SELECTIVE POLYURETHANE PREPOLYMER SYNTHESIS

Abstract

The present invention relates to a selective process for producing polyurethane prepolymers, to the polyurethane prepolymers obtainable from this process, and also to a process for producing moisture-crosslinking silylated polymers, more particularly silane-functional hybrid polymers, and also to the use thereof in CASE sectors (coatings, adhesives, sealants and elastomers).

Claims

1. Polyurethane prepolymers obtainable by a reaction of I. at least one isocyanate-containing compound having a molecular weight of 120 Da to 1000 Da with II. a hydroxy-functionalized polymer having a number-average molecular weight M.sub.n of 3500 to 100000 Da, in the presence of a catalyst, characterized in that the molecular weight profile, measured by gel permeation chromatography, of the polyurethane prepolymers from 2000 Da (x.sub.1) to 200000 Da (x.sub.3) along the x-axis has a first section with an area integral F.sub.I and a second section with an area integral F.sub.II, for which the ratio F.sub.II/F.sub.I is between 0 up to and including 0.4, where the first section extends from x.sub.1 to x.sub.2 and the second section extends from x.sub.2 to x.sub.3, and x.sub.2 defines the extreme point between the last intensity maximum (M1a) in the first section, situated in the region of the molecular weight of the hydroxy-functionalized polymer, and the subsequent intensity maximum (M2) in the second section.

2. Polyurethane prepolymers according to claim 1, characterized in that the molar ratio of NCO groups to hydroxyl groups in the reaction of I. with II. is from 5.0:1 to 1.05:1, preferably from 4:1 to 1.5:1 and more preferably from 3.0:1 to 1.8:1.

3. Polyurethane prepolymers according to claim 1, characterized in that the peak (M1a) corresponds to the molecular weight range of a polyurethane prepolymer of the following formula A, ##STR00012## in which R.sup.Iso is the structural unit of the isocyanate-containing compound and R.sup.Poly is the structural unit of the hydroxy-functionalized polymer, where n is x+y and n indicates the number of OH groups in the polyol (functionality).

4. Polyurethane prepolymers according to claim 1, characterized in that the isocyanate-containing compound is isophorone diisocyanate (IPDI), diphenylmethane 2,4′-diisocyanate (2,4′-MDI) or 4,4′-diphenylmethane diisocyanate (4,4′-MDI), and also mixtures thereof.

5. Polyurethane prepolymers according to claim 1, 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 also mixtures thereof, and also combinations with other isocyanate-containing compounds.

6. Polyurethane prepolymers according to claim 1, characterized in that the hydroxy-functionalized polymer is selected from the group consisting of polyether polyols, polyester polyols, polycarbonate polyols and also mixtures of these polyols having a number-average molecular weight M.sub.n of 3500 to 100000 g/mol, preferably 3800 to 90000, more preferably of 4000 to 80000 g/mol.

7. Polyurethane prepolymer according to claim 1, characterized in that the hydroxy-functionalized polymer is selected from the group consisting of polyoxyalkylene diols or polyoxyalkylene triols, more particularly polyoxyethylene and polyoxypropylene diols and triols, polyols of higher functionality such as sorbitol, pentaerythritol-started polyols, ethylene oxide-terminated polyoxypropylene polyols, polyester polyols, styrene-acrylonitrile, acrylic-methacrylate, (poly)urea-grafted or -containing polyether polyols, polycarbonate polyols, CO.sub.2 polyols, polytetrahydrofuran-based polyethers (PTMEG), OH-terminated prepolymers based on the reaction of a polyetherol or polyesterol with a polyisocyanate, polypropylene diols, polyester polyols or mixtures thereof, preferably polypropylene diols, polyester polyols, or mixtures thereof.

8. Polyurethane prepolymer according to claim 1, characterized in that the hydroxy-functionalized polymer is selected from the group consisting of polyester polyols and polyether polyols, more particularly polyoxyethylene polyols, polyoxypropylene polyol and polyoxypropylene-polyoxyethylene polyol, preferably polyoxyethylene diol, polyoxypropylene diol, polyoxyethylene triol, polyoxypropylene triol, polyoxypropylene-polyoxyethylene diol and polyoxypropylene-polyoxyethylene triol.

9. Polyurethane prepolymers according to claim 1, characterized in that the catalyst is selected from the group consisting of metal-siloxane-silanol(ate) compounds, organometallic compounds of the elements aluminium, tin, zinc, titanium, manganese, iron, bismuth or zirconium, and from the group of the tertiary amines, or mixtures thereof.

10. Polyurethane prepolymers according to claim 1, characterized in that the temperature in the reaction of I. with II. is between 10° C. and 120° C., preferably between 15° C. to 100° C., more preferably between 20° C. and 90° C. and very preferably between 25° C. and 85° C.

11. Polyurethane prepolymers according to claim 1, characterized in that the total catalyst amount is between 1 and 1000 ppm, preferably between 2 and 250 ppm, more preferably between 3 and 100 ppm, based on the total weight of the hydroxy-functionalized polymer used.

12. Polyurethane prepolymers according to claim 1, characterized in that the catalyst is selected from groups A and/or B, where the catalyst A is selected from the group of metal-siloxane-silanol(ate) compounds and the catalyst B is a metal-organic catalyst or a tertiary amine.

13. Polyurethane prepolymers according to claim 12, characterized in that when using a catalyst from group A, a reaction temperature between 10° C. and 120° C., preferably between 15° C. to 100° C., more preferably between 20° C. and 90° C. and very preferably between 25° C. and 85° C. is employed.

14. Polyurethane prepolymers according to claim 12, characterized in that when using a catalyst from group A, the amount of the catalyst A selected is between 1 ppm and 500 ppm, preferably between 2 ppm and 250 ppm, more preferably between 3 ppm and 80 ppm.

15. Polyurethane prepolymers according to claim 12, characterized in that when using a catalyst from group B, a reaction temperature of 20° C. to 80° C., preferably of 20° C. to 70° C., more preferably of 25° C. to 50° C. is employed.

16. Polyurethane prepolymers according to claim 12, characterized in that when using a catalyst from group B, the amount of the catalyst B selected is between 1 ppm to 1000 ppm, preferably between 2 ppm to 250 ppm, more preferably between 3 ppm to 100 ppm.

17. Polyurethane prepolymers according to claim 12, characterized in that the catalyst A is a metal-siloxane-silanol(ate) compound and has a general structure (I), ##STR00013## where X.sup.1, X.sup.2 and X.sup.3 independently of one another are selected from Si or M.sup.1, where M.sup.1 is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and semi-metals, more particularly from the group consisting of metals from transition groups 1., 2., 3., 4., 5., 8., 10. and 11. and metals from main groups 1., 2., 3., 4. and 5., preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi; Z.sup.1, Z.sup.2 and Z.sup.3 independently of one another are selected from the group consisting of L.sup.2, R.sup.5, R.sup.6 and R.sup.7, where L.sup.2 is selected from the group consisting of —OH and —O—(C1 to C10 alkyl), more particularly —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or where L.sup.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.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 and R.sup.7 independently of one another are 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.sup.1 and Y.sup.2 independently of one another are —O-M.sup.2-L.sup.3.sub.Δ, or Y.sup.1 and Y.sup.2 are taken together and together are —O-M.sup.2(L.sup.3.sub.Δ)-O— or —O—, where L.sup.3 is selected from the group consisting of —OH and —O—(C1 to C10 alkyl), more particularly —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or where L.sup.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 where M.sup.2 is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and semi-metals, more particularly from the group consisting of metals from transition groups 1., 2., 3., 4., 5., 8., 10. and 11. and metals from main groups 1., 2., 3., 4. and 5., preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi; and X.sup.4 is -M.sup.3L.sup.1.sub.Δ or M.sup.3 and Q.sup.1 and Q.sup.2 are H or in each case a single bond linked to M.sup.3, where L.sup.1 is selected from the group consisting of —OH and —O—(C1 to C10 alkyl), more particularly —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or where L.sup.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.sup.3 is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and semi-metals, more particularly from the group consisting of metals from transition groups 1., 2., 3., 4., 5., 8., 10. and 11. and metals from 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 particularly preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, or X.sup.4 is -M.sup.3L.sup.1.sub.Δ and Q.sup.2 is H or a single bond linked to M.sup.3, and Q.sup.1 is H, M.sup.4L.sup.4.sub.Δ or —SiR.sup.8, where M.sup.4 is selected from the group consisting of s and p block metals, d and f block transition metals, lanthanide and actinide metals, and semi-metals, more particularly from the group consisting of metals from transition groups 1., 2., 3., 4., 5., 8., 10. and 11. and metals from main groups 1., 2., 3., 4. and 5., preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi; and where L.sup.4 is selected from the group consisting of —OH and —O—(C1 to C10 alkyl), more particularly —O—(C1 to C8 alkyl) or —O—(C1 to C6 alkyl), or where L.sup.4 is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O— isobutyl, and where R.sup.8 is selected from the group consisting of optionally substituted C1 to C20 alkyl, optionally substituted C3 to C8 cycloalkyl, optionally substituted C2 to C20 alkenyl and optionally substituted C5 to C10 aryl, or X.sup.4, Q.sup.1 and Q.sup.2 independently of one another are -M.sup.3L.sup.1.sub.Δ, or X.sup.4 is —Si(R.sup.8)—O-M.sup.3L.sup.1.sub.Δ, Q.sup.2 is a single bond linked to the Si atom of X.sup.4, and Q.sup.1 is -M.sup.4L.sup.4.sub.Δ, or X.sup.4 is —Si(R.sup.8)—O-M.sup.3L.sup.1.sub.Δ, Q.sup.2 is a single bond linked to the Si atom of X.sup.4, and Q.sup.1 is a single bond linked to the M.sup.3 atom of X.sup.4.

18. Polyurethane prepolymer according to claim 12, characterized in that the catalyst B is selected from the group consisting of tetraalkyl titanates, such as tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-sec-butyl titanate, tetraoctyl titanate, tetra-(2-ethylhexyl) titanate, dialkyl titanates ((RO).sub.2TiO.sub.2, in which R, for example, is isopropyl, n-butyl or isobutyl), such as isopropyl n-butyl titanate; titanium acetylacetonate chelates, such as diisopropoxy-bis(acetylacetonate) titanate, diisopropoxy-bis(ethylacetylacetonate) titanate, di-n-butyl-bis(acetylacetonate) titanate, di-n-butyl-bis(ethylacetoacetate) titanate, triisopropoxide-bis(acetylacetonate) titanate, zirconium tetraalkoxides, such as zirconium tetraethoxide, zirconium tetrabutoxide, zirconium tetrabutyrate, zirconium tetrapropoxide, zirconium carboxylates, such as zirconium diacetate; zirconium acetylacetonate chelates, such as zirconium tetra(acetylacetonate), tributoxyzirconium acetylacetonate, dibutoxyzirconium (bisacetylacetonate), aluminium trisalkoxides, such as aluminium triisopropoxide, aluminium trisbutoxide; aluminium acetylacetonate chelates, such as aluminium tris(acetylacetonate) and aluminium tris(ethylacetylacetonate), organotin compounds such as dibutyltin dilaurate (DBTL), dibutyltin maleate, dibutyltin diacetate, tin(II) 2-ethylhexanoate (tin octoate), tin naphthenate, dimethyltin dineodecanoate, dioctyltin dineodecanoate, dimethyltin dioleate, dioctyltin dilaurate, dimethyl mercaptides, dibutyl mercaptides, dioctyl mercaptides, dibutyltin dithioglycolate, dioctyltin glycolate, dimethyltin glycolates, a solution of dibutyltin oxide, reaction products of zinc salts and organic carboxylic acids (carboxylates) such as zinc(II) 2-ethylhexanoate or zinc(II) neodecanoate, mixtures of bismuth carboxylates and zinc carboxylates, reaction products of bismuth salts and organic carboxylic acids such as bismuth(III) tris(2-ethylhexonate) and bismuth(III) tris(neodecanoate) and also bismuth complex compounds, organolead compounds such as lead octoxide, organovanadium compounds, amine compounds such as butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole and 1.8-diazabicylo[5.4.0]undec-7-ene (DBU), salts of these amines with carboxylic acids or other acids, or mixtures thereof.

19. Polyurethane prepolymer according to claim 18, characterized in that the catalyst B is selected from the group consisting of dibutyltin dilaurate (DBTL), tin(II) 2-ethylhexanoate (tinoctoate), zinc(II) 2-ethylhexanoate, zinc(II) neodecanoate, bismuth(III) tris(2-ethylhexonate), bismuth(III) tris(neodecanoate) or mixtures thereof.

20. Polyurethane prepolymer according to claim 12, characterized in that the at least one catalyst A and/or at least one catalyst B are selected from the group of organotin or organotitanium compounds.

21. Polyurethane prepolymer according to claim 12, characterized in that the catalyst A is selected from the group of heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) and heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS).

22. Polyurethane prepolymers according to claim 21, characterized in that the catalyst A is heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS).

23. Polyurethane prepolymer according to claim 19, characterized in that the catalyst B is dibutyltin dilaurate (DBTL).

24. Silylated polyurethanes obtainable by reacting polyurethane prepolymers according to claim 1 with an organosilane.

25. Silylated polyurethanes according to claim 24, characterized in that the silylated polyurethane has at least two end groups of the general formula (V), ##STR00014## where X is C, Si or a heteroatom and these, according to their valency, optionally have one or more radicals R.sup.8, is preferably C, N, O, P or S, more preferably C, N or O, very preferably N or O, and is bonded in each case to a carbon in the polymer backbone, R* is O or an optionally substituted, straight-chain or branched C1 to C25 alkyl group or an optionally substituted C4 to C18 cycloalkyl group or an optionally substituted C4 to C18 aryl group and if R*=0, the Si atom is connected directly to the N atom, each Y independently of any other is either 0 or a direct bond of the Si atom to the respective radical R.sup.9, R.sup.10 or R.sup.11, and preferably at least one Y is 0, R.sup.8 is H, an optionally substituted, straight-chain or branched C1 to C16 alkyl group, an optionally substituted, straight-chain or branched C2 to C16 alkenyl group or an optionally substituted, straight-chain or branched C2 to C16 alkynyl group, an optionally substituted C4 to C14 cycloalkyl group or an optionally substituted C4 to C14 aryl group, or is a radical of the general structure (Vb), R.sup.12 and R.sup.14 each independently of one another are H or a radical from the group consisting of —R.sup.15, —COOR.sup.15 and —CN, R.sup.13 is H or is a radical from the group consisting of —CH.sub.2—COOR.sup.15, —COOR.sup.15, —CONHR.sup.15, —CON(R.sup.15), —CN, —NO.sub.2, —PO(OR.sup.15).sub.2, —SOR.sup.15 and —SO.sub.2OR.sup.15, R.sup.15 is a hydrocarbon radical having 1 to 20 C atoms and optionally containing at least one heteroatom, R.sup.9, R.sup.10 and R.sup.11 independently of one another are H, an optionally substituted, straight-chain or branched C1 to C5 alkyl group, an optionally substituted, straight-chain or branched C2 to C10 alkenyl group or an optionally substituted C4 to C14 cycloalkyl group or an optionally substituted C4 to C14 aryl group, m is 0 or 1 and if m=0, the Si atom is bonded directly to a carbon in the polymer backbone.

26. Silylated polyurethanes according to claim 25, characterized in that the organosilane of the general structure (VIII) is selected or is a mixture thereof, ##STR00015## where R.sup.7 is H, R.sup.8 is H, an optionally substituted, straight-chain or branched C1 to C25 alkyl group, an optionally substituted, straight-chain or branched C2 to C25 alkenyl group or an optionally substituted C4 to C18 cycloalkyl group or an optionally substituted C4 to C18 aryl group or a radical of the general structure (Vb), R* is O or an optionally substituted, straight-chain or branched C1 to C25 alkyl group or an optionally substituted C4 to C18 cycloalkyl group or an optionally substituted C4 to C18 aryl group and if R*=0, the Si atom is connected directly to the N atom, R.sup.12 and R.sup.14 each independently of one another are H or a radical from the group consisting of —R.sup.15, —COOR.sup.15 and —CN, R.sup.13 is H or is a radical from the group consisting of —CH.sub.2—COOR.sup.15, —COOR.sup.15, —CONHR.sup.15, —CON(R.sup.15), —CN, —NO.sub.2, —PO(OR.sup.15).sub.2, —SOR.sup.15 and —SO.sub.2OR.sup.15, R.sup.15 is a hydrocarbon radical having 1 to 20 C atoms and optionally containing at least one heteroatom, R.sup.9, R.sup.10, R.sup.11 and R* are defined according to claim 25, and each Y independently of any other is either O or a direct bond of the Si atom to the respective radical R.sup.9, R.sup.10 or R.sup.11; and preferably at least one Y is O.

27. Silylated polyurethanes according to claim 26, characterized in that at least one organosilane of the general structure (VIII) is selected or is a mixture thereof, ##STR00016## where R.sup.8 is H, an optionally substituted, straight-chain or branched C1 to C10 alkyl group, an optionally substituted, straight-chain or branched C2 to C10 alkenyl group or an optionally substituted, straight-chain or branched C2 to C10 alkynyl group, an optionally substituted C4 to C10 cycloalkyl group or an optionally substituted C4 to C10 aryl group or a succinic acid derivative of the general structure (Vb) according to claim 26, R* is O or an optionally substituted, straight-chain or branched C1 to C20 alkyl group or an optionally substituted C4 to C12 cycloalkyl group or an optionally substituted C4 to C12 aryl group, preferably an optionally substituted, straight-chain or branched C1 to C15 alkyl group, more preferably a C1 alkyl group (=alpha-silane) or a C3 alkyl group (=gamma-silane) and, if R*=0, the Si atom is connected directly to the N atom, preferably R.sup.9, R.sup.10 and R.sup.11 are a methyl or ethyl group or mixtures thereof, and Y in Y—R.sup.9 and Y—R.sup.10 is O and the Y in Y—R.sup.11 is either O or a direct bond of the Si atom to the respective radical R.sup.11.

28. Silylated polyurethanes according to claim 24, characterized in that the organosilane corresponds to an organosilane of the formula (IX), ##STR00017## in which the two radicals R.sup.16 and R.sup.17 are each independent of one another and the radical R.sup.16 is a linear or branched, monovalent hydrocarbon radical having 1 to 8 C atoms, more particularly a methyl or ethyl group, the radical R.sup.17 is an acyl radical or a linear or branched, monovalent hydrocarbon radical having 1 to 5 C atoms, more particularly a methyl or ethyl group, preferably a methyl group, the index a is 0 or 1 or 2, more particularly 0, and the radical R.sup.18 is a linear or branched, divalent hydrocarbon radical having 1 to 12 C atoms, which optionally contains cyclic moieties and optionally one or more heteroatoms, more particularly one or more nitrogen atoms, and more particularly is an alkylene group having 1 to 6 C atoms, preferably 2 to 6 C atoms, more particularly a propylene group, and R.sup.19 is a hydrogen atom or a cyclic, linear or branched, monovalent hydrocarbon radical having 1 to 20 C atoms, which optionally contains cyclic moieties, or is a radical of the following formula: ##STR00018## in which the radicals R.sup.20 and R.sup.21 each independently of one another are a hydrogen atom or a radical from the group consisting of —R.sup.23, —COOR.sup.23 and —CN, the radical R.sup.22 is a hydrogen atom or a radical from the group consisting of —CH.sub.2—COOR*, —COOR.sup.23, —CONHR.sup.23, —CON(R.sup.23).sub.2, —CN, —NO.sub.2, —PO(OR.sup.23).sub.2, —SO.sub.2R.sup.23 and —SO.sub.2OR.sup.23, and the radical R.sup.23 is a hydrocarbon radical having 1 to 20 C atoms and optionally containing at least one heteroatom, and also mixtures thereof.

29. Silylated polyurethanes according to claim 24, characterized in that the aminosilane is selected from the group of primary aminosilanes, preferably 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, of secondary aminosilanes, preferably N-butyl-3-aminopropyltrimethoxysilane, N-phenyl-3-amino-propyltrimethoxysilane, from the group of products obtainable from the Michael-like addition of primary aminosilanes such as 3-aminopropyltrimethoxysilane or 3-aminopropyldimethoxymethylsilane with Michael acceptors such as acrylonitrile, acrylic esters, (meth)acrylic esters, (meth)acrylamides, maleic and fumaric diesters, citraconic diesters and itaconic diesters, preferably dimethyl and diethyl N-(3-trimethoxysilylpropyl)aminosuccinate.

30. Silylated polyurethanes according to claim 24, characterized in that the 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.

31. Composition comprising silylated polyurethanes according to claim 24.

32. Composition comprising one or more polyurethane prepolymers according to claim 1.

33. Use of the polyurethane prepolymers according to claim 1 for producing polyurethane elastomers, polyurethane ureas, one- or two-component reactive polyurethane systems, as polyurethane foams, construction materials, varnishes, coatings, adhesives and sealants, grouts, films or PUR elastomers.

34. Use of the polyurethane prepolymers according to claim 1 for producing reactive PU compositions, preferably in aqueous 1K (1-component) or 2K (two-component) PU compositions.

Description

EXAMPLES

[0284] I. GPC Data

[0285] Instrument and Parameters of STD-GPC Measurement:

[0286] Chromatographic System:

[0287] Degasser: Agilent 1260 Infinity Degasser

[0288] Pump: Agilent 1260 Infinity IsoPump

[0289] Autosampler: Agilent 1260 Infinity ALS

[0290] Column oven: Agilent 1290 Infinity II TCC

[0291] RI detector: Agilent 1260 Infinity RID

[0292] Software: PSS WinGPC UniChrom V 8.31, Build 8417

[0293] Chromatographic Conditions:

[0294] DIN: DIN EN ISO 16014-1, DIN 55672-1

[0295] Column: 1. PLgel 5p Mixed D (Agilent Technologies)

[0296] 2. PLgel 5p Mixed D (Agilent Technologies)

[0297] 3. PLgel 3 μm Mixed E (Agilent Technologies)

[0298] Mobile Phase: Tetrahydrofuran

[0299] Flow rate: 1 mL/min

[0300] Temperature: 35° C.

[0301] Injection volume: 100 μL

[0302] Sample concentration: 1 g/L

[0303] Molecular weight standards:

[0304] PSS Polymer-Standards-Service GmbH, Mainz; Germany

[0305] M.sub.p [Da]: 66000; 42400; 25500; 15700; 8680; 6540; 4920; 3470; 2280; 1306; 370; 266

[0306] *The calibration curve is valid between 266 Da and 66000 Da. Values outside these limits are extrapolated.

[0307] II. Viscosity

[0308] The viscosities were determined using a Brookfield Rheometer DV-3T Extra at 25° C. Spindle size and spindle speed were selected such that the torque is >90%.

[0309] III. Infrared (IR) Spectroscopy:

[0310] IR monitoring was measured using a ThermoScientific Nicolet iS5 and iD7ATR unit. Evaluation took place with Omnic 9 Software.

Examples I)

[0311] Chemicals used: [0312] Acclaim 18200 (Covestro AG; low mono polyoxypropylene diol, OH number 6.0 mg KOH/g, water content approx. 0.02% by weight) [0313] 3-Isocyanatomemyl-3,5,5-trimethyl cyclohexyl isocyanate (Desmodur® I, Covestro AG, Leverkusen) [0314] TiPOSS (heptaisobutyl POSS-titanium(IV) ethoxide), 20% solution in Hexamoll® DINCH, BASF) [0315] DBTL (dibutyltin dilaurate) BNT Chemicals [0316] DBA (di-n-butylamine) purity >99%, TCl Chemicals [0317] N-[3-(trimethoxysilyl)propyl]butylamine, DOG Deutsche Olfabrik [0318] VTMO, vinyltrimethoxysilane, Acros Organics

[0319] A) Production of the Polyurethane Prepolymers of the Invention

Example 1

[0320] 200 g (11 mmol) of polypropylene glycol having an approximate number-average molecular weight M.sub.n of 18000 g/mol (OH number=6.0±1.0 mg KOH/g) were charged to a 500 ml three-necked flask and dried under reduced pressure at 80° C. for one hour. The reduced pressure was subsequently broken with nitrogen. The polyol was cooled to 25° C. 0.01 g (0.016 mmol) of DBTL catalyst and 5.19 g (23 mmol) of isophorone diisocyanate (IPDI) were added with stirring. As soon as the theoretical NCO content of 0.52 wt % was reached, a determination was made of the viscosity of the NCO prepolymer [46000 mPas (25° C., Brookfield viscometer)]. For the GPC analysis the prepolymer was reacted with 3.02 g (23 mmol) of di-n-butylamine and stirred at 25° C. for 20 minutes. The reaction was monitored by IR spectroscopy (disappearance of the NCO band (2270 cm.sup.−1)). The ratio of the area integral F.sub.I in the first section (x.sub.1 to x.sub.2) of the molar weight distribution and the area integral F.sub.II in the second section of the molar weight distribution, F.sub.II/F.sub.I, is 0.29.

Example 2

[0321] 200 g (11 mmol) of polypropylene glycol having an approximate number-average molecular weight M.sub.n of 18000 g/mol (OH number=6.0±1.0 mg KOH/g) were charged to a 500 ml three-necked flask and dried under reduced pressure at 80° C. for one hour. The reduced pressure was subsequently broken with nitrogen. The polyol was cooled to 25° C. 0.01 g (0.011 mmol, pure substance) of TiPOSS catalyst and 5.19 g (23 mmol) of isophorone diisocyanate (IPDI) were added and the reaction mixture was stirred. As soon as the theoretical NCO content of 0.52 wt % was reached, a determination was made of the viscosity of the NCO prepolymer [44000 mPas (25° C., Brookfield viscometer)]. For the GPC analysis the prepolymer was reacted with 3.02 g (23 mmol) of di-n-butylamine and stirred at 25° C. for 20 minutes. The reaction was monitored by IR spectroscopy (disappearance of the NCO band (2270 cm.sup.−1)). The ratio of the area integral F.sub.I in the first section (x.sub.1 to x.sub.2) of the molar weight distribution and the area integral F.sub.II in the second section (x.sub.2 to x.sub.3) of the molar weight distribution, F.sub.II/F.sub.I, is 0.27.

[0322] Examples 3 to 6 were prepared in accordance with the procedure of examples 1 and 2.

TABLE-US-00001 TABLE 1 Example Catalyst Reaction Viscosity Not Area number Catalyst amount temperature [mPas] inventive x ratio 1 DBTL 50 ppm 25° C. 46 000 0.29 2 TiPOSS 50 ppm 25° C. 44 000 0.27 3 TiPOSS 10 ppm 80° C. 43 000 4 TiPOSS 50 ppm 80° C. 48 000 0.23 5 TiPOSS 37.5 ppm   40° C. 48 000 6 TiPOSS 84 ppm 25° C. 43 000 7 DBTL 50 ppm 80° C. 120 800  x 0.43

[0323] B) Production of the Silane-Terminated Polymers (STP), Also Called Silylated Polymers Silane-Terminated Polyols from the Reaction of Isocyanate Prepolymer.

Example 8

[0324] 150.2 g (8.3 mmol) of polypropylene glycol having an approximate number-average molecular weight Ma of 18000 g/mol (OH number=6.0±1.0 mg KOH/g) were charged to a 500 ml three-necked flask and dried under reduced pressure at 90° C. for one hour. The reduced pressure was subsequently broken with nitrogen. The polyol was cooled to 80° C. 1.5 mg (0.0015 mmol, pure substance) of TiPOSS catalyst and 4.01 g (18 mmol) of isophorone diisocyanate (IPDI) were added with stirring. As soon as the theoretical NCO content of 0.52 wt % was reached, 4.97 g (21 mmol) of N-[3-(trimethoxysilyl)propyl]butylamine] were added with stirring and the system was cooled simultaneously to 25° C. The reaction was monitored by IR spectroscopy (disappearance of the NCO band (2270 cm.sup.−1)). 2% by weight of VTMO was added to the completed STP. The viscosity of the product was 43000 mPas (25° C., Brookfield viscosity).