EP4196513A1 - Synthèse sélective de prépolymères de polyuréthane - Google Patents

Synthèse sélective de prépolymères de polyuréthane

Info

Publication number
EP4196513A1
EP4196513A1 EP21763296.7A EP21763296A EP4196513A1 EP 4196513 A1 EP4196513 A1 EP 4196513A1 EP 21763296 A EP21763296 A EP 21763296A EP 4196513 A1 EP4196513 A1 EP 4196513A1
Authority
EP
European Patent Office
Prior art keywords
group
nco
polyol
silylated polyurethanes
functionalized
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21763296.7A
Other languages
German (de)
English (en)
Inventor
Klaus Langerbeins
Michael Senzlober
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PolyU GmbH
Original Assignee
PolyU GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by PolyU GmbH filed Critical PolyU GmbH
Publication of EP4196513A1 publication Critical patent/EP4196513A1/fr
Pending legal-status Critical Current

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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/60—Compositions for foaming; Foamed or intumescent coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/60—Compositions for foaming; Foamed or intumescent adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2190/00—Compositions for sealing or packing joints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/08—Crosslinking by silane

Definitions

  • the present invention relates to a process for the production of polyurethane prepolymers, in particular NCO-functionalized polyols, their use in the production of silylated polyurethanes, a process for the production of silylated polyurethanes and silylated polyurethanes obtainable by a reaction of NCO-functionalized polyol with organosilane and their use in CASE areas (coatings, adhesives, seals and elastomers).
  • the method is preferably selective.
  • Urethane prepolymers also “NCO prepolymers” containing isocyanate groups are particularly widespread and of economic importance. Furthermore, urethane prepolymers are known which contain curable functional groups such as silane groups.
  • polyurethanes with terminal NCO groups
  • polyfunctional alcohols also "polyols”
  • isocyanate-containing compounds in the Rule polyisocyanates
  • These NCO-terminated polyurethane prepolymers can then serve as starting materials for the production of silylated polymers, the NCO prepolymer being reacted with an appropriate aminosilane.
  • Silylated polyurethanes which condense (“crosslink”) on contact with water or humidity and at room temperature, have been known for a long time. They are also referred to as moisture-crosslinking polymers. Depending, among other things, on the content of the silane groups and their structure, long-chain polymers, wide-meshed three-dimensional networks or highly crosslinked systems can form.
  • Moisture-crosslinking polymers in particular silylated polyurethanes, have long been used as adhesives and sealants in a wide variety of applications.
  • the area of traditional silicone adhesives and sealants based on dimethylpolysiloxanes and polyurethane adhesives and sealants with free isocyanate groups developed into silane-terminated adhesives and sealants.
  • High-viscosity silane-modified polymers when used in the field of sealant and adhesive systems, usually require amounts of 30-50% by weight or 30-70% by weight of inorganic fillers such as calcium carbonate or silicates, which leads to poor processability.
  • inorganic fillers such as calcium carbonate or silicates
  • plasticizers and thinners which is necessary for good processing, causes problems due to possible plasticizer migration.
  • viscosity-lowering reactive diluents or monomeric alkoxysilanes results in unfavorable costs and higher methanol emissions from the adhesive systems.
  • EP 1 924 623 A1 describes, for example, urethane prepolymers which have alkoxysilyl groups, which are allophanate-modified and whose allophanate structure has a moisture-curing silane-functional radical.
  • Example 1 it is shown that the conversion of a PPG (polypropylene glycol) with a molecular weight of about 8000 g / mol (Acclaim 8200) with an initial viscosity of about 3000 mPas in the best case and use of secondary aminosilanes to polymers with a viscosity of 20500 mPas leads.
  • PPG polypropylene glycol
  • EP 2 468 759 A1 also describes urethane prepolymers containing alkoxysilyl groups, which are modified with substituted aminosilanes.
  • PPGs with a molecular weight of about 12,000 g/mol (Acclaim 12200) are converted with IPDI in a molar ratio of 1:2.4 to PU prepolymers with a viscosity of 40,000 mPas.
  • the subsequent reaction with various aminosilanes shows the advantage of secondary aminosilanes as endcappers compared to primary aminosilanes. Nevertheless, the lowest viscosity achieved (Example 13) was very high at 81,000 mPas, which also speaks for a high proportion of oligomeric components.
  • the prepolymers bearing NCO groups also referred to as “polyurethane prepolymers” for short
  • the prepolymers bearing NCO groups also referred to as “polyurethane prepolymers” for short
  • residual monomer content can have a disruptive effect on the application of NCO prepolymers or on their further processing, e.g. to form silylated polyurethanes.
  • the proportion of monomeric isocyanate in these products can be more than 50% by weight.
  • Monomeric isocyanates such as aromatic toluylene diisocyanate (TDI), aliphatic hexamethylene-1,6-diisocyanate (HDI) and cycloaliphatic isophorone diisocyanate (IPDI) have a noticeable vapor pressure even at room temperature and are therefore toxic, especially in spray applications, due to the isocyanate vapors that occur .
  • TDI aromatic toluylene diisocyanate
  • HDI aliphatic hexamethylene-1,6-diisocyanate
  • IPDI cycloaliphatic isophorone diisocyanate
  • MDI diphenylmethane diisocyanate
  • MDI diphenylmethane diisocyanate
  • the object of the present invention was therefore to overcome at least one disadvantage of the prior art.
  • the task was to provide silylated polyurethanes with very low viscosities.
  • silylated polyurethanes obtainable according to claim 1. These are obtainable by reacting NCO-functionalized polyol with organosilane. The reaction with at least one aminosilane is particularly preferred. Most preferred are silylated polyurethanes from a reaction of an NCO-functional polyol with at least one aminosilane, where the NCO-functional polyol used was prepared by a reaction of at least one asymmetric isocyanate-containing compound (A) with at least one polyol (B) which has a number-average molecular weight M n of 3500 to 100000 g/mol, preferably 3800 to 90000 g/mol, particularly preferably 4000 to 80000 g/mol and the molar Ratio of NCO groups to OH groups from 3.05:1 to 1.05:1, preferably from 2.8:1 to 1.5:1 and particularly preferably from 2.1:1 to 1.8:1 amounts to.
  • M n number-average molecular weight
  • the invention also relates to compositions containing the NCO-functionalized polyols used according to the invention or the silylated polyurethanes according to the invention.
  • the invention also relates to the use of NCO-functionalized polyols, in particular in the production of silylated polyurethanes and processes for the production of silylated polyols.
  • the invention also relates to the use or further processing of silylated polyurethanes produced in this way, in particular in CASE applications (coatings, adhesives, seals and elastomers) and/or elastomeric material.
  • Silylated polyurethanes according to the invention can be processed particularly well.
  • these silylated polyurethanes according to the invention can also subsequently have advantageous material properties in their respective end products.
  • Both the NCO-functionalized polyols used according to the invention themselves and the silylated polyurethanes produced therefrom advantageously have a low residual monomer content. This results in particular from the previous synthesis of the NCO-functionalized polyols. Accordingly, it is possible to severely restrict work-up or purification steps (such as distillation, etc.). Ideally, they can be dispensed with entirely.
  • a particular advantage of the invention is therefore that the NCO-functionalized polyols used, if possible, require no further purification step after their preparation in order to have low residual monomer contents of the isocyanate-containing compound(s) used.
  • the lowest possible residual monomer contents can also have a positive effect on the silylated polyurethanes of the invention, their compositions and formulations.
  • the residual monomer contents are advantageously less than ( ⁇ )1% by weight, preferably less than or equal to ( ⁇ )0.5% by weight, particularly preferably less than or equal to ( ⁇ )0.1% by weight.
  • the silylated polyurethanes according to the invention can remain “additive-free” since they can already have suitable and advantageous viscosities according to the invention.
  • the Silylated polyurethanes according to the invention are therefore preferably free from plasticizers and/or thinners.
  • Additives that are usually required to influence the viscosities of silylated polyurethanes or compositions thereof generally have a negative effect on the subsequent product properties (e.g. Shore hardness, tensile strength or general product longevity, migration behavior).
  • the silylated polyurethanes according to the invention can already enable a viscosity that is at least 20% lower by their production, ie by a reaction of NCO-functionalized polyol with organosilane, preferably with at least one aminosilane.
  • the lower viscosity in each case relates to the direct comparison with silylated polyurethanes which were produced with conventional NCO-functionalized polyurethane prepolymers, ie with oligomeric or polymeric NCO-functionalized polyurethane prepolymers.
  • NCO-terminated polyurethane prepolymers (here also just “polyurethane prepolymers”) with a narrow molar mass distribution can be prepared, in particular NCO-functionalized polyols used in this way according to the invention can be produced. These have a particularly low viscosity.
  • the reaction kinetics are determined in particular by the parameters reaction temperature, type and amount of catalyst and reaction time.
  • NCO-functionalized polyurethane prepolymers so-called NCO-functionalized polyols, which are particularly suitable for the production of the silylated polyurethanes according to the invention.
  • NCO-functionalized polyols result.
  • NCO-functionalized polyols in particular are obtained as the reaction product from this reaction, while the formation of oligomeric or even polymeric NCO-functionalized compounds, ie those composed of at least two polyol molecules linked to one another via urethane bonds, is significantly reduced.
  • the process is therefore selective for NCO-functionalized polyols.
  • “selective” means that the main product from the reaction of isocyanate-containing compounds with polyols is the desired product, in the present case a polyurethane prepolymer with a narrow molar mass distribution. In particular, it is an NCO-functionalized polyol.
  • Main product is always the product which has a content or proportion in an elugram of gel permeation chromatography (GPC) greater than or equal to (>) 60 area %, preferably greater than or equal to (>) 70 area %, particularly preferably greater than or equal to (>) 80 areas -%, most preferably greater than or equal to (>) 85% by area.
  • GPC gel permeation chromatography
  • NCO-functionalized polyol consequently describes a compound composed of one part polyol and n parts isocyanate-containing compound, where n is at least 2.
  • polyol stands for the origin of the backbone (ergo from the starting material used, the polyol).
  • the previous OH functionalities of the polyol used react in a reaction with an isocyanate-containing compound, resulting in a "polyol with NCO functions", i.e. an NCO-functionalized polyol.
  • NCO stands for the isocyanate groups resulting from the isocyanate-containing compound(s) used.
  • the NCO-functionalized polyol can also be represented by the general structure (I), whereby R iso is the structural unit of the isocyanate-containing compound(s) (A) used in the preparation of the NCO-functionalized polyol and R poly is the structural unit of the polyol (B) used and where n is x+y and n is the number of free OH groups in the polyol (B) used corresponds.
  • the number of free OH groups in the polyol, i.e. per molecule, is also referred to as the "functionality" of the polyol.
  • the structure of the NCO-functionalized polyols used according to the invention can also be described by an A n B structure, where A stands for the isocyanate-containing compound(s) used to prepare the NCO-functionalized polyol, preferably an isocyanate-containing compound. and B is the polyol used and n corresponds to the number of free OH groups in the polyol (B) used
  • polyol to be the collective term for polyhydric alcohols, namely organic compounds which contain at least two hydroxide groups in the molecule (also: hydroxy-functionalized polymer).
  • polyether polyols or polyester polyols are particularly preferred.
  • alkylene glycols form the backbone of the polyol as repeating units.
  • Polyester polyols are built up from the repeating units of carboxylic acid esters or carbonates or from copolymers thereof.
  • isocyanates includes all isocyanate-containing compounds that carry at least one isocyanate group.
  • polyisocyanates includes all isocyanate-containing compounds with at least two isocyanate groups.
  • NCO-terminated polyurethane prepolymers can be produced selectively by controlling the process control, which is fundamentally known to those skilled in the art.
  • the selectivity of the reaction can be shown by analyzing the molecular weight distribution.
  • the polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, can thus be characterized by their molecular weight distribution.
  • the selectivity of the reaction for producing polyurethane prepolymers in particular the NCO-functionalized polyols used according to the invention, can be checked and represented, for example, by means of gel permeation chromatography (GPC for short).
  • GPC gel permeation chromatography
  • An elugram obtained from an investigation of polyurethane prepolymer or of NCO-functionalized polyol by means of GPC can do that with the plot the elution volume progressing with the continuous flow of the eluate against the corresponding signal intensities of the detector.
  • the course of the elugram shows "when", i.e. at which elution volume (V, mL) which component of the sample is detected by the detector.
  • the components with high molecular weights are detected first, followed by components with small molecular weights.
  • the continuous measurement process results in a curve with rising and falling areas (ie the intensity of the signal increases or decreases).
  • the magnitude of the intensity and the area integral underneath reflect, among other things, the amount of the respective components in the sample, depending on the injected sample concentration.
  • an associated molar mass can be determined by comparison with the generated graph or by calculation using a standardized regression analysis. From this, a corresponding molecular weight distribution can be obtained as an inverse plot of the molecular weights against the associated signal intensities of the eluted sample. This plot is referred to herein as the molecular weight curve.
  • the course on the x-axis of the diagram starts with sample components of smaller molecular weight and, as the course of the x-axis progresses, reflects corresponding intensity signals of the higher molecular weights.
  • the molecular weight curve of the polyurethane prepolymers, in particular of the NCO-functionalized polyols used according to the invention, shows in a range from 2000 Da (XT) to 200000 Da (x 3 ) along the x-axis that there is a first section with an area integral F
  • extreme point preferably describes a low point or also a minimum of intensity.
  • Molecular weight can be synonymous with the terms “molecular weight” or “molecular mass' be used. It can be specified both in Dalton (Da) and synonymously in grams per mole (g/mol).
  • FIG. 1 describes the course of the molecular weight for calculating the ratio of the area integrals (F N /F
  • One or more further intensity maxima may be present in the first section.
  • One or more further intensity maxima can likewise lie in the second section.
  • according to the invention is in the range between 0 and 0.4 inclusive, preferably between 0.05 and 0.39 inclusive, particularly preferably between 0.1 and 0.38 inclusive.
  • the position of the intensity maximum M1a is in the range of the molecular weight of the hydroxy-functionalized polymer (polyol) used in each case. It follows from this that the position of x 2 also depends on the molecular weight of the hydroxy-functionalized polymer used.
  • the intensity maximum M1a is accordingly in the molecular weight range of the polyurethane prepolymers, in particular the NCO-functionalized polyols of the following formula (I) used according to the invention
  • n corresponds to the number of OH groups in the polyol/functionality in which R iso stands for the structural unit of the isocyanate-containing compound (A) and R poly for the structural unit of the hydroxy-functionalized polymer, where n is equal to x + y and n indicates the number of OH groups in the polyol (functionality).
  • corresponds to the molecular weight range of the polyurethane prepolymer, in particular of the NCO-functionalized polyol, which is obtained by reacting an NCO group of the polyisocyanate.
  • F N corresponds to the molecular weight range of the higher oligomers, higher oligomers being reaction products obtained in the preparation of the NCO-terminated prepolymers in which the polyisocyanate used has reacted on more than one NCO group, such as allophanate, biuret reaction products, isocyanurates and Oligomer blocks longer than isocyanate polymer isocyanate.
  • the system PSS WinGPC UniChrom V 8.31, Build 8417 from PSS GmbH, DE is preferably used for the computer-controlled software.
  • Polyurethane prepolymers can be obtained by a reaction of
  • a hydroxy-functionalized polymer having a number-average molecular weight M n of 3500 to 100,000 g/mol, preferably 3800 to 90,000, particularly preferably 4000 to 80,000 g/mol, in the presence of a catalyst.
  • inventively used (or "used”) NCO-functionalized polyols are preferably obtainable by a reaction of
  • the molar ratio of NCO groups to OH groups in the reaction of I. with II. being from 3.05:1 to 1.05:1, preferably from 2.8:1 to 1.5:1 and particularly preferably from 2.1:1 to 1.8:1.
  • the isocyanate-containing compound (A) has a molecular weight of 120 g/mol to 1000 g/mol. It is also preferred that the polyol (B) in the reaction of I. with II. has a number-average molecular weight Mn of 3500 to 100,000 g/mol, preferably 3800 to 90,000 g/mol, particularly preferably 4000 to 80,000 g/mol .
  • reaction of I. with II. is suitably carried out at temperatures of less than or equal to ⁇ 80.degree. C., in particular at temperatures of from 15 to 70.degree. C., preferably at temperatures of from 25 to 65.degree.
  • the isocyanate-containing compound (A) is a diisocyanate.
  • An embodiment in which the isocyanate-containing compound (A) is asymmetric is particularly preferred.
  • asymmetric means, as the person skilled in the art knows, that the isocyanate-containing compound (A) has no mirror plane in the molecule itself.
  • the NCO groups contained in the asymmetric isocyanate-containing compound also have different steric surroundings of the NCO groups, which in turn leads to different reactivities of these.
  • Particularly suitable asymmetric isocyanate-containing compounds for this are: isophorone diisocyanate (IPDI), 2,4'-
  • IPDI is used as the isocyanate-containing compound (A).
  • the conversion of the polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, into silylated polyurethanes does not result in any significant change in the molecular weight distribution, which is why a calculation of the area quotient according to the invention based on the silylated polyurethanes is also permissible; with the proviso that no water-induced condensation of the silylated polyurethane occurs.
  • the NCO-functionalized polyol used according to the invention obtainable from the reaction of I. with II., has a greater content of NCO-functionalized polyol according to the structure perfection A n B or the general structure (I) in an elugram of a gel permeation chromatography (GPC) after the reaction has taken place equal to (>) 60% by area, preferably greater than or equal to (>) 70% by area, particularly preferably greater than or equal to (>) 80% by area, extremely preferably greater than or equal to (>) 85% by area.
  • the molecular weight is measured by a molecular weight distribution obtained by GPC under the following conditions:
  • the columns are tempered in an oven heated to 70 degrees Celsius.
  • THF tetrahydrofuran
  • a solvent is fed to the columns, which are maintained at this temperature, at a flow rate of 1 ml per minute, and 50 to 200 ⁇ l of a THF sample solution of a polyurethane prepolymer, in particular the NCO-functionalized polyol, with a sample concentration of 0.5 to 1 .5 g/L, are injected for measurement.
  • the molecular weight distribution ascribed to the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared using several kinds of monodisperse polystyrene standard samples and the efflux time count number.
  • RI detector refractive index detector
  • the GPC columns can preferably be used in combination with a variety of commercially available polystyrene gel columns.
  • they may preferably consist of a combination of Agilent columns PLGEL 5 pm MIXED-D, 7.5 x 300 mm, PLGEL 3 pm MIXED-E, 7.5 x 300 mm, the combination consisting of three columns, the first both columns being PLGEL 5 pm MIXED-D and the third column being PLGEL 3 pm MIXED-E, 7.5 x 300 mm.
  • the molecular weight distribution of the polyurethane prepolymer, in particular of the NCO-functionalized polyol is measured under the conditions specified there.
  • the molar ratio of NCO groups to hydroxyl groups in the reaction of I. with II. is preferably from 5.0:1 to 1.05:1, preferably from 4:1 to 1.5:1 and most preferably from 3.0:1 to 1.8:1.
  • the molar ratio of NCO groups to hydroxyl groups is preferably from 3.05:1 to 1.05:1, preferably from 2.8:1 to 1.5:1 and particularly preferred selected from 2.1:1 to 1.8:1.
  • the NCO-functionalized polyols obtained from the reaction of I. with II have a residual monomer content, ie a residual content of isocyanate-containing compound (A) which has not reacted with the polyol, of less than ( ⁇ ) 1% by weight, preferably less than or equal to ( ⁇ ) 0.5% by weight, particularly preferably less than or equal to ( ⁇ ) 0.1% by weight, based on the weight of the NCO-functionalized polyol.
  • the determination of the residual monomer content i.e.
  • residual content in the context of the invention describes the proportion remaining after a reaction.
  • the residual content or the "residual monomer content” is stated in % by weight and is based on the total weight of the reaction product or the reaction products of a starting material used in the reaction, here based on the weight of the NCO-functionalized polyol.
  • the relevant remaining starting material, of which the residual content is given, has generally not been converted.
  • NCO groups can, for example, react with alcohols to form urethanes or with amines to form urea derivatives.
  • Isocyanate-containing compounds (A) can be described by the general formula (VI).
  • R x is a carbon-containing group, preferably at least one aromatic or aliphatic group or mixtures thereof, more preferably an optionally substituted, straight-chain or branched C1 to C20 alkyl group, an optionally substituted, straight-chain or branched C2 to C20 alkenyl group or an optionally substituted C 2 to C 20 straight-chain or branched alkynyl group, an optionally substituted C 4 to C 14 cycloalkyl group or an optionally substituted C 4 to C 14 aryl group, most preferably diphenylmethane, toluene, dicyclohexylmethane, hexane or methyl-3 ,5,5-trimethylcyclohexyl means or
  • R x is a -(R*)-Si(YR 9/10/11 ) 3 group, where R 9 , R 10 and R 11 are independently H, an optionally substituted, straight-chain or branched C 1 to C 25 alkyl group, represents an optionally substituted, straight-chain or branched C 2 to C 25 alkenyl group or an optionally substituted C 4 to C 18 cycloalkyl group or an optionally substituted C 4 to C 18 aryl group,
  • Each Y independently of one another is either O or a direct bond of the Si atom to the respective radical R 9 , R 10 or R 11 , preferably at least one YO and
  • Polyisocyanates in particular are used for the production of the NCO-functionalized polyols used according to the invention.
  • Polyisocyanates always have at least two isocyanate groups.
  • isocyanates in particular polyisocyanates of the general formula (VI), can be used as polyisocyanates for the production of the polyurethane prepolymer according to the invention, in particular the NCO-functionalized polyol
  • R x is a carbon-containing group, preferably at least one aromatic or aliphatic group or mixtures thereof, more preferably an optionally substituted, straight-chain or branched C1 to C20 alkyl group, an optionally substituted, straight-chain or branched C2 to C20 alkenyl group or an optionally substituted C 2 to C 20 straight or branched alkynyl group, an optionally substituted C 4 to C 14 cycloalkyl group or an optionally substituted C 4 to C 14 aryl group, most preferably diphenylmethane, toluene, dicyclohexylmethane, hexane or methyl-3 ,5,5-trimethylcyclohexyl means and
  • suitable polyisocyanates are diphenylmethane diisocyanate (MDI), in particular of diphenylmethane-4,4'-diisocyanate (4,4'-MDI), diphenylmethane-2,4'-diisocyanate (2,4'-MDI), diphenylmethane-2,2 '-diisocyanate (2,2'-MDI), 4,4'-MDI
  • Diisocyanatodicyclohexylmethane H12MDI
  • 1,12-dodecamethylene diisocyanate 1,12-dodecamethylene diisocyanate
  • lysine and lysine ester diisocyanate 1,12-dodecamethylene 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 IPDI
  • TCDI 1,4-diisocyanato-2,2,6-trimethylcyclohexane
  • HDI 1,6-hexamethylene diisocyanate
  • HDI trimer 1,4-bis(isocyanate)cyclohexane
  • PPDI 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
  • TDI 1,3- and/or p-Tetramethyl-1,3-xylylene diisocyanate
  • TDI 1,3- and
  • 1,4-phenylene diisocyanate 2,4-dioxo-1, 3-diazetidine-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'-diisocyanatodiphenyl (TODI), or mixtures thereof, preferably diphenylmethane-4,4'-diisocyanate (4,4'-MDI), Diphenylmethane-2,4'-diisocyanate (2,4'-MDI) or isophorone diisocyanate (IPDI), 1,6 hexamethylene diisocyanate (HDI) or the trimer thereof (HDI trimer) or mixtures thereof, very particularly preferably diphenylmethane-4,4 '-diisocyanate (4,
  • the different reactivity of the NCO groups of the polyisocyanate is caused by different neighboring substituents to the NCO groups on the molecule, which reduce the reactivity of one NCO group compared to the other NCO group, for example due to steric shielding, and/or due to different binding of an NCO - Group to the rest of the molecule, for example in the form of a primary or secondary NCO group.
  • aromatic polyisocyanates are all isomers of tolylene diisocyanate (TDI), either in isomerically pure form or as a mixture of several isomers, naphthalene-1,5-diisocyanate (NDI), naphthalene-1,4-diisocyanate (NDI), diphenylmethane diisocyanate (4,4 '-MDI), diphenylmethane-2,4'-diisocyanate (2,4'-MDI) and mixtures of 4,4'-diphenylmethane diisocyanate (4,4'-MDI) with the 2,4'-MDI isomer and 1 ,3-phenylene diisocyanate.
  • TDI tolylene diisocyanate
  • NDI naphthalene-1,5-diisocyanate
  • NDI naphthalene-1,4-diisocyanate
  • cycloaliphatic polyisocyanates are 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethylcyclohexane (isophorone diisocyanate, IPDI), 1-methyl-2,4-diisocyanatocyclohexane or hydrogenation products of the aforementioned aromatic polyisocyanates, especially hydrogenated ones MDI in isomerically pure form, preferably hydrogenated 2,4'-MDI.
  • Examples of preferred aliphatic polyisocyanates are 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane and lysine diisocyanate.
  • IPDI Isophorone diisocyanate
  • diphenylmethane-2,4'-diisocyanate (2,4'-MDI) and diphenylmethane-4,4'-diisocyanate (4,4'-MDI) and mixtures thereof are particularly preferred.
  • IPDI and mixtures with the aforementioned are very particularly preferred.
  • IPDI Isophorone diisocyanate
  • diphenylmethane-2,4'-diisocyanate (2,4'-MDI) and diphenylmethane-4,4'-diisocyanate (4,4'-MDI) and mixtures thereof in combination with other isocyanate-containing compounds can also be used will.
  • Hydroxy-functional compounds are understood as meaning hydroxy-functional polymers.
  • Suitable polyols for the production of polyurethane polymers are in particular polyether polyols, polyester polyols and polycarbonate polyols and mixtures of these polyols.
  • the hydroxy-functional compounds preferably have a number-average molecular weight M n of 3500 to 100,000 g/mol, preferably 3800 to 90,000, particularly preferably from 4000 to 80000 g/mol.
  • the hydroxy-functionalized polymer is preferably selected from the group consisting of polyoxyalkylene diols or polyoxyalkylene triols, in particular polyoxyethylene and polyoxypropylene diols and triols, polyols of higher functionality such as sorbitol, petaerythritol-started polyols, ethylene oxide-terminated polyoxypropylene polyols, polyester polyols, styrene-acrylonitrile, acryl-methacrylate, (Poly)urea-grafted or containing polyether polyols, polycarbonate polyols, CO 2 polyols, polytetrahydrofuran-based polyethers (PTMEG), OH-terminated prepolymers based on the reaction of a polyether or polyesterol with a polyisocyanate, polypropylene diols, polyester polyols or mixtures thereof, preferably polypropylene diols , polyester polyols, or mixtures
  • Polyethers represent a class of polymers. They are long-chain compounds comprising at least two identical or different ether groups. According to the invention, polyethers are also used when the polymeric ether groups are interrupted by other groups (e.g. by polymerized/incorporated isocyanates or other polymer or oligomer units of different monomer origin).
  • polyether polyols also called polyoxyalkylene polyols or oligoetherols
  • polyoxyalkylene polyols or oligoetherols are those which are polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, oxetane, tetrahydrofuran or mixtures thereof, optionally polymerized with the aid of a starter molecule with two or more active hydrogen atoms such as water, ammonia or compounds with several OH or NH groups such as 1,2-ethanediol, 1,2- and 1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and Tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octaned
  • polyether polyols with block copolymer structures are used. These can be used by reacting the abovementioned cyclic ethers with oligomeric starting blocks such as polyoxytetramethylene, polyoxyethylene, polybutadiene, polyisoprene, polyamide, polycaprolactone, polyurethane with hydroxyalkyl-substituted polydimethylsiloxanes, hydroxyl-containing polyacrylates or polymethacrylates or polyesters such as in EP 2 546 278 A1, EP 2 271 691 A1, EP 2 493 957 A1 and WO 09/133061 A1.
  • copolymers of carbon dioxide and cyclic ethers are used.
  • Such copolymers can be obtained by various methods, such as in WO 2015/032717 A1, WO 2012/136657 A1, EP 2 321 364 A1 and WO 2018/158389 A1 using organometallic catalysts such as DMC and cobalt and chromium complexes. Because of the high viscosity of these copolymers compared to pure polyethers, the process according to the invention for the synthesis of polyurethane prepolymers, in particular that of the NCO-functionalized polyols, is particularly advantageous.
  • copolymers can also be prepared by reacting alcohols with dialkyl carbonates such as dimethyl carbonate, diaryl carbonates such as diphenyl carbonate or phosgene.
  • dialkyl carbonates such as dimethyl carbonate, diaryl carbonates such as diphenyl carbonate or phosgene.
  • Polycarbonate dioie in particular amorphous polycarbonate dioie, are particularly suitable.
  • Monools can also be used in the process according to the invention.
  • Monofunctional alcohols such as methanol, undecyl alcohol and isopropanol are used as starter molecules for the polymerization with cyclic ethers.
  • Oligomeric monofunctional alcohols such as ethoxylated fatty alcohols can also be used.
  • Both polyoxyalkylene polyols that have a low degree of unsaturation can be used, produced for example with the aid of so-called double metal cyanide complex catalysts (DMC Catalysts) and polyoxyalkylene polyols with a higher degree of unsaturation, produced for example with the aid of anionic catalysts such as NaOH, KOH, CsOH or alkali metal alcoholates.
  • DMC Catalysts double metal cyanide complex catalysts
  • anionic catalysts such as NaOH, KOH, CsOH or alkali metal alcoholates.
  • Polyoxyethylene polyols and polyoxypropylene polyols in particular polyoxyethylene diols, polyoxypropylene diols, polyoxyethylene triols and polyoxypropylene triols, are particularly suitable.
  • polyoxyalkylene diols or polyoxyalkylene triols with a degree of unsaturation below 0.02 meq/g are particularly suitable.
  • So-called ethylene oxide-terminated (“EO-endcapped”) polyoxypropylene polyols are also particularly suitable.
  • polyoxypropylene polyoxyethylene polyols which are obtained, for example, by further alkoxylating pure polyoxypropylene polyols, in particular polyoxypropylene diols and triols, after the polypropoxylation reaction has ended with ethylene oxide and thus having primary hydroxyl groups.
  • hydroxyl-terminated polybutadiene polyols such as those produced by polymerizing 1,3-butadiene and allyl alcohol or by oxidizing polybutadiene, and their hydrogenation products.
  • styrene-acrylonitrile-grafted polyether polyols such as are commercially available, for example, under the trade name Lupranol® from Elastogran GmbH, Germany.
  • polyester polyols are polyesters which carry at least two hydroxyl groups and are produced by known processes, in particular the polycondensation of hydroxycarboxylic acids or the polycondensation of aliphatic and/or aromatic polycarboxylic acids with dihydric or polyhydric alcohols.
  • Polyester polyols which are 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 are particularly suitable , Glycerol, 1,1,1-trimethylolpropane or mixtures of the aforementioned alcohols with 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, dimeric fatty acid, phthalic acid, phthalic anhydride , Isophthalic acid, terephthalic acid, dimethyl terephthalate, hexahydrophthalic acid
  • Polyester diols are particularly suitable, especially those produced from adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer fatty acid, phthalic acid, isophthalic acid and terephthalic acid as dicarboxylic acid or from lactones such as s-caprolactone and from ethylene glycol, diethylene glycol, neopentyl glycol, 1,4-butanediol , 1,6-hexanediol, dimer fatty acid diol and 1,4-cyclohexanedimethanol as a dihydric alcohol.
  • Particularly suitable polyols are polyester polyols and polyether polyols, especially polyoxyethylene polyol, polyoxypropylene polyol and polyoxypropylene polyoxyethylene polyol, preferably polyoxyethylene diol, polyoxypropylene diol, polyoxyethylene triol, polyoxypropylene triol, polyoxypropylene polyoxyethylene diol and polyoxypropylene polyoxyethylene triol.
  • the viscosity of the prepolymers based on polyols with a molecular weight of Mn 12000 g/mol which can be prepared by the process according to the invention is preferably in the range from 10000 to 20000 mPas. With a molecular weight of M n of 18000 g/mol, the viscosity is in the range from 40000 to 50000 mPas (determined using a Brookfield Rheometer DV-3T Extra at 25°C, spindle size and spindle speed were selected so that the torque > 90 % is). It can thus be at least 30% lower than the viscosity of those prepolymers which were not produced by the process according to the invention.
  • the process is preferably carried out at temperatures of at least 0°C, preferably at least 20°C and preferably at most 150°C, in particular at most 80°C.
  • the process according to the invention for preparing silylated polyurethanes from a reaction of NCO-functionalized polyol with aminosilane is preferably carried out at temperatures from 15 to 70.degree. C., particularly preferably at temperatures from 25 to 65.degree.
  • the temperature during production of the polyurethane prepolymers is particularly preferably between 10° C. and 120° C., preferably between 15° C. and 100° C., particularly preferably between 20° C. and 90° C. and very particularly preferably between 25° C. and 85° C
  • Suitable catalysts for the production of polyurethane prepolymers are selected from the group of metal-siloxane-silanol(- ate) compounds and organometallic compounds of the elements aluminum, tin, zinc, titanium, manganese, iron, bismuth, zirconium such as for example dibutyltin laurate, zinc octoate or titanium tetraisopropylate or tertiary amines such as 1,4-diazabicyclo[2.2.2]octane.
  • catalyst describes a substance that lowers the activation energy of a specific reaction and thereby increases the rate of the reaction.
  • metal siloxane silanol(ate) refers to all metal siloxane compounds that contain either one or more silanol and/or silanolate groups. In one embodiment of the invention, it is also possible for only metal siloxane silanolates to be present as the catalyst. As long as no individual differentiation is made between these different constellations, all combinations are included.
  • the metal-siloxane-silanol(ate) compound can be present as a monomer, oligomer and/or polymer for the production of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, with the transition from oligomers to polymers according to the general definition is fluid.
  • the metal or metals were preferably present in the oligomeric and/or polymeric metal-siloxane-silanol(ate) compound at the end and/or within the chain.
  • the metal-siloxane-silanol(ate) compound in chain form is linear, branched and/or a cage.
  • a "cage” or an oligomeric or polymeric "cage structure” is understood within the meaning of the invention as a three-dimensional arrangement of the chain-like metal-siloxane-silanol(-ate) compound, with individual atoms of the chain forming the corner points of a multi-faceted basic structure of the compound . At least two surfaces are spanned by the interconnected atoms, whereby a common intersection is created. In one embodiment of the connection, a cube-shaped basic structure of the connection is formed, for example.
  • the structure (IVc) represents a single-cage structure or also singly present cage structure, i.e. a compound that is defined by an isolated cage (la) to (Id) are described.
  • a cage can be “open” or also “closed”. Depending on whether all corners are connected, linked or coordinated in such a way that a closed cage structure is created.
  • Structures (III), (IV), (IVb), (IVc) represent an example of a closed cage.
  • the term “nuclear” describes the nucleus of a compound, how many metal atoms are contained in it.
  • a mononuclear compound has one metal atom, while a polynuclear or binuclear compound has two metal atoms within one compound. The metals can be connected directly to one another or linked via their substituents.
  • An example of a mononuclear compound according to the invention is e.g. B. the structures (IV), (IVb), (IVc), (la) (Ib) or (Ic); structure (Id) represents a binuclear compound.
  • the metal siloxane silanol(ate) compounds (IV), (IVb) and (IVc) represent a mononuclear monocage structure.
  • the metal siloxane silanol(ate) compound in the production of polyurethane prepolymers in particular the NCO-functionalized polyols used according to the invention, preferably comprises an oligomeric metal silsesquioxane.
  • the metal-siloxane-silanol(-ate) compound in the preparation of the polyurethane prepolymers in particular the NCO-functionalized polyols used according to the invention, comprises a polyhedral metal silsesquioxane.
  • the metal siloxane silanol(ate) compound has the general formula R* q Si r O s Mt wherein each R* is independently selected from the group consisting of optionally substituted C 1 to C 20 alkyl , optionally substituted C 3 to C 8 cycloalkyl, optionally substituted C 2 to C 20 alkenyl, optionally substituted C 5 to C 10 aryl, -OH and -O-(C 1 to C 10 alkyl), each M are independently selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group consisting of metals of the 1st, 2nd, 3rd, 4th, 5th, 8th, 10th and 11th subgroup and metals of main groups 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu ,
  • the metal siloxane silanol(ate) compound has the general formula R # 4 Si 4 OnY 2 Q2X 4 Z3 where each X is independently selected from the group consisting of Si, M 1 , - M 3 L 1 A , M 3 , or -Si(R 8 )-OM 3 L 1 A , where M 1 and M 3 are independently selected from the group consisting of s and p block metals, d and f block transition metals, Lanthanide and actinide metals and semimetals, in particular from the group consisting of metals of the 1st, 2nd, 3rd, 4th, 5th, 8th, 10th and 11th subgroup and metals of the 1st, 2nd, 3rd , 4th and 5th main group, 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, Z
  • the metal-siloxane-silanol(ate) compound in the production of polyurethane prepolymers has the general formula (Y 0 ,25R # SiOi, 2 5)4(Z 0 , 75Yo,25XO) 4 (OQ) 2 wherein each X is independently selected from the group consisting of Si, M 1 , -M 3 L 1 A , M 3 , or -Si(R 8 )-OM 3 L 1 A , where M 1 and M 3 are independently selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group consisting of metals of the 1st, 2nd, Subgroups 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd
  • the metal siloxane silanol(ate) compound preferably has the general formula Si 4 O 9 R 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 where X 1 , X 2 and X 3 are independently selected from Si or M 1 where M 1 is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals , in particular from the group consisting of metals of the 1st, 2nd, 3rd, 4th, 5th, 8th, 10th and 11th subgroup and metals of the 1st, 2nd, 3rd, 4th and 5th main group, 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,
  • Z 1 , Z 2 and Z 3 are independently selected from the group consisting of L 2 , R 5 , R 6 and R 7 , where L 2 is selected from the group consisting of -OH and -O-(C1- to C10 -alkyl), in particular -O-(C1- to C8-alkyl) or -O-(C1- to C6-alkyl), or where L2 is selected from the group consisting of -OH, -O-methyl, -O- ethyl, -O-propyl, -O-butyl, -O-octyl, -O-isopropyl, and -O-isobutyl;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from the group consisting of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 cycloalkyl, optionally substituted C2 - to C20 alkenyl and optionally substituted C5 to C10 aryl;
  • Y 1 and Y 2 independently represent -OM 2 -L 3 A , or Y 1 and Y 2 are taken together and together represent -OM 2 (L 3 A )-O- or -O-, where L 3 is selected from the Group consisting of -OH and -O-(C1- to C10-alkyl), in particular -O-(C1- to C8-alkyl) or -O-(C1- to C6-alkyl), or where 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 is selected from the Group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group consisting of metals of the
  • X 4 is -M 3 L 1 A and Q 2 is H or a single bond linked to M 3 and Q 1 is H, M 4 L 4 A or -SiR 8 where 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 semimetals, in particular from the group consisting of metals of the 2nd, 3rd, 4th, 5th and 8th subgroup and metals of the 1st, 2nd, 3rd ., 4th and 5th main group, in particular from the group consisting of Zn, Sc, Ti, Zr, Hf, V, Pt, Ga, Sn and Bi, where L 4 is selected from the group consisting of -OH and -O -(C1- to C10-alkyl), in particular -O-(C1- to C8-alkyl) or -O-(C1- to C6-alkyl), or where L 4 is selected from the group consisting
  • X 4 , Q 1 and Q 2 are independently -M 3 L 1 A , or
  • X 4 represents -Si(R 8 )-OM 3 L 1
  • Q 2 represents a single bond attached to the Si atom of X 4
  • Q 1 represents -M 4 L 4 A , or
  • X 4 represents -Si(R 8 )-OM 3 L 1 A
  • Q 2 represents a single bond attached to the Si atom of X 4
  • Q 1 represents a single bond attached to the M 3 atom of X 4 .
  • the metal silsesquioxane in the production of polyurethane prepolymers in particular the NCO-functionalized polyols used according to the invention, has the general formula
  • X 1 , X 2 and X 3 are independently selected from Si or M 1 where M 1 is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals and metalloids, in particular from the group consisting from metals of the 1st, 2nd, 3rd, 4th, 5th, 8th, 10th and 11th subgroup and metals of the 1st, 2nd, 3rd, 4th and 5th main group, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from the group consisting
  • Z 1 , Z 2 and Z 3 are independently selected from the group consisting of L 2 , R 5 , R 6 and R 7 , where L 2 is selected from the group consisting of -OH and -O-(C1- to C10 -alkyl), in particular -O-(C1- to C8-alkyl) or -O-(C1- to C6-alkyl), or where 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;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from the group consisting of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C6 cycloalkyl, optionally substituted C2 - to C20 alkenyl and optionally substituted C6 to C10 aryl;
  • Y 1 and Y 2 independently represent -OM 2 -L 3 A , or Y 1 and Y 2 are taken together and together represent -OM 2 (L 3 A )-O- or -O-, where L 3 is selected from the Group consisting of -OH and -O-(C1- to C10-alkyl), in particular -O-(C1- to C8-alkyl) or -O-(C1- to C6-alkyl), or where 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 is selected from the Group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group consisting of metals of the
  • X 4 is -M 3 L 1 A or M 3 and Q 1 and Q 2 each represent H or a single bond attached to M 3 wherein L 1 is selected from the group consisting of -OH and -O-(C1- to C10 -alkyl), in particular -O-(C1- to C8-alkyl) or -O-(C1- to C6-alkyl), or where 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 wherein M 3 is selected from the group consisting of s and p block metals, d and f block Transition metals, lanthanide and actinide metals and semimetals, in particular from the group consisting of metals of the 1st, 2nd, 3rd, 4th, 5th
  • X 4 is -M 3 L 1 A and Q 2 is H or a single bond linked to M 3 and Q 1 is H, M 4 L 4 A 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, in particular from the group consisting of metals of the 2nd, 3rd, 4th, 5th and 8th subgroup and metals of the 1st, 2nd, 3rd, 4th and 5th main group, in particular from the group consisting of Zn, Sc, Ti, Zr, Hf, V, Pt, Ga, Sn and Bi, where L 4 is selected from the group consisting of -OH and -O-( C1- to C10-alkyl), in particular -O-(C1- to C8-alkyl) or -O-(C1- to C6-alkyl), or where L 4 is selected from the group consisting of
  • X 4 , Q 1 and Q 2 are independently -M 3 L 1 A , or
  • X 4 represents -Si(R 8 )-OM 3 L 1 A
  • Q 2 represents a single bond attached to the Si atom of X 4
  • Q 1 represents -M 4 L 4 A
  • X 4 represents -Si(R 8 )-OM 3 L 1 A
  • Q 2 represents a single bond attached to the Si atom of X 4
  • Q 1 represents a single bond attached to the M 3 atom of X 4 .
  • the catalyst based on a metal-siloxane-silanol(-ate) compound can be described by the structure (II),
  • X 1 , X 2 and X 3 are independently selected from Si or M 1 , where M 1 is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the Group consisting of metals of the 1st, 2nd, 3rd, 4th, 5th, 8th, 10th and 11th subgroup and metals of the 1st, 2nd, 3rd, 4th and 5th main group, 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,
  • Z 1 , Z 2 and Z 3 are independently selected from the group consisting of L 2 , R 5 , R 6 and R 7 , where L 2 is selected from the group consisting of -OH and -0-(C1- to C10 -alkyl), in particular -0-(C1- to C8-alkyl) or -0-(C1- to C6-alkyl), or where 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;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from the group consisting of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 cycloalkyl, optionally substituted C2 - to C20 alkenyl and optionally substituted C5 to C10 aryl;
  • Y 1 and Y 2 independently represent -OM 2 -L 3 A , or Y 1 and Y 2 are taken together and together represent -OM 2 (L 3 A )-O- or -O-, where L 3 is selected from the Group consisting of -OH and -O-(C1 to C10 alkyl), in particular -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or where 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 wherein M 2 is selected from the group consisting of s and p blocks Metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group consisting of metals of the 1st,
  • X 4 is -M 3 L 1 and Q 2 is H or a single bond linked to M 3 and Q 1 is H, M 4 L 4 A or -SiR 8 where 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 semimetals, in particular from the group consisting of metals of the 1st, 2nd, 3rd, 4th, 5th, 8th, 10th and 11th subgroup and metals of 1st, 2nd, 3rd, 4th and 5th main group, 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 wherein L 4 is selected from the group consisting of -OH and -O-(C1- to C10-alkyl), in
  • X 4 , Q 1 and Q 2 are independently -M 3 L 1 A , or
  • X 4 represents -Si(R 8 )-OM 3 L 1 A
  • Q 2 represents a single bond attached to the Si atom of X 4 and Q 1 represents -M 4 L 4 A
  • X 4 represents -Si(R 8 )-OM 3 L 1 A
  • Q 2 represents a single bond attached to the Si atom of X 4
  • Q 1 represents a single bond attached to the M 3 atom of X 4 .
  • the metal siloxane silanol(ate) compound in the production of polyurethane prepolymers in particular the NCO-functionalized polyols used according to the invention, has the general formula (II), where X 1 , X 2 and X 3 are independent from each other Si mean
  • X 4 is -M 3 L 1 A and Q 1 and Q 2 each represent a single bond linked to M 3
  • L 1 is selected from the group consisting of -OH and -O-(C1 to C10 alkyl), especially -O-(C1 to C8 alkyl) or -O-(C1 to C6 alkyl), or wherein 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 wherein M 3 is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and Actinide metals and semimetals, in particular from the group consisting of metals of the 1st, 2nd, 3rd, 4th, 5th, 8th, 10th and 11th subgroup and
  • Main group 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,
  • Z 1 , Z 2 and Z 3 are each independently selected from optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 cycloalkyl, optionally substituted C2 to C20 alkenyl and optionally substituted C5 to C10 aryl,
  • R 1 , R 2 , R 3 are each independently selected from optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C5- to C10-aryl,
  • Y 1 and Y 2 are taken together and together form -O-.
  • the metal siloxane silanol(ate) compound of the formula (II) can, depending on the equivalents of metal present, be mononuclear as a monomer or polynuclear as a dimer (two-nuclear), trimer (three-nuclear), multimer (multi-nuclear) and/or or mixtures thereof are present, so that, for example, structures according to the formulas (Ia) to (Id) are possible.
  • polynuclear metal siloxane silanol(ate) compounds that can be used according to the invention are the structures (Ia), (Ib), (IC) or (Id), (lc) where
  • M is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group consisting of metals of the 1st, 2nd, 3rd, 4th, 5th, 8th, 10th and 11th subgroup and metals of the 1st, 2nd, 3rd, 4th and 5th main group, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; more preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and each R (R 1 to R 4 ) is independently selected from the group consisting of optionally substituted C 1 to C 20 alkyl , optionally substituted C 3 to C 8 cycloalkyl, optionally substituted C 2 to C 20 alkenyl, optionally substituted C 5 to C 10 aryl,
  • the tetravalent metal M here represents a common part of several cages. It is known to those skilled in the art that the number of bonds to the metal M depends on the valency of the metal M. The structural formulas (1a) to (1c) may need to be adjusted accordingly.
  • a mixture of the metal siloxane silanol(ate) compounds of the formula (II), (Ia), (Ib) and (Ic) is used in the production of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention .
  • polynuclear metal siloxane silanol(ate) compound of the formula (Id) can have 6-fold coordinated metal centers, so that structures of the formula (Id) are possible
  • each M is independently selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and semimetals, particularly from the group consisting of 1st, 2nd, 3rd, 4th, Subgroups 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf , V, Fe, Pt, Cu, Ga, Sn and Bi; more preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and each R is independently selected from the group consisting of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 -cycloalkyl, optionally substituted C2 to C20 alkenyl, optionally substituted C5 to C10 aryl, -OH and -O-(C1 to C10 alkyl).
  • Mononuclear describes the isolated, ie singularly present, cage structure of the catalyst according to the invention based on a metal-siloxane-silanol(ate) compound.
  • Mononuclear catalysts based on a metal-siloxane-silanol(ate) compound can be encompassed by structure (IV) as well as by structures (II) and (III).
  • X 4 is -M 3 L 1 A , where L 1 is selected from the group consisting of -OH and -O-(C1- to C10-alkyl), in particular -O-(C1- to C8-alkyl) or -O -(C1- to C6-alkyl), or where 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 where M 3 is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group consisting of 1st class metals.
  • 2nd, 3rd, 4th, 5th, 8th, 10th and 11th subgroup and metals of the 1st, 2nd, 3rd, 4th and 5th main group 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,
  • Z 1 , Z 2 and Z 3 are independently selected from the group consisting of optionally substituted C 1 to C 20 alkyl, optionally substituted C 3 to C 8 cycloalkyl, optionally substituted C 2 to C 20 alkenyl and optionally substituted C 5 to C 10 -aryl;
  • R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of optionally substituted C 1 to C 20 alkyl, optionally substituted C 3 to C 8 cycloalkyl, optionally substituted C 2 to C 20 alkenyl and optionally substituted 05- to 010- aryl.
  • metal silsesquioxanes which are used to produce polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, are metal-siloxane-silanol(ate) compounds of the general structural formula (III), where X 4 -M 3 L 1 A means where L 1 is selected from the group consisting of -OH and -O-(C1- to C10-alkyl), in particular -O-(C1- to C8-alkyl) or -O-(C1- to C6-alkyl), or wherein 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 where M 3 is selected from the group consisting of s and p block metals, d and f block transition
  • Subgroup and metals of the 1st, 2nd, 3rd, 4th and 5th main group 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,
  • Z 1 , Z 2 and Z 3 are independently selected from the group consisting of L 2 , R 5 , R 6 and R 7 , where L 2 is selected from the group consisting of -OH and -O-(C1- to C10 -alkyl), in particular -O-(C1- to C8-alkyl) or -O-(C1- to C6-alkyl), or where 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 7 are independently selected from the group consisting of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 cycloalkyl, optionally substituted C2 - to C20 alkenyl and optionally substituted C5 to C10 aryl.
  • polyurethane prepolymers in particular the NCO-functionalized polyols used according to the invention, can have been produced by a catalyzed reaction with heptaisobutyl POSS titanium(IV) ethoxide (TiPOSS) as a metal siloxane silanol(ate) compound.
  • TiPOSS heptaisobutyl POSS titanium(IV) ethoxide
  • TiPOSS stands for the mononuclear titanium-metallized silsesquioxane of the structural formula (IV) and can be used equivalently to “heptaisobutyl POSS titanium(I) ethoxide” within the meaning of the invention.
  • the metal-siloxane-silanol(ate) compound can preferably be a mixture containing the structures (II), (la), (Ib), (Ic) , (Id), (III), (IV), (IVb), (IVc).
  • the metal in the metal siloxane silanol(ate) compound is a titanium.
  • catalysts from the group of metal siloxane silanol(ate) compounds are heptaisobutyl POSS titanium(IV) ethoxide (TiPOSS) and heptaisobutyl POSS tin(IV) ethoxide (SnPOSS). Heptaisobutyl POSS titanium(IV) ethoxide (TiPOSS) is very particularly preferred.
  • Organometallic compounds suitable as catalysts are organotin, bismuth, zinc, zirconium, aluminum or titanium compounds. Tertiary amines are also suitable as catalysts.
  • Suitable organometallic compounds are, for example, tetraalkyl titanate, such as tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetrasec-butyl titanate, tetraoctyl titanate, tetra-(2-ethylhexyl) titanate, dialkyl titanate ((RO) 2 TiO 2 , in which R is, for example, isopropyl, n-butyl, isobutyl), such as isopropyl n-butyl titanate; Titanium acetylacetonate chelates such as diisopropoxy bis(acetylacetonate) titanate, diisopropoxy bis(ethyl acetylacetonate) titanate, di-n-
  • Suitable amine compounds are, for example, butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-trisdimethylaminomethyl)phenol, morpholine , N-methylmorpholine, 2-ethyl-4-methylimidazole and 1,8-diazabicylo(5.4.0)undecene-7 (DBU), salts of these amines with carboxylic acids or other acids or mixtures thereof.
  • DBU 1,8-diazabicylo(5.4.0)undecene-7
  • Organotin or organotitanium compounds are preferred.
  • Preferred organometallic compounds as catalysts are dibutyl and dioctyltin diacetate, maleate, bis(2-ethylhexoate), dilaurate, dichloride, bisdodecyl mercaptide, tributyltin acetate, bis( ⁇ -methoxycarbonylethyl)tin dilaurate and bis( ⁇ -acetylethyl)tin dilaurate .
  • organometallic compounds as catalysts are selected from the group consisting of dibutyltin dilaurate (DBTL), tin(II) 2-ethylhexanoate (tin octoate), zinc(II) 2-ethylhexanoate, zinc(II) neodecanoate, bismuth(III) tris(2-ethylhexonate), bismuth(III) tris(neodecanoate) or mixtures thereof.
  • DBTL dibutyltin dilaurate
  • tin(II) 2-ethylhexanoate tin octoate
  • zinc(II) 2-ethylhexanoate zinc(II) neodecanoate
  • bismuth(III) tris(2-ethylhexonate) bismuth(III) tris(neodecanoate) or mixtures thereof.
  • DBTL Dibutyltin dilaurate
  • the catalysts are selected from groups A and/or B, where catalyst A is selected from the group of metal siloxane silanol(ate) compounds and catalyst B is an organometallic catalyst or an amine catalyst .
  • Catalyst A and/or B is preferably an organotin or organotitanium compound.
  • the catalyst B is particularly preferably selected from the group of tin(IV) compounds.
  • the total amount of catalyst is between 1.0 and 1000 ppm, preferably between 2 and 250 ppm, particularly preferably between 3 and 100 ppm, based on the total weight of the hydroxy-functionalized polymer used.
  • a reaction temperature between 10° C. and 120° C., preferably between 15° C. and 100° C., particularly preferably between 20° C. and 90° C. and very particularly preferred applied between 25°C and 85°C.
  • a reaction temperature of between 15° C. and 70° C., preferably between 25° C. and 65° C. more preferably between 30°C and 50°C and most preferably between 35°C and 45°C.
  • the amount of catalyst A is between 1 ppm and 500 ppm, preferably between 2 ppm and 250 ppm. particularly preferably chosen between 3 ppm and 80 ppm.
  • heptaisobutyl POSS titanium(IV) ethoxide is used as catalyst A in the production of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention.
  • a reaction temperature of 10°C to 120°C, preferably 15°C to 100°C, particularly preferably 20°C to 90°C, is used in the production of polyurethane prepolymers when using a catalyst from group A and very particularly preferably between 25° C. and 85° C. and the amount of catalyst A between 1.0 ppm and 500 ppm, preferably between 2 ppm and 250 ppm, particularly preferably between 3 ppm and 80 ppm.
  • a reaction temperature of 10° C. to 120° C., preferably from 15° C. to 100°C, more preferably from 20°C to 90°C and more preferably from 25°C to 85°C.
  • the amount of 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.
  • POSS titanium(IV) ethoxide is used in the production of polyurethane prepolymers when heptaisobutyl is used (TiPOSS) as catalyst from group A, a reaction temperature of 10°C to 120°C, preferably 15°C to 100°C, particularly preferably 20°C to 90°C and particularly preferably 25°C to 85°C applied and amount of catalyst A between 1 ppm and 500 ppm, preferably between 2 ppm and 250 ppm, more preferably between 3 ppm and 80 ppm.
  • TiPOSS heptaisobutyl
  • a reaction temperature of from 20°C to 80°C, preferably from 20°C to 70°C, particularly preferably from 25°C to 50°C, is used in the production of polyurethane prepolymers when using a catalyst from group B applied.
  • a reaction temperature between 20° C. and 70° C., preferably between 25° C. and 50° C., particularly preferably between 30° C and 45°C and most preferably between 35°C and 45°C.
  • the amount of catalyst B between 1 ppm and 1000 ppm, preferably between 2 ppm and 250 ppm, is particularly preferred in the production of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention, when using a catalyst from group B selected between 3 ppm and 100 ppm.
  • a reaction temperature of from 20° C. to 80° C. and preferably from 20° C. to 70° C. is particularly preferred preferably used from 25 ° C to 50 ° C and the amount of catalyst B between 1 ppm and 1000 ppm, preferably between 2 ppm and 250 ppm, particularly preferably between 3 ppm and 100 ppm.
  • dibutyltin dilaurate is used as the catalyst in the production of polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention.
  • the amount of catalyst B is between 20 ppm and 100 ppm, preferably between 30 ppm and 85 ppm , particularly preferably between 40 ppm and 50 ppm.
  • the reaction temperature is from 20° C. to 70° C., preferably from 25° C. to 50° C, applied and the amount of catalyst B between 20 ppm and 100 ppm, preferably between 30 ppm and 85 ppm, more preferably between 40 ppm and 50 ppm chosen.
  • DBTL dibutyltin dilaurate
  • polyurethane prepolymers serve as building blocks for the production of polyurethane elastomers, polyurethane ureas, one- or two-component reactive polyurethane systems, polyurethane dispersions, which are used as polyurethane foams, construction materials, paints, coatings, adhesives and sealants, Potting compounds, foils, PUR elastomers, etc. are widely used.
  • the polyurethane prepolymers, in particular the NCO-functionalized polyols used according to the invention also serve as building blocks for the targeted production of block copolymers, star polymers or dendrimers.
  • the isocyanate-functional polyurethane prepolymers in particular the NCO-functionalized polyols used according to the invention, can be used directly as crosslinking components in reactive PU compositions, for example in aqueous 1K or 2K PU compositions, without further reaction or work-up.
  • Aqueous 1-component PU dispersions are OH- or NH-functional dispersions in combination with raw materials containing thermally reversibly blocked isocyanate groups.
  • the blocked polyisocyanates which come into consideration here can, for example, be used unmodified, ie in their hydrophobic form, whereby the resin dispersion (OH- or NH-terminated) must have a co-dispersing function.
  • Hydrophilically modified blocked polyisocyanates form stable dispersions themselves; they are added to the resin dispersion.
  • the blocked isocyanate function can also be bonded directly to the OH- or NH-terminated polymer structure. Such systems are known as self-crosslinking dispersions.
  • Aqueous 2K PU dispersions consist of a binder component and a crosslinker component, which are manufactured and stored separately from one another and are only combined shortly before application.
  • the processing time or pot life i.e. the time in which the coating composition according to the invention can be processed preferably at room temperature (15 to 25 ° C, in particular 20 ° C) without, for example, due to corresponding crosslinking reactions at room temperature, such a strong increase in viscosity occurs that no application more is possible), is known to depend on the components used.
  • polyurethane prepolymers namely the NCO-functionalized polyols used according to the invention
  • a silane in particular with an organosilane, preferably with an aminosilane, to form silylated polyurethanes.
  • the present invention therefore relates to silylated polyurethanes obtainable by reacting polyurethane prepolymers, namely the NCO-functionalized polyols used according to the invention, with organosilanes, preferably with aminosilanes.
  • organosilanes preferably one or more aminosilanes
  • one or more organosilanes can be used.
  • An aminosilane, ie only one “type” of aminosilane, is particularly preferably used according to the invention.
  • silylated polyurethanes obtainable in this way and compositions containing the silylated polyurethanes are also a subject of the present invention.
  • silane or "organosilane” refers to compounds which on the one hand have at least one, usually two or three, hydrolyzable groups, preferably alkoxy groups or acyloxy groups, bonded directly to the silicon atom via Si-O bonds, and on the other hand at least have an organic radical bonded directly to the silicon atom via a Si—C bond.
  • Silanes which have alkoxy groups or acyloxy groups are also known to those skilled in the art as organoalkoxysilanes or organoacyloxysilanes.
  • silane group refers to the silicon-containing group attached to the organic residue of the silane attached to a compound through the Si-C bond.
  • the silanes or their silane groups have the property of hydrolyzing on contact with moisture. This forms organosilanols, i.e. organosilicon compounds containing one or more silanol groups (Si-OH groups) and, as a result of subsequent condensation reactions, organosiloxanes, i.e. organosilicon compounds containing one or more siloxane groups (Si-O-Si groups).
  • Suitable silanes for the purposes of the invention contain at least one group that is reactive toward isocyanate groups.
  • This reaction is preferably carried out in a stoichiometric ratio of isocyanate-reactive groups to isocyanate groups of 1:1 or with a slight excess of isocyanate-reactive groups, so that the resulting silane-functional polyurethane polymer is free of isocyanate groups.
  • the silane in principle, although not preferably, be used substoichiometrically, so that a silane-functional polymer is obtained which has both silane groups and Has isocyanate groups.
  • the remaining NCO groups can be quenched with compounds containing a nucleophilic group (OH, SH, NH2, NHR) such as 2-ethylhexyl alcohol, dibutylamine, benzyl alcohol, stearylamine,
  • a silane which has at least one group which is reactive toward isocyanate groups is, for example, a mercaptosilane or an aminosilane.
  • silane-modified polyurethanes are silane-modified, Silane-functional or silane-terminated polyurethanes, also referred to interchangeably as SPUR.
  • the definition includes polymers, polycondensates or polyadducts.
  • Silane-functional polymers are commonly referred to as hybrid polymers, and are also referred to according to the invention. These polymers can combine the curing chemistry of alkoxysilane groups with the chemistry of polyols or polyurethanes.
  • Alkoxysilane groups are known from silicone chemistry, the isocyanate-functional polymers, in particular hydroxy-functional polymers, contribute at least parts of the backbone (“polymer backbone”) of the hybrid polymer.
  • Crosslinking occurs via the reactive silane end groups through the ingress of, for example, atmospheric moisture. The curing mechanism of these systems is preferably neutral.
  • Alkoxy means an alkyl group attached through an oxygen atom to the main carbon chain or backbone of the compound.
  • Silane-functional polyurethanes contain a polymer backbone (P) and at least two end groups or functional groups or modifications of the following general formula (V)
  • - X is C, Si or a heteroatom and these optionally have one or more radicals R 8 depending on their bond, preferably C, N, O, P, S, particularly preferably C, N or O, very particularly preferably N or O and each bonded to a carbon in the polymer backbone,
  • each Y independently of one another is either O or a direct bond of the Si atom to the respective radical R 9 , R 10 or R 11 , preferably at least one YO,
  • R 8 H an optionally substituted, straight or branched C1 to C25 alkyl group, an optionally substituted, straight or branched C2 to C25 alkenyl group or an optionally substituted, straight or branched C2 to C18 alkynyl group, an optionally substituted C4 - to C18 cycloalkyl group or an optionally substituted C4 to C18 aryl group or a radical of the general structure (Vb),
  • R 12 and R 14 each independently represent H or a radical selected from the group consisting of -R 15 , -COOR 15 and -CN,
  • R 13 is H or a radical from the group consisting of -CH 2 -COOR 15 , -COOR 15 , -CONHR 15 , -CON(R 15 ), -ON, -NO 2 , -PO(OR 15 ) 2 , -SOR 15 and -SO 2 OR 15 ,
  • R 15 is a hydrocarbon radical having 1 to 20 carbon atoms which may have at least one heteroatom
  • polyurethane prepolymers in particular the NCO-functionalized polyols used according to the invention, with an organosilane of the formula (IX) wherein the two radicals R 16 and R 17 are each independent of one another and the radical R 16 is a linear or branched, monovalent hydrocarbon radical having 1 to 8 carbon atoms, in particular a methyl or ethyl group, the radical R 17 is an acyl radical or a is a linear or branched, monovalent hydrocarbon radical having 1 to 5 carbon atoms, in particular a methyl or ethyl group, preferably a methyl group, the index a is 0 or 1 or 2, in particular 0, and the radical R 18 is a linear or branched, divalent hydrocarbon radical having 1 to 12 carbon atoms, which optionally has cyclic moieties and optionally one or more heteroatoms, in particular one or more nitrogen atoms, in particular an alkylene group having 1 to 6 carbon atoms, preferably 2 to
  • R 16 and R 17 each independently represent the radicals described.
  • R 19 is a hydrogen atom or a cyclic, linear or branched, monovalent hydrocarbon radical having 1 to 20 carbon atoms, which may contain cyclic moieties, or a radical of the following formula: wherein the radicals R 20 and R 21 are each independently a hydrogen atom or a radical from the group consisting of -R 23 , -COOR 23 and -CN, the radical R 22 is a hydrogen atom or a radical from the group consisting of -CH 2 -COOR*, -COOR 23 , -CONHR 23 , -CON(R 23 ) 2 , -CN, -NO 2 , -PO(OR 23 ) 2 , -SO 2 R 23 and -SO 2 OR 23 , and der The radical R 23 is a hydrocarbon radical having 1 to 20 carbon atoms and optionally containing at least one heteroatom.
  • R 19 can also be a hydrocarbon radical containing alkoxysilyl groups, such as, for example, a trimethoxysilylpropyl radical.
  • aminosilanes suitable according to the invention are primary aminosilanes, preferably 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane; secondary aminosilanes, preferably N-butyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane; the products from the Michael-like addition of primary aminosilanes, such as the products from 3-aminopropyltrimethoxysilane or 3-aminopropyldimethoxymethylsilane to Michael acceptors such as acrylonitrile, acrylic acid esters, (meth)acrylic acid esters, (meth)acrylic acid amides, maleic acid and fumaric acid diesters, citraconic acid diesters and itaconic acid diesters, preferably dimethyl and diethyl N-(3-trimethoxysilyl-propyl)-amino-s
  • Michael acceptors are compounds which contain double bonds activated by electron acceptor residues and can therefore enter into nucleophilic addition reactions with primary amino groups (NH 2 groups) in a manner analogous to the Michael addition (hetero-Michael addition).
  • N-alkylaminosilanes such as N-butyl-3-aminopropyltrimethoxysilane, bis[3-
  • Suitable mercaptosilanes have the general formula (X):
  • suitable organosilanes are those that are all reaction products of the Michael-type addition of primary aminosilanes such as 3-aminopropyltrimethoxysilane or 3-aminopropyldimethoxymethylsilane to Michael acceptors such as acrylonitrile, acrylic acid esters, (meth)acrylic acid esters, (meth)acrylic acid amides, maleic acid - and fumaric acid diesters, citraconic acid diesters and itaconic acid diesters and mixtures thereof.
  • primary aminosilanes such as 3-aminopropyltrimethoxysilane or 3-aminopropyldimethoxymethylsilane to Michael acceptors such as acrylonitrile, acrylic acid esters, (meth)acrylic acid esters, (meth)acrylic acid amides, maleic acid - and fumaric acid diesters, citraconic acid diesters and itaconic acid diesters and mixtures thereof.
  • N denotes in particular nitrogen.
  • O denotes in particular oxygen, unless otherwise indicated.
  • S designates sulfur unless otherwise indicated.
  • P designates in particular phosphorus, unless otherwise indicated.
  • C designates carbon unless otherwise indicated.
  • H designates in particular hydrogen, unless otherwise indicated.
  • Si refers in particular to silicon, unless otherwise indicated.
  • “Optionally substituted” means that hydrogen atoms in the corresponding group or in the corresponding radical can be replaced by substituents.
  • Substituents can in particular be selected from the group consisting of C1- to C4-alkyl, methyl, ethyl, propyl, butyl, phenyl, benzyl, halogen, fluorine, chlorine, bromine, iodine, Hydroxy, amino, alkylamino, dialkylamino, C1 to C4 alkoxy, phenoxy, benzyloxy, cyano, nitro, and thio,
  • 0 to 50 in particular 0 to 20 hydrogen atoms of the group can be replaced by substituents.
  • When a group is substituted at least one hydrogen atom is replaced with a substituent.
  • alkyl group is meant a saturated hydrocarbon chain.
  • alkyl groups have the general formula -C n H 2n +i.
  • C1 to C16 alkyl group refers in particular to a saturated hydrocarbon chain with 1 to 16 carbon atoms in the chain. Examples of C1 to C16 alkyl groups are methyl, ethyl, propyl, butyl, isopropyl, isobutyl, secbutyl, tertbutyl, n-pentyl and ethylhexyl.
  • a “C1 to C8 alkyl group” designates in particular a saturated hydrocarbon chain having from 1 to 8 carbon atoms in the chain.
  • alkyl groups can also be substituted, even if this is not specifically stated.
  • Straight chain alkyl groups refer to alkyl groups that do not contain branches. Examples of straight-chain alkyl groups are methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl.
  • Branched alkyl groups refer to alkyl groups that are not straight-chain, ie in which the hydrocarbon chain in particular has a fork. Examples of branched alkyl groups are isopropyl, isobutyl, secbutyl, tertbutyl, secpentyl, 3-pentyl, 2-methylbutyl, isopentyl, 3-methylbut-2-yl , 2-methylbut-2-yl, neopentyl, ethylhexyl, and 2-ethylhexyl.
  • alkenyl groups refer to hydrocarbon chains containing at least one double bond along the chain.
  • an alkenyl group having a double bond specifically has the general formula -CnH2n-1.
  • alkenyl groups can also have more than one double bond.
  • C2 to C16 alkenyl group specifically designates a hydrocarbon chain having from 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 are vinyl, allyl, 2-butenyl and 2-hexenyl,
  • Straight chain alkenyl groups means alkenyl groups that do not contain branches. Examples of straight-chain alkenyl groups are vinyl, allyl, n-2-butenyl and n-2-hexenyl,
  • Branched alkenyl groups refer to alkenyl groups that are not straight-chain, ie in which the hydrocarbon chain in particular has a fork. Examples of branched alkenyl groups are 2-methyl-2-propenyl, 2-methyl-2-butenyl and 2-ethyl-2-pentenyl,
  • Aryl groups mean monocyclic (e.g., phenyl), bicyclic (e.g., indenyl, naphthalenyl, tetrahydronapthyl, or tetrahydroindenyl), and tricyclic (e.g., fluorenyl, Tetrahydrofluorenyl, anthracenyl, or tetrahydroanthracenyl) ring systems in which the monocyclic ring system or at least one of the rings in a bicyclic or tricyclic ring system is aromatic.
  • a C4 to C14 aryl group denotes an aryl group having 4 to 14 carbon atoms.
  • aryl groups can also be substituted, even if this is not specifically stated.
  • sils are organic silicon compounds in which at least one hydroxyl group (OH) is bonded to the silicon atom (-Si-OH).
  • silates are organic silicon compounds in which at least one deprotonated hydroxy function (RO-) is bonded to the silicon atom (-Si-O-), this negatively charged oxygen atom also being bonded to other compounds such as metals, chemically covalently bonded and/or coordinated.
  • RO- deprotonated hydroxy function
  • the silylated polyurethanes are prepared by a catalyzed synthesis of at least one isocyanate-reactive compound, in particular a hydroxy-functionalized polymer, a polyol (B), and a compound (A) containing at least one isocyanate group.
  • the synthesis takes place via a catalyzed synthesis of an isocyanate-reactive compound, in particular a hydroxy-functionalized polymer, a polyol (B), and a polyisocyanate compound.
  • an isocyanate-reactive compound in particular a hydroxy-functionalized polymer, a polyol (B), and a polyisocyanate compound.
  • a polyisocyanate is preferably used.
  • the prepolymer containing isocyanate groups which can be obtained in this way, in particular the NCO-functionalized polyol which can be obtained in this way and used according to the invention, is then reacted with an organosilane to give the silylated polyurethane according to the invention.
  • R 8 H an optionally substituted C1 to C25 straight-chain or branched alkyl group, an optionally substituted C2 to C25 straight-chain or branched alkenyl group, or an optionally substituted C4 to C18 cycloalkyl group, or an optionally substituted C4 to C18 aryl group or a radical of the general structure (Vb),
  • R 12 and R 14 each independently represent H or a radical selected from the group consisting of -R 15 , -COOR 15 and -CN,
  • R 13 is H or a radical from the group consisting of -CH 2 -COOR 15 , -COOR 15 , -CONHR 15 , -CON(R 15 ), -ON, -NO 2 , -PO(OR 15 ) 2 , -SOR 15 and -SO 2 OR 15 ,
  • R 15 is a hydrocarbon radical having 1 to 20 carbon atoms which may have at least one heteroatom
  • R 9 , R 10 and R 11 are independently H, an optionally substituted, straight-chain or branched C1 to C25 alkyl group, an optionally substituted, straight-chain or branched C2 to C25 alkenyl group or an optionally substituted C4 to C18 cycloalkyl group or an optionally substituted C4 to C18 aryl group, preferably at least R 9 is a C2 alkyl group, particularly preferably R 9 and R 10 is a C2 alkyl group and
  • Each Y independently of one another is either O or a direct bond of the Si atom to the respective radical R 9 , R 10 or R 11 , preferably at least one YO.
  • End groups according to the invention in the silylated polyurethane can be described by the general formula (V). whereby - X is C, Si or a heteroatom and these optionally have one or more radicals R 8 depending on their bond, preferably C, N, O, P, S, particularly preferably C, N or O, very particularly preferably N or O and is attached to a carbon in the polymer backbone,
  • R* 0 or an optionally substituted C1 to C25 straight-chain or branched alkyl group or an optionally substituted C4 to C18 cycloalkyl group or an optionally substituted C4 to C18 aryl group, preferably an optionally substituted C1 to C15 straight-chain or branched chain -alkyl group and when R* 0, the Si atom is directly connected to the N atom,
  • each Y independently of one another is either O or a direct bond of the Si atom to the respective radical R 9 , R 10 or R 11 , preferably at least one YO,
  • R 8 H an optionally substituted, straight or branched C1 to C25 alkyl group, an optionally substituted, straight or branched C2 to C25 alkenyl group or an optionally substituted, straight or branched C2 to C18 alkynyl group, an optionally substituted C4 - to C18 cycloalkyl group or an optionally substituted C4 to C18 aryl group or a radical of the general structure (Vb),
  • R 12 and R 14 each independently represent H or a radical selected from the group consisting of -R 15 , -COOR 15 and -CN,
  • R 13 is H or a radical from the group consisting of -CH 2 -COOR 15 , -COOR 15 , -CONHR 15 , -CON(R 15 ), -ON, -NO 2 , -PO(OR 15 ) 2 , -SOR 15 and -SO 2 OR 15 ,
  • R 15 is a hydrocarbon radical having 1 to 20 carbon atoms which may have at least one heteroatom
  • the silylated polyurethane according to the invention is selected from the group consisting of N-[3-(triethoxysilyl)methyl]butylamine, N-[3-(triethoxysilyl)propyl]butylamine, N- (3-Triethoxysilyl-propyl)-amino-succinic acid diethyl ester or a mixture thereof.
  • the polyurethane prepolymer according to the invention in particular the NCO-functionalized polyol, is produced by a catalyzed synthesis of polypropylene glycol with isophorone diisocyanate (IPDI).
  • the polyurethane prepolymer according to the invention in particular the NCO-functionalized polyol, is produced by a catalyzed synthesis of polypropylene glycol with isophorone diisocyanate (IPDI) using DBTL.
  • IPDI isophorone diisocyanate
  • the polyurethane prepolymer according to the invention in particular the NCO-functionalized polyol, is produced by a catalyzed synthesis of polypropylene glycol with isophorone diisocyanate (IPDI).
  • IPDI isophorone diisocyanate
  • the silylated polyurethane polymer according to the invention is produced by a catalyzed synthesis of polypropylene glycol with isophorone diisocyanate (IPDI) and subsequent silanization with N-[3-(trimethoxysilyl)propyl]butylamine].
  • IPDI isophorone diisocyanate
  • inventive silylated polyurethane polymer is prepared by a catalyzed synthesis of polypropylene glycol with isophorone diisocyanate (IPDI) and subsequent silanization with N-[3-(trimethoxysilyl)propyl]butylamine] using TiPOSS.
  • IPDI isophorone diisocyanate
  • a polypropylene glycol with a number-average molecular weight of 18000 g/mol is used in the above-mentioned embodiments.
  • these additives from the group comprising one or more fillers selected from the group of inorganic and organic fillers, in particular natural, ground or precipitated calcium carbonates, which are optionally coated with fatty acids, in particular stearic acid, baryte (heavy spar) , talc, quartz powder, quartz sand, dolomite, wollastonite, kaolin, calcined kaolin, mica (potassium aluminum silicate), molecular sieves, aluminum oxide, aluminum hydroxide, magnesium hydroxide, silicic acid including highly disperse silicic acid from pyrolysis processes, industrially produced soot, graphite, metal powder such as Aluminum, copper, iron, silver or steel, PVC powder or hollow spheres, one or more adhesion promoters from the group consisting of the silanes, in particular aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, N-(
  • Methoxymethylsilanes, orthoformic esters, and calcium oxide or molecular sieves one or more plasticizers from the group consisting of carboxylic acid esters such as phthalates, in particular diisononyl 1,2-cyclohexanedicarboxylate, dioctyl phthalate, diisononyl phthalate or diisodecyl phthalate, adipates, in particular dioctyl adipate, azelates, sebacates, polyols, in particular polyoxyalkylene polyols or polyester polyols, Glycol ethers, glycol esters, citrates, in particular triethyl citrate, organic phosphoric and sulfonic acid esters, polybutenes or fatty acid methyl or ethyl esters derived from natural fats or oils, one or more UV stabilizers from the group consisting of organic (benzophenones, benzotriazoles, oxalanilides
  • the composition according to the invention additionally contains a water scavenger, preferably a vinylalkoxysilane, particularly preferably vinyltrimethoxysilane (VTMO).
  • VTMO vinyltrimethoxysilane
  • the entire isocyanate-containing compound (component I or also (A)) or the entire isocyanate-reactive compound, in particular the hydroxy-functionalized polymer (component II or else (B)) is then added, at least one catalyst is then added and the components are reacted.
  • the catalyst can be introduced before component I/(A) and II/(B) or added to the component introduced in each case or added to a mixture of component I/(A) and II/(B).
  • the silylated polyurethane according to the invention is then produced from the resulting polyurethane prepolymers, in particular the resulting NCO-functionalized polyols used according to the invention, by a reaction with the organosilane, in particular with aminosilane. If one or more components are additionally used, these can in principle be added to the reaction mixture at any point in time.
  • the method according to the invention is preferably carried out with the exclusion of (atmospheric) moisture and at the pressure of the surrounding atmosphere, ie about 900 to 1100 hPa.
  • the process according to the invention can be carried out continuously, e.g. B. in a conventional reaction vessel with stirrer.
  • the silylated polyurethanes according to the invention are obtained from a reaction of NCO-functionalized polyol with aminosilane, where
  • the resulting NCO-functionalized polyol has a residual monomer content, i.e. a residual content of isocyanate-containing compound (A) that has not reacted with the polyol (B), of less than ( ⁇ ) 1% by weight, preferably less than or equal to ( ⁇ ) 0.5% by weight %, particularly preferably less than or equal to ( ⁇ ) 0.1% by weight, based on the weight of the NCO-functionalized polyol.
  • IPDI isophorone diisocyanate
  • the polyol (B) used in II. is a polyether polyol or a polyester polyol, preferably a polyether polyol.
  • Polyether polyols with a number-average molecular weight Mn of 4000 to 80000 g/mol are even more preferred.
  • the catalyst is in the reaction of I. with II heptaisobutyl POSS titanium(IV) ethoxide (TiPOSS), dibutyltin dilaurate (DBTL) or a mix of them.
  • TiPOSS heptaisobutyl POSS titanium(IV) ethoxide
  • DBTL dibutyltin dilaurate
  • the silylated polyurethanes according to the invention are built up from the NCO-functionalized polyols described above by reacting them with an organosilane, preferably with an aminosilane.
  • aminosilanes selected from the group consisting of the primary aminosilanes, preferably 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, the secondary aminosilanes, preferably N-butyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane the group of products obtainable from the Michael-type addition of primary aminosilanes such as 3-aminopropyltrimethoxysilane or 3-aminopropyldimethoxymethylsilane to Michael acceptors such as acrylonitrile, acrylic acid esters, (meth)acrylic acid esters, (meth)acrylic acid
  • silylated polyurethanes in CASE applications (coatings, adhesives, gaskets and elastomers) and/or for elastomeric materials.
  • the flexible foams obtained from the use of the silylated polyurethanes according to the invention are characterized by a Shore A hardness according to ASTM D2240-15 in the range from 0-100, this is preferably in the range from 5 to 95, more preferably in the range from 10 to 90, particularly preferably in the range of 15 to 85.
  • the silylated polyurethanes according to the invention have unformulated, which means that no further additives, apart from optional vinyltrimethoxysilane (VTMO), were added to them after their synthesis, preferably have a Shore A hardness according to ASTM D2240-15 in the range from 0 to 100 in the cured state in the range from 15 to 100, more preferably in the range from 20 to 95, particularly preferably in the range from 25 to 90.
  • VTMO vinyltrimethoxysilane
  • Silylated polyurethanes according to the invention have unformulated, which means that after their synthesis no further additives, except optionally vinyltrimethoxysilane (VTMO), were added, in the cured state an elongation at break according to DIN 53504-S2 (:2017-03) in the range of 0 up to 1000%, preferably in the range from 15 to 500%, particularly preferably in the range from 50 to 250%.
  • VTMO vinyltrimethoxysilane
  • NCO-functionalized polyols According to one of the embodiments described above, it is therefore very particularly preferred to use NCO-functionalized polyols according to one of the embodiments described above in the production of silylated polyurethanes.
  • NCO-functionalized polyols results in silylated polyurethanes which, at 25° C., have a viscosity that is at least 20%, preferably at least 30%, particularly preferably at least 40% lower than silylated polyurethanes which are produced with conventional NCO functionalized polyurethane prepolymers, ie oligomeric or polymeric NCO-functionalized polyurethane prepolymers were produced.
  • a method according to the invention comprises the following steps:
  • NCO-functionalized polyol is used, which in turn was produced in a method which comprises the following steps:
  • the NCO-functionalized polyol used therein has from its production process from step III.
  • a content of NCO-functionalized polyol in an elugram of a gel permeation chromatography (GPC) greater than or equal to (>) 60% by area, preferably greater than or equal to (>) 70% by area, particularly preferably greater than or equal to (>) 80% by area, extremely preferred greater than or equal to (>) 85% by area.
  • the NCO-functionalized polyol used therein has from its production process from step III. a residual monomer content, i.e. a residual content of isocyanate-containing compound (A), of less than ( ⁇ ) 1% by weight, preferably less than or equal to ( ⁇ ) 0.5% by weight, particularly preferably less than or equal to ( ⁇ ) 0.1% by weight. -% based on the weight of the NCO-functionalized polyol.
  • a residual monomer content i.e. a residual content of isocyanate-containing compound (A)
  • a residual monomer content i.e. a residual content of isocyanate-containing compound (A)
  • NCO-functionalized polyols can still be obtained which have a residual monomer content, i.e. a residual content of isocyanate-containing compound (A), of less than ( ⁇ ) 1% by weight, preferably less than or equal to ( ⁇ ) 0.5% by weight, particularly preferably less than or equal to ( ⁇ ) 0.1% by weight, based on the weight of the NCO-functionalized polyol.
  • a residual monomer content i.e. a residual content of isocyanate-containing compound (A)
  • the NCO-functionalized polyols used in a particularly preferred process for preparing silylated polyurethanes have a structure in accordance with the structure perfection A n B or the general structure (I).
  • Another particularly preferred method for producing silylated polyurethanes is characterized in particular by the fact that the NCO-functionalized polyol used from isocyanate-containing compound (A) according to any one of claims 10 to 13 and polyol (B) with a number-average molecular weight M n from 3500 to 100000 g/mol, preferably from 3800 to 90000 g/mol, particularly preferably from 4000 to 80000 g/mol, is constructed.
  • isocyanate-containing compound (A) is one of the isocyanate-containing compounds specified herein.
  • Isophorone diisocyanate (IPDI) is very particularly preferred as the isocyanate-containing compound (A).
  • the organosilane is an aminosilane in the process according to the invention for the production of silylated polyurethanes. Also extremely preferred are the aminosilanes mentioned herein as being particularly preferred.
  • the silylated polyurethanes obtained therefrom having at least 20%, preferably at least 30%, particularly preferably at least 40% lower viscosity at 25° C. compared to silylated polyurethanes which were produced using processes in which conventional NCO-functionalized polyurethane prepolymers, ie oligomers and/or polymeric NCO-functionalized polyurethane prepolymers, were used.
  • polyurethane prepolymers obtainable by a reaction of
  • Polyurethane prepolymers according to embodiment 1 or 2 characterized in that the peak (M1a) corresponds to the molecular weight range of a polyurethane prepolymer of the following formula (I),
  • n corresponds to the number of OH groups in the polyol/functionality
  • polyurethane prepolymers according to one of embodiments 1 to 4, characterized in that the isocyanate-containing compound is isophorone diisocyanate (IPDI), diphenylmethane-2,4'-diisocyanate (MDI) or 4,4'-diphenylmethane diisocyanate (4,4'-MDI) and their mixtures and combinations with other isocyanate-containing compounds.
  • IPDI is isophorone diisocyanate
  • MDI diphenylmethane-2,4'-diisocyanate
  • 4,4'-MDI 4,4'-diphenylmethane diisocyanate
  • Polyurethane prepolymers according to one of embodiments 1 to 5, characterized in that the hydroxy-functionalized polymer is selected from the group consisting of polyether polyols, polyester polyols, polycarbonate polyols and mixtures of these polyols with a number-average molecular weight M n of 3500 to 100000 g/mol, preferably 3800 to 90000 , particularly preferably from 4000 to 80000 g/mol.
  • Polyurethane prepolymer according to one of embodiments 1 to 6, characterized in that the hydroxy-functionalized polymer is selected from the group consisting of polyoxyalkylene diols or polyoxyalkylene triols, in particular polyoxyethylene and polyoxypropylene diols and triols, polyols with higher functionality such as sorbitol, petaerythritol-started polyols, ethylene oxide-terminated Polyoxypropylene polyols, polyester polyols, styrene-acrylonitrile, acrylic methacrylate, (poly) urea-grafted or containing polyether polyols, polycarbonate polyols, CO 2 polyols, polytetrahydrofuran-based polyether (PTMEG), OH-terminated prepolymers based on the reaction of a polyether or polyesterol with a polyisocyanate, polypropylene diols, polyester polyols or mixtures thereof, preferably polyprop
  • Polyurethane prepolymer according to one of embodiments 1 to 7, characterized in that the hydroxy-functionalized polymer is selected from the group consisting of polyester polyols and polyether polyols, in particular polyoxyethylene polyol, polyoxypropylene polyol and
  • Polyoxypropylene polyoxyethylene polyol preferably polyoxyethylene diol
  • polyoxypropylene diol polyoxyethylene triol
  • polyoxypropylene triol polyoxypropylene triol
  • polyoxypropylene polyoxyethylene diol and polyoxypropylene polyoxyethylene triol 9. Polyurethane prepolymers according to any one of embodiments 1 to 8, characterized in that the catalyst is selected from the group consisting of metal siloxane silanol (ate) compounds, organometallic compounds of the elements aluminum, tin, zinc, titanium, manganese, iron , bismuth or zirconium and from the group of tertiary amines or mixtures thereof.
  • the catalyst is selected from the group consisting of metal siloxane silanol (ate) compounds, organometallic compounds of the elements aluminum, tin, zinc, titanium, manganese, iron , bismuth or zirconium and from the group of tertiary amines or mixtures thereof.
  • polyurethane prepolymers according to any one of embodiments 1 to 11, characterized in that the catalyst is selected from groups A and / or B, wherein the catalyst A is selected from the group of metal-siloxane-silanol (ate) - compounds and the Catalyst B is an organometallic catalyst or a tert. amine is.
  • Polyurethane prepolymers according to embodiment 12 characterized in that when using a catalyst from group B, a reaction temperature of 20°C to 80°C, preferably from 20°C to 70°C, particularly preferably from 25°C to 50°C is applied.
  • X 1 , X 2 and X 3 are independently selected from Si or M 1 , where M 1 is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the Group consisting of metals of the 1st, 2nd, 3rd, 4th, 5th, 8th, 10th and 11th subgroup and metals of the 1st, 2nd, 3rd, 4th and 5th main group, 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,
  • Z 1 , Z 2 and Z 3 are independently selected from the group consisting of L 2 , R 5 , R 6 and R 7 , where L 2 is selected from the group consisting of -OH and -O- (C1- to C10 -alkyl), in particular -O-(C1- to C8-alkyl) or -O-(C1- to C6-alkyl), or where 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;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from the group consisting of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 cycloalkyl, optionally substituted C2 - to C20 alkenyl and optionally substituted C5 to C10 aryl; Y 1 and Y 2 independently represent -OM 2 -L 3 A , or Y 1 and Y 2 are taken together and together represent -OM 2 (L 3 A )-O- or -O-, where L 3 is selected from the Group consisting of -OH and -O-(C1- to C10-alkyl), in particular -O-(C1- to C8-alkyl) or -O-(C1- to C6-alkyl), or where L 3 is selected from the group consisting of -OH, -O-methyl, -O-ethyl, -O-propyl, -O-
  • X 4 is -M 3 L 1 A or M 3 and Q 1 and Q 2 are H or each a single bond attached to M 3
  • L 1 is selected from the group consisting of -OH and -O-(C1- to C10 -alkyl), in particular -O-(C1- to C8-alkyl) or -O-(C1- to C6-alkyl), or where 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 wherein M 3 is selected from the group consisting of s and p block metals, d and f block Transition metals, lanthanide and actinide metals and semimetals, in particular from the group consisting of metals of the 1st, 2nd, 3rd, 4th, 5th
  • X 4 is -M 3 L 1 A and Q 2 is H or a single bond linked to M 3 and Q 1 is H, M 4 L 4 A or -SiR 8 where 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 semimetals, in particular from the group consisting of metals of the 1st, 2nd, 3rd, 4th, 5th, 8th, 10th and 11th subgroup and metals of the 1st, 2nd, 3rd, 4th and 5th main group, 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 wherein L 4 is selected from the group consisting of -OH and -O-(C1 to C10 alkyl),
  • X 4 , Q 1 and Q 2 are independently -M 3 L 1 A , or
  • X 4 represents -Si(R 8 )-OM 3 L 1 A
  • Q 2 represents a single bond attached to the Si atom of X 4
  • Q 1 represents -M 4 L 4 A
  • X 4 represents -Si(R 8 )-OM 3 L 1 A
  • Q 2 represents a single bond attached to the Si atom of X 4
  • Q 1 represents a single bond attached to the M 3 atom of X 4 .
  • the catalyst B is selected from the group consisting of tetraalkyl titanate, 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) 2 TiO 2 where R is, for example, isopropyl, n-butyl, isobutyl), such as is
  • zirconium tetraalkylates such as zirconium tetraethylate, zirconium tetrabutylate, zirconium tetrabutyrate, zirconium tetrapropylate, zirconium carboxylates such as zirconium diacetate; zirconium - acetylacetonate chelates such as zirconium tetra(acetylacetonate), tributoxyzirconium acetylacetonate, dibutoxyzirconium(bisacetylacetonate), aluminum trisalkylates such as aluminum triisopropylate, aluminum trisbutylate; Aluminum acetylacetonate chelates, such as
  • Aluminum tris(acetylacetonate) and aluminum tris(ethyl acetylacetonate), organotin compounds such as dibutyltin dilaurate (DBTL), dibutyltin maleate, dibutyltin diacetate, tin(II) 2-ethylhexanoate (tin octoate), tin naphthenate, dimethyltin dineodecanoate, dioctyltin dineodecanoate, dimethyltin dioleate, dioctyltin dilaurate, dimethyloctylmercaptide, dibutylidemercaptide, dibutylidemercaptide , dibutylidemercaptide , dibutyltin dithioglycolate, dioctyltin glycolate, dimethyltin glycolate, a solution of Dibutyltin oxide, reaction products of zinc salts and organic carb
  • DBTL dibutyltin dilaurate
  • tin(II) 2-ethylhexanoate tin octoate
  • zinc(II) 2-ethylhexanoate zinc(II )-neodecanoate
  • bismuth(III) tris(2-ethylhexonate) bismuth(III) tris(neodecanoate
  • catalyst A is selected from the group consisting of heptaisobutyl POSS titanium(IV) ethoxide (TiPOSS) and heptaisobutyl POSS tin(IV) ethoxide (Sn POSS).
  • DBTL dibutyltin dilaurate
  • Silylated polyurethanes obtainable by reacting polyurethane prepolymers according to any one of embodiments 1 to 23 with an organosilane.
  • - X is C, Si or a heteroatom and these optionally have one or more radicals R 8 depending on their bond, preferably C, N, O, P, S, particularly preferably C, N or O, very particularly preferably N or O and each bonded to a carbon in the polymer backbone,
  • each Y independently of one another is either O or a direct bond of the Si atom to the respective radical R 9 , R 10 or R 11 , preferably at least one YO,
  • R 8 H an optionally substituted, straight or branched C1 to C16 alkyl group, an optionally substituted, straight or branched C2 to C16 alkenyl group, or an optionally substituted, straight or branched C2 to C16 alkynyl group, an optionally substituted C4 - to C14 cycloalkyl group or an optionally substituted C4 to C14 aryl group or a radical of the general structure (Vb),
  • R 12 and R 14 each independently represent H or a radical selected from the group consisting of -R 15 , -COOR 15 and -CN,
  • R 13 is H or a radical from the group consisting of -CH 2 -COOR 15 , -COOR 15 , -CONHR 15 , -CON(R 15 ), -ON, -NO 2 , -PO(OR 15 ) 2 , -SOR 15 and -SO 2 OR 15 , R 15 is a hydrocarbon radical having 1 to 20 carbon atoms which may have at least one heteroatom,
  • Silylated polyurethanes according to embodiment 25 characterized in that the organosilane of general structure (VIII) is selected or a mixture thereof,
  • R 8 H an optionally substituted C1 to C25 straight-chain or branched alkyl group, an optionally substituted C2 to C25 straight-chain or branched alkenyl group, or an optionally substituted C4 to C18 cycloalkyl group, or an optionally substituted C4 to C18 aryl group or a radical of the general structure (Vb),
  • R 12 and R 14 each independently represent H or a radical selected from the group consisting of -R 15 , -COOR 15 and -CN,
  • R 13 is H or a radical from the group consisting of -CH 2 -COOR 15 , -COOR 15 , -CONHR 15 , -CON(R 15 ), -ON, -NO 2 , -PO(OR 15 ) 2 , -SOR 15 and -SO 2 OR 15 ,
  • R 15 is a hydrocarbon radical having 1 to 20 carbon atoms which may have at least one heteroatom
  • R 9 , R 10 , R 11 and R* are defined according to claim 25 and
  • Each Y independently of one another is either O or a direct bond of the Si atom to the respective radical R 9 , R 10 or R 11 , preferably at least one YO.
  • R 8 H an optionally substituted, straight or branched C1 to C10 alkyl group, an optionally substituted, straight or branched C2 to C10 alkenyl group, or an optionally substituted, straight or branched C2 to C10 alkynyl group, an optionally substituted C4 - to C10 cycloalkyl group or an optionally substituted C4 to C10 aryl group or a succinic acid derivative according to the general structure (Vb) according to claim 26,
  • R 9 , R 10 , R 11 are defined according to claim 25, preferably R 9 , R 10 , R 11 are a methyl or ethyl group or mixtures thereof and
  • Silylated polyurethanes according to embodiment 24, characterized in that the organosilane corresponds to an organosilane of the formula (IX), wherein the two radicals R 16 and R 17 are each independent of one another and the radical R 16 is a linear or branched, monovalent hydrocarbon radical having 1 to 8 carbon atoms, in particular a methyl or ethyl group, the radical R 17 is an acyl radical or a is a linear or branched, monovalent hydrocarbon radical having 1 to 5 carbon atoms, in particular a methyl or ethyl group, preferably a methyl group, the index a is 0 or 1 or 2, in particular 0, and the radical R 18 is a linear or branched, divalent hydrocarbon radical having 1 to 12 carbon atoms, which optionally has cyclic moieties and optionally
  • R 19 is a hydrogen atom or a cyclic, linear or branched, monovalent hydrocarbon radical having 1 to 20 carbon atoms, which may contain cyclic moieties, or a radical of the following formula: wherein the radicals R 20 and R 21 are each independently a hydrogen atom or a radical from the group consisting of -R 23 , -COOR 23 and -CN, the radical R 22 is a hydrogen atom or a radical from the group consisting of -CH 2 -COOR*, -COOR 23 , -CONHR 23 , -CON(R 23 ) 2 , -CN, -NO 2 , -PO(OR 23 ) 2 , -SO 2 R 23 and -SO 2 OR 23 , and der Radical R 23 is a hydrocarbon radical with 1 to 20 carbon atoms, optionally containing at least one heteroatom, and mixtures thereof. Silylated polyurethanes according to one of embodiments 24 to 28, characterized in that the aminosilane is selected
  • Michael acceptors such as acrylonitrile, acrylic esters, (meth)acrylic esters, (meth)acrylamides, maleic and fumaric diesters, citraconic and it
  • aminosilane is an N-alkylaminosilane, preferably 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 or N-ethyl-4-amino-3,3 - dimethylbutyltrimethoxysilane.
  • composition containing silylated polyurethanes according to embodiment 24 to 30 Composition containing silylated polyurethanes according to embodiment 24 to 30.
  • polyurethane prepolymers according to one of embodiments 1 to 23 for the production of polyurethane elastomers, polyurethane ureas, one- or two-component reactive polyurethane systems as polyurethane foams, engineering materials, paints, coatings, adhesives and sealants, casting compounds, films or PUR elastomers .
  • the viscosities were determined at 25° C. using a Brookfield Rheometer DV-3T Extra.
  • IR monitoring was measured using a ThermoScientific Nicolet iS5 and iD7ATR unit.
  • the viscosity of the NCO prepolymer was determined [46000 mPas (25° C., Brookfield viscometer)].
  • 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).
  • is 0.29.
  • the viscosity of the NCO prepolymer was determined [44000 mPas (25° C., Brookfield viscometer)].
  • 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).
  • is 0.27.
  • Examples 3 to 6 were prepared according to the procedure of examples 1 and 2.
  • STP silane-terminated polymers
  • Silane-terminated polyols from the reaction of isocyanate prepolymer.
  • Table 1a lists examples of NCO-functionalized polyols produced according to the invention or of the oligomeric polyurethane prepolymers not according to the invention (where at least two or more polyol molecules are linked to the diisocyanates via polyurethane bonds)—for examples 1 to 10, the viscosities are the NGO -functional compounds specified.
  • the viscosities of the silylated polyurethanes prepared from the NCO-functional compounds (prepared by reacting the respective NCO-functional compounds with aminosilane) are given in Examples 11 to 19.

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Abstract

La présente invention concerne un procédé sélectif pour la préparation de polyols NCO-fonctionnalisés, leur utilisation dans la préparation de polyuréthanes silylés, des procédés de préparation de polyuréthanes silylés et des polyuréthanes silylés pouvant être obtenus par réaction d'un polyol à fonction NCO avec un aminosilane ainsi que leur utilisation dans des applications de revêtements, adhésifs, agents d'étanchéité et élastomères.
EP21763296.7A 2019-03-26 2021-08-12 Synthèse sélective de prépolymères de polyuréthane Pending EP4196513A1 (fr)

Applications Claiming Priority (3)

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EP19165363 2019-03-26
PCT/EP2020/072688 WO2021028511A1 (fr) 2019-03-26 2020-08-12 Synthèse sélective de prépolymères de polyuréthane
PCT/EP2021/072543 WO2022034192A1 (fr) 2019-03-26 2021-08-12 Synthèse sélective de prépolymères de polyuréthane

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EP4196513A1 true EP4196513A1 (fr) 2023-06-21

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EP19191328.4A Pending EP3715396A1 (fr) 2019-03-26 2019-08-12 Composition et procédé de fabrication de polymères silylées et son utilisation
EP19191330.0A Withdrawn EP3715397A1 (fr) 2019-03-26 2019-08-12 Composition et procédé de fabrication de polymères réticulaires sous l'effet de l'humidité et leur utilisation
EP19206679.3A Withdrawn EP3715398A1 (fr) 2019-03-26 2019-10-31 Composé de métal-siloxane-silanol (at) en tant que catalyseur constitué d'un gel
EP20713278.8A Withdrawn EP3947498A1 (fr) 2019-03-26 2020-03-20 Composition et procédé pour produire des polymères réticulant à l'humidité et utilisation correspondante
EP20754257.2A Pending EP4013802A1 (fr) 2019-03-26 2020-08-12 Synthèse sélective de prépolymères de polyuréthane
EP21763296.7A Pending EP4196513A1 (fr) 2019-03-26 2021-08-12 Synthèse sélective de prépolymères de polyuréthane

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EP19191328.4A Pending EP3715396A1 (fr) 2019-03-26 2019-08-12 Composition et procédé de fabrication de polymères silylées et son utilisation
EP19191330.0A Withdrawn EP3715397A1 (fr) 2019-03-26 2019-08-12 Composition et procédé de fabrication de polymères réticulaires sous l'effet de l'humidité et leur utilisation
EP19206679.3A Withdrawn EP3715398A1 (fr) 2019-03-26 2019-10-31 Composé de métal-siloxane-silanol (at) en tant que catalyseur constitué d'un gel
EP20713278.8A Withdrawn EP3947498A1 (fr) 2019-03-26 2020-03-20 Composition et procédé pour produire des polymères réticulant à l'humidité et utilisation correspondante
EP20754257.2A Pending EP4013802A1 (fr) 2019-03-26 2020-08-12 Synthèse sélective de prépolymères de polyuréthane

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CN (2) CN113631606B (fr)
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WO2020193435A1 (fr) 2020-10-01
EP3715398A1 (fr) 2020-09-30
WO2020193432A1 (fr) 2020-10-01
EP3947498A1 (fr) 2022-02-09
CN114729092B (zh) 2024-04-26
WO2022034192A1 (fr) 2022-02-17
CN114729092A (zh) 2022-07-08
US20220259365A1 (en) 2022-08-18
WO2021028511A1 (fr) 2021-02-18
CN113631606B (zh) 2024-07-09
KR20210145173A (ko) 2021-12-01
EP4013802A1 (fr) 2022-06-22
US20220372285A1 (en) 2022-11-24
EP3715396A1 (fr) 2020-09-30
CA3150038A1 (fr) 2021-02-18
US20220235169A1 (en) 2022-07-28
KR20220099536A (ko) 2022-07-13
US20220235171A1 (en) 2022-07-28
CN113631606A (zh) 2021-11-09
WO2020193430A1 (fr) 2020-10-01
EP3715397A1 (fr) 2020-09-30
JP2022525266A (ja) 2022-05-11
CA3133585A1 (fr) 2020-10-01

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