【Chemistry 19】 (In the formula, Two R １６ and R １７ Each radical is independent of the others, and the R １６ A radical is a monovalent hydrocarbon radical that is linear or branched and has 1 to 8 carbon atoms. The aforementioned R １７ A radical is an acyl radical, or a linear or branched monovalent hydrocarbon radical having 1 to 5 carbon atoms, where the subscript a is 0, 1, or 2. R １８ A radical is a linear or branched divalent hydrocarbon radical having 1 to 12 carbon atoms, optionally containing a cyclic portion and optionally one or more heteroatoms. R １９ is a cyclic, linear, or branched monovalent hydrocarbon radical having a hydrogen atom or 1 to 20 carbon atoms (the hydrocarbon radical may optionally contain a cyclic portion), or the following formula: 【Chemistry 20】 It is a radical of, In the formula, R ２０ and R ２１ radicals are each independently a hydrogen atom or a radical from the group consisting of -R ２３ , -COOR ２３ , and -CN, and R ２２ radical is a hydrogen atom or a radical from the group consisting of -COOR ２３ , -CONHR ２３ , -CON(R ２３ ), -CN, -NO ２ , -PO(OR ２ ), -SO ２３ R ２ , and -SO ２ OR ２３ , and -SO ２ OR ２３ , and R ２３ radical is a hydrocarbon radical having 1 to 20 C atoms and optionally containing at least one heteroatom, and is also a mixture thereof) A silylated polyurethane according to claim 7 or 8, characterized in that it corresponds to an aminosilane.

13. A silylated polyurethane according to any one of claims 7 to 12, or A composition comprising one or more polyurethane prepolymers as described in claim 6.

14. Use of the polyurethane prepolymer according to claim 6 for producing polyurethane elastomers, polyurethane urea, or one- or two-component reactive polyurethane systems as polyurethane foams, construction materials, varnishes, coatings, adhesives and sealants, grouts, films, or PUR elastomers.

15. Use of the polyurethane prepolymer according to claim 6 for producing a reactive PU composition.

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