Selective polyurethane prepolymer synthesis

Abstract

The present invention relates to a selective process for the preparation of NCO-functionalized polyols, to their use in the preparation of silylated polyurethanes, to processes for preparing silylated polyurethanes and to silylated polyurethanes obtainable by a reaction of NCO-functionalized polyol with amino silane and to their use in CASE applications (coatings, adhesives, sealants and elastomers).

1 . Silylated polyurethanes obtainable by a reaction of NCO-functionalized polyol with organosilane. 
     
     
         2 . Silylated polyurethanes as claimed in  claim 1 , characterized in that the NCO-functionalized polyol corresponds to the NCO-functionalized polyol has an (I), 
       
         
           
           
               
               
           
         
         wherein 
         R iso  denotes the structural unit of the isocyanate-containing compound(s) used in preparing the NCO-functionalized polyol (A) and R poly  denotes the structural unit of the polyol (B) used and wherein n is equal to x+y and n corresponds to the number of free OH groups in the polyol used (B) (=functionality). 
       
     
     
         3 . Silylated polyurethanes as claimed in  claim 1 , characterized in that the NCO-functionalized polyol as an A n B-structure, wherein A denotes the isocyanate-containing compound(s) used for preparing the NCO-functionalized polyol and B denotes the polyol used and n corresponds to the number of free OH groups in the polyol used (B). 
     
     
         4 . Silylated polyurethanes as claimed in  claim 1 , characterized in that the NCO-functionalized polyol is obtainable due to a reaction of
 I. at least one isocyanate-containing compound (A) with   II. at least one polyol (B), in the presence of at least one catalyst, and wherein the molar ratio of NCO groups to OH groups in the reaction of I with II is 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.   
     
     
         5 . Silylated polyurethanes as claimed in  claim 4 , characterized in that an asymmetrical isocyanate-containing compound (A) with a molecular weight of 120 g/mol to 1000 g/mol is used. 
     
     
         6 . Silylated polyurethanes as claimed in  claim 4 , characterized in that a polyol (B) with a number average molecular weight M n  of 3,500 to 100,000 g/mol, preferably 3,800 to 90,000 g/mol, particularly preferably from 4,000 to 80,000 g/mol is used. 
     
     
         7 . Silylated polyurethanes as claimed in  claim 4 , characterized in that the reaction of I with II is carried out at temperatures of 15 to 70° C., preferably from 25 to 65° C. 
     
     
         8 . Silylated polyurethanes as claimed in  claim 4 , characterized in that the NCO-functionalized polyol obtainable from the reaction has, after the reaction is carried out, a content of NCO-functionalized polyol according to structure (I) on a gel permeation chromatography (GPC) elugram of greater than or equal to (≥) 60 area %, preferably greater than or equal to (≥) 70 area %, particularly preferably greater than or equal to (≥) 80 area %, most preferably greater than or equal to (≥) 85 area %, wherein the structure (I) is: 
       
         
           
           
               
               
           
         
         wherein 
         R iso  denotes the structural unit of the isocyanate-containing compound(s) used in preparing the NCO-functionalized polyol (A) and R poly  denotes the structural unit of the polyol (B) used and wherein n is equal to x+y and n corresponds to the number of free OH groups in the polyol used (B) (=functionality). 
       
     
     
         9 . Silylated polyurethanes as claimed in  claim 1 , characterized in that the NCO-functionalized polyol has a residual monomer content, i.e. a residual content of isocyanate-containing compound (A), of less than (<) 1 wt %, preferably less than or equal to (≤) 0.5 wt %, particularly preferably less than or equal to (≤) 0.1 wt %, based on the weight of the NCO-functionalized polyol. 
     
     
         10 . Silylated polyurethanes as claimed  claim 4 , characterized in that the isocyanate-containing compound (A) has at least two NCO groups. 
     
     
         11 . Silylated polyurethanes as claimed in  claim 4 , characterized in that the isocyanate-containing compound (A) is a diisocyanate. 
     
     
         12 . Silylated polyurethanes as claimed in  claim 4 , characterized in that the isocyanate-containing compound (A) is asymmetrical. 
     
     
         13 . Silylated polyurethanes as claimed in  claim 12 , characterized in that the asymmetrical isocyanate-containing compound (A) is isophorone diisocyanate (IPDI), diphenylmethane-2,4′-diisocyanate (2,4′-MDI) or toluene-2,4-diisocyanate (TDI), or mixtures thereof. 
     
     
         14 . Silylated polyurethanes as claimed in  claim 4 , characterized in that the polyol (B) is a hydroxyfunctionalized compound, which is preferably selected from the group of the polyether polyols, polyester polyols, polycarbonate polyols as well as mixtures of these polyols. 
     
     
         15 . Silylated polyurethanes as claimed in  claim 4 , characterized in that the polyol (B) is selected from polyoxyalkylene diols or polyoxyalkylene triols, in particular polyoxyethylene and polyoxypropylene di- and -triols, polyols of higher functionality such as sorbitol, pentaerythritol-initiated 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 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 polypropylene diols, polyester polyols, or mixtures thereof. 
     
     
         16 . Silylated polyurethanes as claimed in  claim 1 , characterized in that the polyol is selected from polyester polyols and polyether polyols, in particular polyoxyethylene polyol, polyoxypropylene polyol and polyoxypropylene polyoxyethylene polyol, preferably polyoxyethylene diol, polyoxypropylene diol, polyoxyethylene triol, polyoxypropylene triol, polyoxypropylene polyoxyethylene diol, and polyoxypropylene polyoxyethylene triol. 
     
     
         17 . Silylated polyurethanes as claimed in  claim 4 , characterized in that the catalyst is selected from metal-siloxane-silanol(ate) compounds, organometal compounds of the elements aluminum, tin, zinc, titanium, manganese, iron, bismuth or zirconium and from the group of the tertiary amines or mixtures thereof. 
     
     
         18 . Silylated polyurethanes as claimed in  claim 4 , characterized in that the catalyst is selected from groups A and/or B, wherein catalyst A is selected from the group of the metal-siloxane-silanol(ate) compounds and catalyst B is a metalorganic catalyst or a tertiary amine. 
     
     
         19 . Silylated polyurethanes as claimed in  claim 4 , characterized in that a catalyst amount is between 1 and 1000 ppm, preferably between 2 and 250 ppm, particularly preferably between 3 and 100 ppm, based on the total weight of the polyol (B) used. 
     
     
         20 . Silylated polyurethanes as claimed in  claim 18 , characterized in that in using a catalyst from group A, a reaction temperature of between 15° C. and 70° C., preferably between 25° C. to 65° C., particularly preferably between 30° C. and 50° C. and most particularly preferably between 30° C. and 45° C. is used. 
     
     
         21 . Silylated polyurethanes as claimed in  claim 18 , characterized in that in using a catalyst from group A, the amount of catalyst A is between 1 ppm and 500 ppm, preferably between 2 ppm and 250 ppm, particularly preferably between 3 ppm and 80 ppm, based on the total weight of the polyol (B) used. 
     
     
         22 . Silylated polyurethanes as claimed in  claim 18 , characterized in that in using a catalyst from group B, a reaction temperature of 20° C. to 70° C., preferably from 25° C. to 50° C., particularly preferably from 30° C. to 45° C., is used. 
     
     
         23 . Silylated polyurethanes as claimed in  claim 18 , characterized in that in using a catalyst from group B, the amount of catalyst B is between 1 ppm to 1000 ppm, preferably between 2 ppm to 250 ppm, particularly preferably between 3 ppm to 100 ppm, based on the total weight of the polyol (B) used. 
     
     
         24 . Silylated polyurethanes as claimed in  claim 18 , characterized in that catalyst A is a metal-siloxane-silanol(ate) compound and has general structure (II), 
       
         
           
           
               
               
           
         
         wherein
 X 1 , X 2  and X 3  are selected independently of one another from Si or M 1 , wherein M 1  is selected from s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, Z 1 , Z 2  and Z 3  are selected independently of one another from L 2 , R 5 , R 6  and R 7 , wherein L 2  is selected from —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L 2  is selected from —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 selected independently of one another 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  denote independently of each another —O-M 2 -L 3   Δ , or Y 1  and Y 2  are taken together and together denote —O-M 2 (L 3   Δ )-O— or —O—, wherein L 3  is selected from —OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L 3  is selected from —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and wherein M 2  is selected from s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the group composed of the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from the group composed of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, 
 and 
 X 4  denotes -M 3 L 1   Δ  or M 3  and Q 1  and Q 2  denote in each case denote H or a single bond linked to M 3 , wherein L 1  is selected from —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 —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and wherein M 3  is selected from s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, 
 or 
 X 4  denotes -M 3 L 1   Δ  and Q 2  H denotes a single bond linked to M 3  and Q1 denotes H, M 4 L 4   Δ  or —SiR 8 , wherein M 4  is selected from s and p block metals, d and f block transition metals, lanthanide and actinide metals and semimetals, in particular from the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and wherein L 4  is selected from OH and —O—(C1 to C10 alkyl), in particular —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or wherein L 4  is selected from —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and wherein R 8  is 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, 
 or 
 X 4 , Q 1  and Q 2  denote independently of one another -M 3 L 1   Δ , 
 or 
 X 4  denotes —Si(R 8 )—O-M 3 L 1   Δ , Q 2  denotes a single bond linked to the Si atom of X 4  and Q 1  denotes -M 4 L 4   Δ , 
 or 
 X 4  denotes —Si(R 8 )—O-M 3 L 1   Δ , Q 2  denotes a single bond linked to the Si atom of X 4  and Q 1  denotes a single bond linked to the M 3  atom of X 4 . 
 
       
     
     
         25 . Silylated polyurethanes as claimed in claim  18 , characterized in that catalyst A is the metal-siloxane-silanol(ate) compound of structure (IV), 
       
         
           
           
               
               
           
         
         wherein
 X 4  is selected from the metals of subgroups 1, 2, 3, 4, 5, 8, 10 and 11 and the metals of main groups 1, 2, 3, 4 and 5, preferably from Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; particularly preferably from Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, most particularly preferably from Ti and Sn, most particularly preferably Ti, and X 4  is linked with OR, wherein R is selected from —H, -methyl, -ethyl, -propyl, -butyl, -octyl, -isopropyl, and -isobutyl, Z 1 , Z 2  and Z 3  in each case denote independently of one another C1 to C20 alkyl, C3 to C8 cycloalkyl, C2 to C20 alkenyl and C5 to C10 aryl, and in particular are selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, heptyl, octyl, vinyl, allyl, butenyl- and phenyl, and benzyl, and R 1 , R 2 , R 3  and R 4  in each case denote independently of one another C1 to C20 alkyl, C3 to C8 cycloalkyl, C2 to C20 alkenyl, and C5 to C10 aryl, and in particular are selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, heptyl, octyl, vinyl, allyl, butenyl and phenyl, and benzyl. 
 
       
     
     
         26 . Silylated polyurethanes as claimed in  claim 25 , characterized in that X 4  is Sn or Ti, and X 4  is linked with OR, wherein R is selected from —H, -methyl, -ethyl, -propyl, -butyl, -octyl, -isopropyl, and -isobutyl, preferably -ethyl, -propyl or -butyl, particularly preferably -ethyl or -butyl, and Z 1 , Z 2  and Z 3  as well as R 1 , R 2 , R 3  and R 4  are selected independently of one another from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, heptyl, octyl, vinyl, allyl, butenyl- and phenyl, and benzyl, and preferably independently of one another are isopropyl- or isobutyl, particularly preferably Z 1 , Z 2  and Z 3  as well as R 1 , R 2 , R 3  and R 4  isobutyl-. 
     
     
         27 . Silylated polyurethanes as claimed in  claim 18 , characterized in that catalyst A is heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS) or mixtures thereof. 
     
     
         28 . Silylated polyurethanes as claimed in  claim 18 , characterized in that catalyst A is heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS). 
     
     
         29 . Silylated polyurethanes as claimed in  claim 18 , characterized in that catalyst B is selected from tetraalkyl titanates such as tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, tetra-sec-butyl titanate, tetraoctyl titanate, tetra-(2-ethylhexyl) titanate, dialkyl titanates ((RO) 2 TiO 2 , where R denotes e.g. iso-propyl, n-butyl, iso-butyl), such as isopropyl-n-butyl titanate; titanium-acetylacetonate chelates such as di-isopropoxy-bis(acetylacetonate) titanate, di-isopropoxy-bis(ethyl acetoacetate) titanate, di-n-butyl-bis(acetylacetonate) titanate, di-n-butyl-bis(ethyl acetoacetate) titanate, tri-isopropoxide-bis(acetylacetonate) titanate, 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 acetoacetate), organotin compounds such as dibutyltin dilaurate (DBTL), dibutyltin maleate, dibutyltin diacetate, tin(II)-2-ethyl hexanoate (tin octoate), tin naphthenate, dimethyltin dineodecanoate, dioctyltin dineodecanoate, dimethyltin dioleate, dioctyltin dilaurate, dimethylmercaptides, dibutylmercaptides, dioctylmercaptides, dibutyltin dithioglycolate, dioctyltin glycolate, dimethyltin glycolates, a solution of dibutyltin oxide, reaction products of zinc salts and organic carboxylic acids (carboxylates) such as zinc(II)-2-ethyl hexanoate or zinc(II)-neodecanoate, mixtures of bismuth and zinc carboxylates, reaction products of bismuth salts and organic carboxylic acids such as bismuth(III)-tris(2-ethylhexanoate) and bismuth(III)-tris(neodecanoate) as well as bismuth complex compounds, organolead compounds such as lead octylate, organovanadium compounds, amine compounds such as butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole and 1,8-diazabicylo(5.4.0)undec-7-ene (DBU), salts of these amines with carboxylic acids or other acids or mixtures thereof. 
     
     
         30 . Silylated polyurethanes as claimed in  claim 18 , characterized in that catalyst B is dibutyltin dilaurate (DBTL) ist. 
     
     
         31 . Silylated polyurethanes as claimed in  claim 1 , characterized in that the organosilane is an aminosilane. 
     
     
         32 . Silylated polyurethanes as claimed in  claim 31 , characterized in that the aminosilane is selected from the group of the primary aminosilanes, preferably 3-aminopropyl trimethoxysilane, 3-aminopropyl dimethoxymethylsilane, the secondary aminosilanes, preferably N-butyl-3-aminopropyl trimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, from the group of products obtainable from the Michael like addition of primary aminosilanes such as 3-aminopropyl trimethoxysilane or 3-aminopropyl dimethoxymethylsilane to Michael acceptors such as acrylonitrile, acrylic esters, (meth)acrylic acid esters, (meth)acrylic acid amides, malic acid and fumaric acid diesters, citraconic acid diesters and itaconic acid diesters, preferably N-(3-trimethoxysilyl-propyl)-amino-succinic acid dimethyl- and -diethylesters. 
     
     
         33 . Silylated polyurethanes as claimed in f  claim 1 , characterized in that the aminosilane is an N-alkylamino silane, preferably N-butyl-3-aminopropyl trimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, [(N-cyclohexylamino)methyl]-methyldiethoxysilane, N-ethylamino-methyl methyldiethoxysilane, N-butyl-3-amino-2-methylpropyl trimethoxysilane, N-ethyl-4-amino-3,3-dimethylbutyl dimethoxymethylsilane or N-ethyl-4-amino-3,3-dimethylbutyl trimethoxysilane. 
     
     
         34 . Silylated polyurethanes, characterized by being obtainable due to a reaction of NCO-functionalized polyol with organosilane, preferably with aminosilane, particularly preferably with an aminosilane as claimed in  claim 33 , wherein the polyol used in preparing the NCO-functionalized polyol used in the reaction is a polyol (B) with a number average molecular weight M n  of 3,500 to 100,000 g/mol, preferably 3,800 to 90,000 g/mol, particularly preferably 4,000 to 80,000 g/mol and the isocyanate-containing compound (A) used is asymmetrical, preferably an asymmetrical isocyanate-containing compound (A) which is isophorone diisocyanate (IPDI), diphenylmethane-2,4′-diisocyanate (2,4′-MDI) or toluene-2,4-diisocyanate (TDI), or mixtures thereof. 
     
     
         35 . Silylated polyurethanes as claimed in  claim 1 , characterized in that the silylated polyurethanes are unformulated, which means that no further additives are included in them after they are synthesized, with the optional exception of vinyltrimethoxysilane (VTMO), and that they have a Shore A hardness in a cured state according to ASTM D2240-15 in the range of 0 to 100, preferably in the range of 15 to 100, more preferably in the range of 20 to 95, particularly preferably in the range of 25 to 90. 
     
     
         36 . Silylated polyurethanes as claimed in f  claim 1 , characterized in that the silylated polyurethanes are unformulated, which means that no further additives are included in them after they are synthesized, with the optional exception of vinyltrimethoxysilane (VTMO), and that they have an elongation at break in a cured state according to DIN 53504-S2 (:2017-03) in the range of 0 to 1000%, preferably in the range of 15 to 500%, particularly preferably in the range of 50 to 250%. 
     
     
         37 . Composition containing silylated polyurethanes as claimed in  claim 1 . 
     
     
         38 . Formulation containing silylated polyurethanes as claimed in  claim 1 . 
     
     
         39 . Use of silylated polyurethanes as claimed in  claim 1  in CASE applications (coatings, adhesives, sealants and elastomers) and/or elastomeric materials. 
     
     
         40 . Composition containing one or more NCO-functionalized polyols as claimed in  claim 2 . 
     
     
         41 . Method of using NCO-functionalized polyols comprising preparing silylated polyurethane as claimed in  claim 2  with said NCO-functionalized polyols. 
     
     
         42 . Method of using NCO-functionalized polyols as claimed in  claim 41 , characterized in that the silylated polyurethanes resulting therefrom show viscosity at 25° C. that is at least 20%, preferably at least 30%, and particularly preferably at least 40% lower compared to silylated polyurethanes that were produced with conventional NCO-functionalized polyurethane prepolymers, i.e. oligomeric and/or polymeric NCO-functionalized polyurethane prepolymers. 
     
     
         43 . Method for the preparation of silylated polyurethanes comprising the following steps:
 provision of NCO-functionalized polyol,   reaction of NCO-functionalized polyol with organosilane, preferably with aminosilane.   
     
     
         44 . Method for the preparation of silylated polyurethanes comprising the following steps:
 provision of a mixture of NCO-functionalized polyol and oligomeric and/or polymeric polyurethane prepolymers,   reaction of the provided mixture with organosilane, preferably with aminosilane.   
     
     
         45 . Method as claimed in  claim 43 , wherein the NCO-functionalized polyol in a method that comprises the following steps:
 I. provision of at least one isocyanate-containing compound (A),   II. provision of at least one polyol (B),   III. reaction of I with II in the presence of at least one catalyst, wherein the molar ratio of NCO groups to OH groups in the reaction of I with II is 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.   
     
     
         46 . Method as claimed in  claim 45 , characterized in that the reaction of I with II is carried out at temperatures of 15 to 70° C., preferably 25 to 65° C. 
     
     
         47 . Method as claimed in  claim 45 , characterized in that the NCO-functionalized polyol of step III has a content of NCO-functionalized polyol on a gel permeation chromatography (GPC) elugram of greater than or equal to (≥) 60 area %, preferably greater than or equal to (≥) 70 area %, particularly preferably greater than or equal to (≥) 80 area %, most preferably greater than or equal to (≥) 85 area %. 
     
     
         48 . Method as claimed in  claim 45 , characterized in that the NCO-functionalized polyol of step III has a residual monomer content, i.e. a residual content of isocyanate-containing compound (A), of less than (<) 1 wt %, preferably less than or equal to (≤) 0.5 wt %, particularly preferably less than or equal to (≤) 0.1 wt %, based on the weight of the NCO-functionalized polyol. 
     
     
         49 . Method as claimed in  claim 43 , characterized in that the NCO-functionalized polyol has a structure (I): 
       
         
           
           
               
               
           
         
         wherein 
         R iso  denotes the structural unit of the isocyanate-containing compound(s) used in preparing the NCO-functionalized polyol (A) and R poly  denotes the structural unit of the polyol (B) used and wherein n is equal to x+y and n corresponds to the number of free OH groups in the polyol used (B) (=functionality). 
       
     
     
         50 . Method as claimed in  claim 43 , characterized in that the NCO-functionalized polyol is composed of isocyanate-containing compound (A), wherein the isocyanate-containing compound (A) has at least two NCO groups, and polyol (B) is composed with a number average molecular weight M n  of 3,500 to 100,000 g/mol, preferably 3,800 to 90,000 g/mol, particularly preferably 4,000 to 80,000 g/mol. 
     
     
         51 . Method as claimed in  claim 45 , characterized in that the isocyanate-containing compound (A) is an asymmetrical isocyanate-containing compound (A) which is isophorone diisocyanate (IPDI), diphenylmethane-2,4′-diisocyanate (2,4′-MDI) or toluene-2,4-diisocyanate (TDI), or mixtures thereof. 
     
     
         52 . Method as claimed in  claim 51 , characterized in that the isocyanate-containing compound (A) is isophorone diisocyanate (IPDI). 
     
     
         53 . Method as claimed in  claim 45 , characterized in that in step III, one or more catalyst(s) is/are selected from metal-siloxane-silanol(ate) compounds, organometal compounds of the elements aluminum, tin, zinc, titanium, manganese, iron, bismuth or zirconium and from the group of the tertiary amines or mixtures thereof. 
     
     
         54 . Method as claimed in  claim 45 , characterized in that the catalyst is heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS) or dibutyltin dilaurate (DBTL) or a mixture thereof. 
     
     
         55 . Method as claimed in  claim 45 , characterized in that the reaction of I with II is carried out at temperatures depending on the catalyst and/or a catalyst amount, wherein the catalyst is selected from groups A and/or B, wherein catalyst A is selected from the group of the metal-siloxane-silanol(ate) compounds and catalyst B is a metalorganic catalyst or a tertiary amine, and wherein the catalyst amount is between 1 and 1000 ppm, preferably between 2 and 250 ppm, particularly preferably between 3 and 100 ppm, based on the total weight of the polyol (B) used. 
     
     
         56 . Method as claimed in  claim 43 , characterized in that the organosilane is an aminosilane and is selected from an N-alkylamino silane, preferably N-butyl-3-aminopropyl trimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, [(N-cyclohexylamino)methyl]-methyldiethoxysilane, N-ethylamino-methyl methyldiethoxysilane, N-butyl-3-amino-2-methylpropyl trimethoxysilane, N-ethyl-4-amino-3,3-dimethylbutyl dimethoxymethylsilane or N-ethyl-4-amino-3,3-dimethylbutyl trimethoxysilane. 
     
     
         57 . Use of a method in preparing silylated polyurethanes as claimed in  claim 43 . 
     
     
         58 . Use of the method as claimed in  claim 57 , characterized in that the silylated polyurethanes show viscosity at 25° C. that is at least 20%, preferably at least 30%, and particularly preferably at least 40% lower compared to silylated polyurethanes that were manufactured by methods in which conventional NCO-functionalized polyurethane prepolymers, i.e. oligomeric and/or polymeric NCO-functionalized polyurethane prepolymers, were used. 
     
     
         59 . Silylated polyurethanes produced according to one of the above methods as claimed in  claim 43 .