US20220235171A1 - Composition and process for preparing moisture-crosslinking polymers and use thereof - Google Patents

Composition and process for preparing moisture-crosslinking polymers and use thereof Download PDF

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US20220235171A1
US20220235171A1 US17/439,604 US202017439604A US2022235171A1 US 20220235171 A1 US20220235171 A1 US 20220235171A1 US 202017439604 A US202017439604 A US 202017439604A US 2022235171 A1 US2022235171 A1 US 2022235171A1
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Klaus Langerbeins
Michael SENZLOBER
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PolyU GmbH
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PolyU GmbH
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Publication of US20220235171A1 publication Critical patent/US20220235171A1/en
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00—Manufacture of cellular products
    • 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
    • C08G2110/0008—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 compositions comprising moisture-crosslinking polymers and to processes for preparation thereof, especially of silane-functional hybrid polymers, and to the moisture-crosslinking polymers as such.
  • the present invention relates to the use of these compositions in CASE sectors (coatings, adhesives, sealants and elastomers), for example in adhesives and sealants.
  • Polymers such as silylated polyurethanes, for example, that condense (“crosslink”) on contact with water or air humidity and at room temperature have long been known. They are also referred to as moisture-crosslinking polymers. Depending on factors including the content of silane groups and the structure thereof, it is possible for long-chain polymers, wide-mesh three-dimensional networks or highly crosslinked systems to form.
  • Moisture-crosslinking polymers especially silylated polyurethanes, have long found various uses as adhesives and sealants.
  • adhesives and sealants For instance, the field of traditional silicone adhesives and sealants based on dimethylpolysiloxanes and of polyurethane adhesives and sealants having free isocyanate groups has developed to include silane-terminated adhesives and sealants.
  • methoxy-substituted silanes are used.
  • the use of these compounds has become generally established since these have good reactivity.
  • methoxysilane-substituted polymers have the disadvantage of eliminating methanol on curing. This is a matter of toxicological concern.
  • the core of the invention is accordingly that of providing a composition comprising at least two catalysts A and B and at least one silylated polymer (SiP), wherein catalyst A is selected from the group of the metal-siloxane-silanol(ate) compounds.
  • the silylated polymer (SiP) has preferably been prepared from a metal-siloxane-silanol(ate) compound-catalysed synthesis of at least one hydroxy-functionalized polymer (also “hydroxy-functional polymer”), and a compound having at least one isocyanate group.
  • the composition according to claim 1 permits the use of ethoxy-substituted silanes.
  • the curing of the SiP accordingly eliminates not methanol but ethanol, which is of no toxicological concern.
  • it is possible to achieve acceptable fibre times and tack-free times (similarly to the case of methoxy-functional hybrid polymers).
  • the invention therefore permits provision of formulations, for example for the adhesives and sealants sectors, in which it is possible to dispense with the methanol-eliminating hybrid polymers.
  • catalyst B is likewise a metal-siloxane-silanol(ate) compound.
  • Catalyst B may advantageously also be an organometallic compound.
  • a composition according to the invention advantageously comprises moisture-curing silylated polymers (SiP) and at least one metal-siloxane-silanol(ate) compound, wherein the metal-siloxane-silanol(ate) compound is present with a proportion by weight in the range from 0.001% to 5%, preferably from 0.002% to 1%, based in each case on the total weight of the composition.
  • compositions according to the invention preferably comprise silylated polymers that have been prepared by means of catalysis by metal-siloxane-silanol(ate) compounds in molar concentrations in the range from 0.000001 to 0.0001 mol/kg or 0.0001 to 0.1 mol/kg, especially from 0.00001 to 0.00005 mol/kg or 0.001 to 0.01 mol/kg, based in each case on the total weight of the composition.
  • catalyst relates to a substance that lowers the activation energy of a particular reaction and hence increases the reaction rate.
  • metal-siloxane-silanol(ate) refers to all metal-siloxane compounds that contain either one or more silanol and/or silanolate groups. In one embodiment of the invention, it is likewise possible that there are exclusively metal-siloxane-silanolates. If no specific differentiation is made between these different configurations, all combinations are included.
  • POMS oligomeric metallosilsesquioxanes
  • the metal-siloxane-silanol(ate) compound may take the form of a monomer, oligomer and/or polymer for preparation of the silylated polymers (SiP) of the composition according to the invention, the transition from oligomers to polymers being fluid according to the general definition.
  • the metal(s) was/were preferably present terminally and/or within the chain in the oligomeric and/or polymeric metal-siloxane-silanol(ate) compound.
  • the catenated metal-siloxane-silanol(ate) compound is linear, branched and/or a cage.
  • the catenated metal-siloxane-silanol(ate) compound in the composition according to the invention and/or in the preparation of the silylated polymers (SiP) in the composition according to the invention has a cage structure.
  • a “cage” or an oligomeric or polymeric “cage structure” for the purposes of the present invention is a three-dimensional arrangement of the catenated metal-siloxane-silanol(ate) compound, wherein individual atoms in the chain form the vertices of a multifaceted base structure of the compound. In this case, the mutually linked atoms form at least two surfaces, giving rise to a common intersection. In one embodiment of the compound, for example, a cubic base structure of the compound is formed.
  • a one-cage structure or else a cage structure in singular form, i.e. a compound that has an isolated cage, is the structure (IVc).
  • a cage may be “open” or else “closed”, depending on whether all vertices are bonded, joined or coordinated so as to form a closed cage structure.
  • a closed cage is the structures (II), (IV), (IVb), (IVc).
  • the term “-nuclear” gives the nuclearity of a compound, how many metal atoms are present therein.
  • a mononuclear compound has one metal atom, whereas a dinuclear compound has two metal atoms within a compound.
  • the metals may be bonded directly to one another or linked via their substituents.
  • One example of a mononuclear compound according to the invention is, for example, the structures (IV), (IVb), (IVc), (Ia), (Ib) or (Ic); a dinuclear compound is represented by structure (Id).
  • a mononuclear one-cage structure is represented by the metal-siloxane-silanol(ate) compounds (IV), (IVb) and (IVc).
  • Mononuclear two-cage structures are, for example, the structures (Ia), (Ib) or (Ic).
  • the metal-siloxane-silanol(ate) compound in the preparation of the silylated polymers (SiP) of the composition according to the invention preferably comprises an oligomeric metal silsesquioxane.
  • the metal-siloxane-silanol(ate) compound in the preparation of the silylated polymers (SiP) of the composition according to the invention especially comprises a polyhedral metal silsesquioxane.
  • the metal-siloxane-silanol(ate) compound in the composition according to the invention and/or in the preparation of the silylated polymers (SiP) has the general formula R* q Si r O s M t where each R* is independently selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl, optionally substituted C5- to C10-aryl, —OH and —O—(C1- to C10-alkyl), each M is independently selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc
  • q is an integer from 4 to 19
  • r is an integer from 4 to 10
  • s is an integer from 8 to 30, and
  • t is an integer from 1 to 8.
  • the metal-siloxane-silanol(ate) compound in the composition according to the invention and/or in the preparation of the silylated polymers (SiP) has the general formula R # 4 Si 4 O 11 Y 2 Q 2 X 4 Z 3 where each X is independently selected from the group consisting of Si, M 1 , -M 3 L 1 ⁇ , M 3 , or —Si(R 8 )—O-M 3 L 1 ⁇ , 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, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially
  • 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 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 R 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;
  • each Z is 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), especially —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;
  • each R # , R 5 , R 6 and R 7 is independently selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C5- to C10-aryl; each Y is independently —O-M 2 -L 3 ⁇ , or two Y are associated and together are —O-M 2 (L 3 ⁇ )-O— or —O—, where L 3 is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L 3 is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octy
  • each Q is independently H, M 4 L 4 ⁇ , —SiR 8 , -M 3 L 1 ⁇ , a single bond joined to M 3 of X or a single bond joined to the silicon atom of the —Si(R 8 )—O-M 3 L 1 ⁇ radical, where M 3 , R 8 and L 1 are as defined for X, 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, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and where L 4 is selected from the
  • At least one X is M 3 , -M 3 L 1 ⁇ or —Si(R 8 )—O-M 3 L 1 ⁇ .
  • the metal-siloxane-silanol(ate) compound in the composition according to the invention and/or in the preparation of the silylated polymers (SiP) has the general formula (Y 0.25 R # SiO 1.25 ) 4 (Z 0.75 Y 0.25 XO) 4 (OQ) 2 where each X is independently selected from the group consisting of Si, M 1 , -M 3 L 1 ⁇ , M 3 , or —Si(R 8 )—O-M 3 L 1 ⁇ , 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, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe,
  • each Z is 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), especially —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;
  • each R # , R 5 , R 6 and R 7 is independently selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C6-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C6- to C10-aryl;
  • each Y is independently —O-M 2 -L 3 ⁇ , or two Y are associated and together are —O-M 2 (L 3 ⁇ )-O— or —O—, where L 3 is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where 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 each M 2 is independently selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from
  • each Q is independently H, M 4 L 4 ⁇ , —SiR 8 , -M 3 L 1 ⁇ , a single bond joined to M 3 of X or a single bond joined to the silicon atom of the —Si(R 8 )—O-M 3 L 1 ⁇ radical, where M 3 , R 8 and L 1 are as defined for X, 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, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and where L 4 is selected from the
  • At least one X is M 3 , -M 3 L 1 ⁇ or —Si(R 8 )—O-M 3 L 1 ⁇ .
  • the metal-siloxane-silanol(ate) compound in the composition according to the invention and/or the preparation of the silylated polymers (SiP) 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 and 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, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr
  • 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), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L2 is selected from the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl;
  • 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 are independently —O-M 2 -L 3 ⁇ , or Y 1 and Y 2 are associated and together are —O-M 2 (L 3 ⁇ )-O— or —O—, where L 3 is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where 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, especially from the group
  • X 4 is -M 3 L 1 ⁇ or M 3 and Q 1 and Q 2 are each H or a single bond joined to M 3 , where 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 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, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main
  • X 4 is -M 3 L 1 ⁇ and Q 2 is H or a single bond joined to M 3 and Q 1 is H, M 4 L 4 ⁇ 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, especially from the group consisting of metals from transition group 2, 3, 4, 5 and 8 and metals from main group 1, 2, 3, 4 and 5, especially from the group consisting of Zn, Sc, Ti, Zr, Hf, V, Pt, Ga, Sn and Bi, where L 4 is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L 4 is selected from the group consisting of —OH, —O-methyl, —O-ethyl,
  • X 4 , Q 1 and Q 2 are independently -M 3 L 1 ⁇ , or
  • X 4 is —Si(R 8 )—O-M 3 L 1
  • Q 2 is a single bond joined to the silicon atom of X 4 and Q 1 is -M 4 L 4 ⁇ , or
  • X 4 is —Si(R 8 )—O-M 3 L 1 ⁇
  • Q 2 is a single bond joined to the silicon atom of X 4
  • Q 1 is a single bond joined to the M 3 atom of X 4 .
  • the metal silsesquioxane in the composition according to the invention and/or in the preparation of the silylated polymers (SiP) has the general formula (X 4 )(Z 1 Y 1 X 2 O)(Z 2 X 1 O 2 )(Z 3 X 3 O 2 )(R 1 Y 2 SiO)(R 3 SiO)(R 4 SiO 2 )(R 2 SiO 2 )(Q 1 )(Q 2 )
  • X 1 , X 2 and X 3 are independently selected from Si and 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, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V
  • 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), especially —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 are independently —O-M 2 -L 3 ⁇ , or Y 1 and Y 2 are associated and together are —O-M 2 (L 3 ⁇ )-O— or —O—, where L 3 is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where 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, especially from the group
  • X 4 is -M 3 L 1 ⁇ or M 3 and Q 1 and Q 2 are each H or a single bond joined to M 3 , where 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 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, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main
  • X 4 is -M 3 L 1 ⁇ and Q 2 is H or a single bond joined to M 3 and Q 1 is H, M 4 L 4 ⁇ or —SiR 8 , where M4 is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 2, 3, 4, 5 and 8 and metals from main group 1, 2, 3, 4 and 5, especially from the group consisting of Zn, Sc, Ti, Zr, Hf, V, Pt, Ga, Sn and Bi, where L 4 is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L 4 is selected from the group consisting of —OH, —O-methyl, —O-ethyl,
  • X 4 , Q 1 and Q 2 are independently -M 3 L 1 ⁇ , or
  • X 4 is —Si(R 8 )—O-M 3 L 1 ⁇
  • Q 2 is a single bond joined to the silicon atom of X 4 and Q 1 is -M 4 L 4 ⁇ , or
  • X 4 is —Si(R 8 )—O-M 3 L 1 ⁇
  • Q 2 is a single bond joined to the silicon atom of X 4
  • Q 1 is a single bond joined to the M 3 atom of X 4 .
  • the catalyst used in accordance with the invention and based on a metal-siloxane-silanol(ate) compound may be described by the structure (I)
  • X 1 , X 2 and X 3 are independently selected from Si and 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, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,
  • 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), especially —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 are independently —O-M 2 -L 3 ⁇ , or Y 1 and Y 2 are associated and together are —O-M 2 (L 3 ⁇ )-O— or —O—, where L 3 is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where 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 where 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, especially from the
  • 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 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, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main
  • X 4 is -M 3 L 1 and Q 2 is H or a single bond joined to M 3 and Q 1 is H, M 4 L 4 ⁇ 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, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and where L 4 is selected from the group consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C
  • X 4 , Q 1 and Q 2 are independently -M 3 L 1 ⁇ , or
  • X 4 is —Si(R 8 )—O-M 3 L 1 ⁇
  • Q 2 is a single bond joined to the silicon atom of X 4 and Q 1 is -M 4 L 4 ⁇ , or
  • X 4 is —Si(R 8 )—O-M 3 L 1 ⁇
  • Q 2 is a single bond joined to the silicon atom of X 4
  • Q 1 is a single bond joined to the M 3 atom of X 4 .
  • the metal-siloxane-silanol(ate) compound in the preparation of the silylated polymers has the general formula (I) where X 1 , X 2 and X 3 are independently Si,
  • X 4 is -M 3 L 1 ⁇ and Q 1 and Q 2 are each a single bond joined to M 3 , where 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 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, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4
  • 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 and R 3 are each independently 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 associated and together form —O—.
  • the metal-siloxane-silanol(ate) compound of formula (I) in the composition according to the invention and/or in the preparation of the silylated polymers (SiP), depending on the equivalents of metal present may be in mononuclear form as a monomer or in polynuclear form as a dimer (dinuclear), trimer (trinuclear), multimer (multinuclear) and/or mixtures thereof, such that, for example, structures of the formulae (Ia) to (Id) are possible.
  • polynuclear metal-siloxane-silanol(ate) compounds usable in accordance with the invention are the structures (Ia), (Ib), (Ic) and (Id)
  • M is selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and each R (R 1 to R 4 ) is independently selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl, optionally substituted C5- to C10-aryl, —OH and —O—(C1- to C10-alkyl).
  • the tetravalent metal M here is a shared part of multiple cages. It is known here to the person skilled in the art that the number of bonds to the metal M depends on the valency of the metal M.
  • the structural formulae (Ia) to (Ic) should be adjusted correspondingly if necessary.
  • composition according to the invention a mixture of the metal-siloxane-silanol(ate) compounds of formula (I), (Ia), (Ib) and (Ic) is used therein and/or in the preparation of the silylated polymers (SiP).
  • polynuclear metal-siloxane-silanol(ate) compound of formula (Id) in the composition according to the invention and/or in the preparation of the silylated polymers (SiP) may have hexacoordinated metal centres, enabling structures of formula (Id)
  • each M is independently selected from the group consisting of s- and p-block metals, d- and f-block transition metals, lanthanide and actinide metals and semimetals, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, 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 refers to the isolated cage structure, i.e. present in singular form, 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 may be encompassed by the structure (IV) and likewise by the structures (I) and (II)
  • X 4 is -M 3 L 1 ⁇ where 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 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, especially from the group consisting of metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc, N
  • Z 1 , Z 2 and Z 3 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;
  • R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of optionally substituted C1- to C20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionally substituted C5- to C10-aryl.
  • the invention further relates to the metal-siloxane-silanol(ate) compounds of the general structural formula (II) that are used for preparation of the silylated polymers according to the invention
  • X 4 is -M 3 L 1 ⁇
  • 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 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
  • 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), especially —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.
  • the silylated polymers (SiP) of the composition according to the invention may have been prepared by a catalysed reaction with heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) as a metal-siloxane-silanol(ate) compound and/or the composition may include the latter.
  • TiPOSS heptaisobutyl POSS-titanium(IV) ethoxide
  • TiPOSS represents the monovalent titanium-metallized silsesquioxane of the structural formula (IV) and can be used in an equivalent manner to “heptaisobutyl POSS-titanium(IV) ethoxide” for the purposes of the invention.
  • the metal-siloxane-silanol(ate) compound may be a mixture comprising structures (I), (Ia), (Ib), (Ic), (Id), (II), (IV), (IVb), (IVc).
  • the metal in the metal-siloxane-silanol(ate) compound is a titanium.
  • catalysts from the group of the metal-siloxane-silanol(ate) compounds are heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) and heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS).
  • TiPOSS heptaisobutyl POSS-titanium(IV) ethoxide
  • SnPOSS heptaisobutyl POSS-tin(IV) ethoxide
  • catalyst B is not selected from the group of the metal-siloxane-silanol(ate) compounds, it preferably comprises organometallic compounds. Particular preference is given to organotin, organobismuth, organozinc, organozirconium, organoaluminium or organotitanium compounds. Very particular preference is given to organotin or organotitanium compounds.
  • catalyst B may be 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) 2 TiO 2 in which R is, for example, isopropyl, n-butyl, isobutyl), such as isopropyl n-butyl titanate; titanium acetylacetonate chelates, such as diisopropoxybis(acetylacetonate) titanate, diisopropoxybis(ethylacetylacetonate) titanate, di-n-butyl
  • Catalyst B may preferably be selected from the group consisting of dibutyltin dilaurate (DBTL), tin(II) 2-ethylhexanoate (tin octoate), zinc(II) 2-ethylhexanoate, zinc(II) neodecanoate, bismuth(III) tris(2-ethylhexanoate), bismuth(III) tris(neodecanoate) or mixtures thereof.
  • DBTL dibutyltin dilaurate
  • tin(II) 2-ethylhexanoate tin octoate
  • zinc(II) 2-ethylhexanoate zinc(II) neodecanoate
  • bismuth(III) tris(2-ethylhexanoate) bismuth(III) tris(neodecanoate) or mixtures thereof.
  • Catalyst B is more preferably dibutyltin dilaurate (DBTL).
  • the catalysts are preferably present in a relative ratio between 1:10 and 10:1; catalysts A and B are further preferably present in a relative ratio between 1:8 and 8:1; catalysts A and B are especially preferably present in a relative ratio between 1:5 and 5:1; catalysts A and B are more especially preferably present in a relative ratio between 1:2 and 2:1, most preferably in a relative ratio of 0.9:1.1 to 1.1:0.9, based on percent by weight.
  • the total amount of catalyst, composed of at least one catalyst A and one catalyst B is between 5 and 30 000 ppm, further preferably between 15 and 20 000 ppm, more preferably between 20 and 15 000 ppm, most preferably between 20 and 10 000 ppm, based on the total weight of the composition.
  • silane-modified polymers are silane-modified, silane-functional or silane-terminated polymers that are also referred to interchangeably as SMP, STP or SiP.
  • SMP silane-modified polymer
  • STP silane-terminated polymers
  • SiP silane-terminated polymers
  • the definition includes polymers, polycondensates or polyadducts.
  • This also includes moisture-crosslinking polymers that can cure under the influence of water, either via addition or mixture constituents of or including water or by contacting with air humidity, preferably with additional use of a catalyst.
  • Silane-functional polymers are also referred to as hybrid polymers in general use and in accordance with the invention. These polymers can combine the curing chemistry of alkoxysilane groups with the chemistry of the polyols or polyurethanes. Alkoxysilane groups are known from silicone chemistry; the isocyanate-functional polymers, especially hydroxy-functional polymers, contribute at least parts of the polymer backbone of the hybrid polymer. Crosslinking (“curing”) takes place via the reactive silane end groups through ingress of air humidity, for example. The curing mechanism of these systems is preferably neutral.
  • Alkoxy refers to an alkyl group joined via an oxygen atom to the main carbon chain or the main skeleton of the compound.
  • SiP Silane-functional polymers
  • P polymer backbone
  • V silane-functional polymers
  • N especially denotes nitrogen.
  • O especially denotes oxygen, unless stated otherwise.
  • S especially denotes sulfur, unless stated otherwise.
  • P especially denotes phosphorus, unless stated otherwise.
  • C especially denotes carbon, unless stated otherwise.
  • H especially denotes hydrogen, unless stated otherwise.
  • Si especially denotes silicon, unless stated otherwise.
  • “Optionally substituted” means that hydrogen atoms in the corresponding group or in the corresponding radical may be replaced by substituents.
  • Substituents may especially be selected from the group consisting of C1- to C4-alkyl, methyl, ethyl, propyl, butyl, phenyl, benzyl, halogen, fluorine, chlorine, bromine, iodine, hydroxy, amino, alkylamino, dialkylamino, C1- to C4-alkoxy, phenoxy, benzyloxy, cyano, nitro, and thio.
  • a group is referred to as optionally substituted, it is possible for 0 to 50, especially 0 to 20, hydrogen atoms of the group to be replaced by substituents. If a group is substituted, at least one hydrogen atom is replaced by a substituent.
  • alkyl group means a saturated hydrocarbyl chain. Alkyl groups especially have the general formula —C n H 2n+1 .
  • C1- to C16-alkyl group especially denotes a saturated hydrocarbyl chain having 1 to 16 carbon atoms in the chain. Examples of C1- to C16-alkyl groups are methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, n-pentyl and ethylhexyl.
  • a “C1- to C8-alkyl group” especially denotes a saturated hydrocarbyl chain having 1 to 8 carbon atoms in the chain. Alkyl groups may especially also be substituted even if this is not stated specifically.
  • Straight-chain alkyl groups denote alkyl groups containing no branches. Examples of straight-chain alkyl groups are methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl.
  • Branched alkyl groups denote alkyl groups that are not straight-chain, i.e. in which the hydrocarbyl chain especially has a fork.
  • Examples of branched alkyl groups are isopropyl, isobutyl, sec-butyl, tert-butyl, sec-pentyl, 3-pentyl, 2-methylbutyl, isopentyl, 3-methylbut-2-yl, 2-methylbut-2-yl, neopentyl, ethylhexyl, and 2-ethylhexyl.
  • Alkenyl groups denote hydrocarbyl chains containing at least one double bond along the chain.
  • an alkenyl group having a double bond especially has the general formula —CnH2n ⁇ 1.
  • alkenyl groups may also have more than one double bond.
  • C2- to C16-alkenyl group especially denotes a hydrocarbyl chain having 2 to 16 carbon atoms in the chain.
  • the number of hydrogen atoms varies according to the number of double bonds in the alkenyl group. Examples of alkenyl groups are vinyl, allyl, 2-butenyl and 2-hexenyl.
  • Straight-chain alkenyl groups denote alkenyl groups containing no branches. Examples of straight-chain alkenyl groups are vinyl, allyl, n-2-butenyl and n-2-hexenyl.
  • Branched alkenyl groups denote alkenyl groups that are not straight-chain, i.e. in which the hydrocarbyl chain especially has a fork. Examples of branched alkenyl groups are 2-methyl-2-propenyl, 2-methyl-2-butenyl and 2-ethyl-2-pentenyl.
  • Aryl groups denote monocyclic (for example phenyl), bicyclic (for example indenyl, naphthalenyl, tetrahydronapthyl or tetrahydroindenyl) and tricyclic (for example fluorenyl, tetrahydrofluorenyl, anthracenyl or tetrahydroanthracenyl) ring systems in which the monocyclic ring system or at least one of the rings in a bicyclic or tricyclic ring system is aromatic. More particularly, a C4- to C14-aryl group denotes an aryl group having 4 to 14 carbon atoms. Aryl groups may especially also be substituted even if this is not stated specifically.
  • silylated polymers that are moisture-curing especially silylated polyethers and/or silylated polyurethane polymers (SPURs).
  • Silylated polymers or silane-terminated polymers that may be used in the composition according to the invention include at least two or more reactive silane groups, for example alkoxysilanes.
  • silylated polymers usable in accordance with the invention is that of oxyalkylene polymers having at least one reactive silane group at each end of the polymer molecule.
  • the backbone of the silane-terminated oxyalkylene polymer according to the invention has repeating units of the general formula (1):
  • R is a divalent organic group, preferably a straight or branched alkylene group including 1 to 14 carbon atoms, more preferably a straight or branched alkylene group including 2 to 4 carbon atoms, or mixtures thereof.
  • R is a divalent organic group, preferably a straight or branched alkylene group including 1 to 14 carbon atoms, more preferably a straight or branched alkylene group including 2 to 4 carbon atoms, or mixtures thereof.
  • polypropylene oxide backbones, polyethylene oxide backbones and copolyethylene oxide/copolypropylene oxide backbones are or mixtures thereof.
  • Other repeating units may include, but are not limited to, the following units:
  • the reactive silane groups in the silylated polymers (SiP) may be described by the following formula (2):
  • each R 2 is independently a C1- to C20-alkyl group, a C6- to C20-aryl group, a C7- to C20-aralkyl group or a mixture thereof,
  • At least one hydrolysable or hydroxy group is represented by G.
  • hydrolysable groups are those that can enter into hydrolysis reactions through the influence of water, for example from air humidity or through the addition of water or aqueous constituents, and can form silanols as a result thereof.
  • Hydrolysable groups may, for example, be alkoxy groups, and less commonly also —Cl. In a similar manner, these groups (or the silanols formed thereby) may react with OH or COOH groups on surfaces and form a composite.
  • siliconols 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 (R—O—) is bonded to the silicon atom (—Si—O—), where this negatively charged oxygen atom may also be chemically covalently bonded and/or coordinated to further compounds, for example metals.
  • isocyanate-reactive compounds are those that can react with an isocyanate. These compounds may have one or more NH, OH or SH functions.
  • the isocyanate-reactive compounds especially include the class of the hydroxy-functional compounds.
  • Polyols are hydroxy-functional compounds, especially hydroxy-functional polymers.
  • Suitable polyols for the preparation of polyurethane polymers are especially polyether polyols, polyester polyols and polycarbonate polyols, and mixtures of these polyols.
  • Polyethers are a class of polymers. They are long-chain compounds comprising at least two identical or different ether groups. According to the invention, polyethers also include those where the polymeric ether groups are interrupted by another group (for example by copolymerized/incorporated isocyanates or further polymer or oligomer units of a different monomer origin).
  • Suitable polyether polyols also called polyoxyalkylene polyols or oligoetherols, are especially those that are polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, oxetane, tetrahydrofuran or mixtures thereof, optionally polymerized with the aid of a starter molecule having two or more active hydrogen atoms, for example water, ammonia or compounds having multiple OH or NH groups, for example ethane-1,2-diol, propane-1,2- or -1,3-diol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanedi
  • polyoxyalkylene polyols having a low degree of unsaturation (measured in accordance with ASTM D-2849-69 and expressed in milliequivalents of unsaturation per gram of polyol (meq/g)), produced for example using so-called double metal cyanide complex catalysts (DMC catalysts), or polyoxyalkylene polyols having a relatively high degree of unsaturation, produced for example using anionic catalysts such as NaOH, KOH, CsOH or alkali metal alkoxides.
  • DMC catalysts double metal cyanide complex catalysts
  • anionic catalysts such as NaOH, KOH, CsOH or alkali metal alkoxides.
  • Polyoxyethylene polyols and polyoxypropylene polyols are particularly suitable, especially polyoxyethylene diols, polyoxypropylene diols, polyoxyethylene triols, and polyoxypropylene triols.
  • polyoxyalkylene diols or polyoxyalkylene triols having a degree of unsaturation lower than 0.02 meq/g and having a molecular weight within a range from 1000 g/mol to 30 000 g/mol, as are polyoxyethylene diols, polyoxyethylene triols, polyoxypropylene diols, and polyoxypropylene triols having a molecular weight of 200 to 20 000 g/mol.
  • polyoxypropylene polyoxyethylene polyols that are obtained for example when pure polyoxypropylene polyols, in particular polyoxypropylene diols and triols, are at the end of the polypropoxylation reaction further alkoxylated with ethylene oxide and thus have primary hydroxyl groups.
  • Preference in this case is given to polyoxypropylene polyoxyethylene diols and polyoxypropylene polyoxyethylene triols.
  • hydroxyl-terminated polybutadiene polyols for example those produced by polymerization of 1,3-butadiene and allyl alcohol or by oxidation of polybutadiene and also the hydrogenation products thereof.
  • styrene-acrylonitrile grafted polyether polyols such as those commercially available for example under the trade name Lupranol® from Elastogran GmbH, Germany.
  • Suitable polyester polyols include in particular polyesters that bear at least two hydroxyl groups and are produced by known processes, in particular polycondensation of hydroxycarboxylic acids or polycondensation of aliphatic and/or aromatic polycarboxylic acids with dihydric or polyhydric alcohols.
  • polyester polyols produced from dihydric to trihydric alcohols such as ethane-1,2-diol, diethylene glycol, propane-1,2-diol, dipropylene glycol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, neopentyl glycol, glycerol, 1,1,1-trimethylolpropane or mixtures of the abovementioned alcohols with organic dicarboxylic acids or the anhydrides or esters thereof, for example succinic acid, glutaric acid, adipic acid, trimethyladipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, dimer fatty acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, dimethyl terephthalate, hex
  • polyester diols in particular those produced from adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, dimer fatty acid, phthalic acid, isophthalic acid and terephthalic acid as the dicarboxylic acid or from lactones such as ⁇ -caprolactone and from ethylene glycol, diethylene glycol, neopentyl glycol, butane-1,4-diol, hexane-1,6-diol, dimer fatty acid diol, and cyclohexane-1,4-dimethanol as the dihydric alcohol.
  • Suitable polycarbonate polyols include in particular those obtainable by reaction for example of the abovementioned alcohols used to form the polyester polyols with dialkyl carbonates such as dimethyl carbonate, diaryl carbonates such as diphenyl carbonate, or phosgene.
  • Polycarbonate diols in particular amorphous polycarbonate diols, are particularly suitable.
  • polycarbonate diols or polyether polycarbonate diols may be obtainable via polymerization of propylene oxide with CO 2 .
  • poly(meth)acrylate polyols are poly(meth)acrylate polyols.
  • polyhydroxy-functional fats and oils for example natural fats and oils, in particular castor oil, or so-called oleochemical polyols obtained by chemical modification of natural fats and oils, the epoxy polyesters or epoxy polyethers obtained for example by epoxidation of unsaturated oils and subsequent ring opening with carboxylic acids or alcohols respectively, or polyols obtained by hydroformylation and hydrogenation of unsaturated oils.
  • polyols obtained from natural fats and oils by degradation processes such as alcoholysis or ozonolysis and subsequent chemical linking, for example by transesterification or dimerization, of the thus obtained degradation products or derivatives thereof.
  • Suitable breakdown products of natural fats and oils are in particular fatty acids and fatty alcohols and also fatty acid esters, in particular the methyl esters (FAME), which can be derivatized to hydroxy fatty acid esters, for example by hydroformylation and hydrogenation.
  • FAME methyl esters
  • polyhydrocarbon polyols also referred to as oligohydrocarbonols
  • polyhydroxy-functional ethylene-propylene, ethylene-butylene or ethylene-propylene-diene copolymers for example those produced by Kraton Polymers, USA
  • polyhydroxy-functional copolymers of dienes such as 1,3-butadiene or diene mixtures
  • vinyl monomers such as styrene, acrylonitrile or isobutylene
  • polyhydroxy-functional polybutadiene polyols for example those which are produced by copolymerization of 1,3-butadiene and allyl alcohol and which may also be hydrogenated.
  • polyhydroxy-functional acrylonitrile/butadiene copolymers such as those that can be produced for example from epoxides or amino alcohols and carboxyl-terminated acrylonitrile/butadiene copolymers that are commercially available under the Hypro® CTBN name from Emerald Performance Materials, LLC, USA.
  • These likewise particularly preferred polyols have an average molecular weight of 250 to 40 000 g/mol, especially of 1000 to 30 000 g/mol, and an average OH functionality in the range from 1.6 to 3.
  • 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.
  • di- or polyhydric alcohols for example ethane-1,2-diol, propane-1,2- and -1,3-diol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, cyclohexane-1,3- and -1,4-dimethanol, hydrogenated bisphenol A, dimeric fatty alcohols, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol, pentaerythr
  • NCO groups may react, for example, with alcohols to give urethanes or with amines to give urea derivatives.
  • the isocyanate-containing compounds of the invention may be described by the general formula (VI)
  • silylated polymers SiP
  • the synthesis is effected via a metal-siloxane-silanol(ate) compound-catalysed synthesis of an isocyanate-reactive compound, especially a hydroxy-functionalized polymer, and a di- or polyisocyanate compound (Iso).
  • an isocyanate-reactive compound especially a hydroxy-functionalized polymer
  • a di- or polyisocyanate compound Iso
  • the resultant isocyanate group-containing prepolymer is reacted with an aminosilane (AmSi) to give the silylated polymer (SiP) according to the invention.
  • AmSi aminosilane
  • Di- or polyisocyanates (Iso) used for the preparation of the polymer of the invention may be conventional isocyanates, especially di- or polyisocyanates of the general formula (VI)
  • suitable diisocyanates are hexamethylene 1,6-diisocyanate (HDI) or the trimer thereof (HDI trimer), methylene diphenyl isocyanate (MDI), especially 4,4′-methylene diphenyl isocyanate (4,4′-MDI), 2,4′-methylene diphenyl isocyanate (2,4′-MDI), 2,2′-methylene diphenyl isocyanate (2,2′-MDI), 4,4′-diisocyanatodicyclohexylmethane (H12MDI), 2-methylpentamethylene 1,5-diisocyanate, 2,2,4- and 2,4,4-trimethylhexamethylene 1,6-diisocyanate (TMDI), dodecamethylene 1,12-diisocyanate, lysine and lysine ester diisocyanate, cyclohexane 1,3-diisocyanate, cyclohexane 1,4-diisocyanate,
  • Aminosilanes refer to organosilanes wherein the organic radical has an amino group.
  • Primary aminosilanes refer to aminosilanes having a primary amino group, i.e. an NH2 group bonded to one organic radical.
  • Secondary aminosilanes refer to aminosilanes having a secondary amino group, i.e. an NH group bonded to two organic radicals.
  • the silylated polymer (SiP) according to the invention can be obtained by a second route.
  • This second synthesis route is referred to in accordance with the invention as “Iso-Si route” or “isocyanate route”.
  • This reaction can be effected in a stoichiometric ratio of the isocyanate groups to the functional end groups reactive toward isocyanate groups of 0.9:1.1 to 1.1:0.9, or with a slight excess of the functional end groups reactive toward isocyanate groups, for example at temperatures of 20° C. to 100° C., with additional use of at least one metal-siloxane-silanol(ate) compound as catalyst.
  • the isocyanatosilane (Iso-Si) is preferably selected from the group consisting of the following compounds of the general formula (VII):
  • the composition of the invention comprises two catalysts A and B, where A is heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) or heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS) and B is dibutyltin laurate (DBTL) or heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS) when A is not heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS).
  • A is heptaisobutyl POSS-titanium(IV) ethoxide
  • SnPOSS heptaisobutyl POSS-tin(IV) ethoxide
  • B is dibutyltin laurate (DBTL) or heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS)
  • the silylated polymer (SiP) is prepared by a synthesis of at least one isocyanate-reactive compound (component A) selected from the group of compounds having NH, OH or SH functions, and one or more compounds having at least one isocyanate group, selected from the group of isocyanates (Iso) and/or isocyanatosilanes (Iso-Si), catalysed by at least one mononuclear metal-siloxane-silanol(ate) compound.
  • component A selected from the group of compounds having NH, OH or SH functions
  • one or more compounds having at least one isocyanate group selected from the group of isocyanates (Iso) and/or isocyanatosilanes (Iso-Si), catalysed by at least one mononuclear metal-siloxane-silanol(ate) compound.
  • the silylated polymer (SiP) is prepared by a synthesis of at least one hydroxy-functionalized polymer (component A) selected from the group of polypropylene diols, polyester polyols, or mixtures thereof, and one or more compounds having at least one isocyanate group, selected from the group of 4,4′-methylene diphenyl isocyanate (4,4′-MDI), isophorone diisocyanate (IPDI) or mixtures thereof and/or 3-(triethoxysilyl)methyl isocyanate, 3-(triethoxysilyl)propyl isocyanate, or mixtures thereof, catalysed by at least one mononuclear single-cage metal-siloxane-silanol(ate) compound.
  • component A selected from the group of polypropylene diols, polyester polyols, or mixtures thereof
  • one or more compounds having at least one isocyanate group selected from the group of 4,4′-methylene dipheny
  • the silylated polymer (SiP) is prepared by a synthesis of at least one hydroxy-functionalized polymer (component A) selected from the group of polypropylene diols, polyester polyols, or mixtures thereof, and one or more compounds having at least one isocyanate group, selected from the group of 4,4′-methylene diphenyl isocyanate (4,4′-MDI), isophorone diisocyanate (IPDI) or mixtures thereof and/or 3-(triethoxysilyl)methyl isocyanate, 3-(triethoxysilyl)propyl isocyanate, or mixtures thereof, catalysed by at least one mononuclear titanium-siloxane-silanol(ate) compound, especially by heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS).
  • component A selected from the group of polypropylene diols, polyester polyols, or mixtures thereof
  • the silylated polymer (SiP) is prepared by reaction with an aminosilane (AmSi) selected from the group of N-[3-(triethoxysilyl)methyl]butylamine, N-[3-(triethoxysilyl)propyl]butylamine, N-(3-triethoxysilylpropyl)aminosuccinic acid diethyl ester or a mixture thereof.
  • AmSi aminosilane
  • the silylated polymer (SiP) of the composition according to the invention is prepared by a heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS)-catalysed synthesis of a component A selected from the group of polypropylene diols, polyester polyols, or mixtures thereof, with a component B selected from the group of 3-(triethoxysilyl)methyl isocyanate, 3-(triethoxysilyl)propyl isocyanate or mixtures thereof.
  • a component A selected from the group of polypropylene diols, polyester polyols, or mixtures thereof
  • component B selected from the group of 3-(triethoxysilyl)methyl isocyanate, 3-(triethoxysilyl)propyl isocyanate or mixtures thereof.
  • the silylated polymer (SiP) of the composition according to the invention is prepared by a heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS)-catalysed synthesis of a component A selected from the group of polypropylene diols, polyester polyols, or mixtures thereof, with a component B selected from the group of 4,4′-methylene diphenyl isocyanate (4,4′-MDI), isophorone diisocyanate (IPDI) or mixtures thereof, followed by silanization with an aminosilane selected from the group of N-[3-(triethoxysilyl)methyl]butylamine, N-[3-(triethoxysilyl)propyl]butylamine, N-(3-triethoxysilylpropyl)aminosuccinic acid diethyl ester or a mixture thereof.
  • a component A selected from the group of polypropylene diol
  • all the above combinations include heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) as catalyst in the synthesis of the silylated polymer (SiP).
  • all the above combinations in the embodiments rather than heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) in the synthesis of the silylated polymer (SiP), include heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS) or a mixture of the two catalysts.
  • heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) only is present as catalyst in the synthesis of the silylated polymer (SiP).
  • composition of the invention in all the above combinations includes a further catalyst selected from metal-siloxane-silanol(ate) compounds, especially heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) or heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS), dibutyltin dilaurate (DBTL) or mixtures thereof.
  • a further catalyst selected from metal-siloxane-silanol(ate) compounds, especially heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) or heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS), dibutyltin dilaurate (DBTL) or mixtures thereof.
  • all the above combinations of the composition of the invention include dibutyltin dilaurate (DBTL) as second catalyst.
  • DBTL dibutyltin dilaurate
  • this comprises additives from the group comprising one or more fillers selected from the group of inorganic and organic fillers, especially natural, ground or precipitated calcium carbonates optionally coated with fatty acids, especially stearic acid, barite (heavy spar), talcs, quartz flours, quartz sand, dolomites, wollastonites, kaolins, calcined kaolins, mica (potassium aluminium silicate), molecular sieves, aluminium oxides, aluminium hydroxides, magnesium hydroxide, silicas including finely divided silicas from pyrolysis processes, industrially produced carbon blacks, graphite, metal powders such as aluminium, copper, iron, silver or steel, PVC powders or hollow beads, one or more adhesion promoters from the group of the silanes, especially aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, N-(2-amin
  • 3-glycidoxypropyltrimethoxysilane 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-N′-[3-(trimethoxysilyl)propyl]ethylenediamine, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane and the corresponding silanes having ethoxy groups in place of the methoxy groups, and oligomeric forms of these silanes, one or more moisture scavengers from the group of silanes, especially tetraethoxysilane, vinyltrimethoxy- or vinyltriethoxysilane or organoalkoxysilanes having a functional group in the a position to the silane group, especially N-(methyldimethoxysilylmethyl)-O-methyl carba
  • the composition of the invention additionally includes a water scavenger, preferably a vinylalkoxysilane, more preferably vinyltrimethoxysilane (VTMO).
  • VTMO vinyltrimethoxysilane
  • a preferred process for producing the composition comprises the following steps:
  • either the entirety of the isocyanate-containing compound (component B) or else the entirety of the isocyanate-reactive compound, especially the hydroxy-functionalized polymer (component A) is preferably first initially charged, then the respective other component A or B is added, followed by addition of at least one metal-siloxane-silanol(ate) compound, and the components are left to react with one another.
  • the end product is optionally then prepared from the resulting intermediate by reaction with the aminosilane (AmSi). If one or more components are used in addition, these may in principle be added to the reaction mixture at any time.
  • the process according to the invention is preferably conducted at temperatures of at least 0° C., more preferably at least 20° C., and preferably at most 150° C., especially at most 80° C.
  • the process according to the invention is preferably conducted with exclusion of (air) humidity and at the pressure of the surrounding atmosphere, i.e. about 900 to 1100 hPa.
  • the process according to the invention can be effected continuously, for example in a tubular reactor or tube reactor having multiple metering sites in parallel or else in series, or batchwise, for example in a conventional reaction tank with stirrer system.
  • a reaction vessel was initially charged with 50 g of 3-aminopropyltriethoxysilane, and 38.9 g of diethyl maleate was added at room temperature within 30 min. The mixture was stirred at 80° C. for a further 12 h. 87 g of N-(3-triethoxysilylpropyl)aminosuccinic acid diethyl ester was obtained as a water-clear liquid.
  • step 1 of reaction sequence A1 was repeated using 0.625 g of a 1% DBTL solution in DINCH as catalyst.
  • the subsequent steps were conducted analogously to the manner described above.
  • a triethoxysilane-terminated polymer ESTP 2 with viscosity of 28 000 mPa ⁇ s was obtained.
  • a reaction vessel was initially charged with 51 g of 3-aminopropyltrimethoxysilane, and 49 g of diethyl maleate was added at room temperature within 30 min. The mixture was stirred at room temperature for a further 2 h. 97.8 g of N-(3-trimethoxysilylpropyl)aminosuccinic acid diethyl ester was obtained as a water-clear liquid.
  • step 1 of reaction sequence A1 was repeated using 0.625 g of a 1% DBTL solution in DINCH as catalyst.
  • the subsequent steps were conducted analogously to the manner described above.
  • a reaction vessel under a nitrogen atmosphere was initially charged with 250 g of PolyU L 12000, and 6.25 g of a 20% TiPOSS solution in DINCH was added while stirring. Subsequently, 10.98 g of 3-(triethoxysilyl)propyl isocyanate was added dropwise within 30 min. The reaction was ended after 2 h; it was no longer possible to detect any free isocyanate. The viscosity of the resultant triethoxysilane-terminated polymer was 7300 mPa ⁇ s. Finally, 2% VTEO was added.
  • a reaction vessel under a nitrogen atmosphere was initially charged with 250 g of PolyU L 12000, and 6.25 g of a 20% DBTL solution in DINCH was added while stirring. Subsequently, 10.98 g of 3-(triethoxysilyl)propyl isocyanate was added dropwise within 30 min. The reaction was ended after 2 h; it was no longer possible to detect any free isocyanate. The viscosity of the resultant triethoxysilane-terminated polymer was 7700 mPa ⁇ s. Finally, 2% VTEO was added.
  • a reaction vessel under a nitrogen atmosphere was initially charged with 200 g of PolyU L 12000, and 5 g of a 20% DBTL solution in DINCH was added while stirring. Subsequently, 7.31 g of 3-(trimethoxysilyl)propyl isocyanate was added dropwise within 30 min. The reaction was ended after 2 h; it was no longer possible to detect any free isocyanate. The viscosity of the resultant trimethoxysilane-terminated polymer was 8900 mPa ⁇ s. Finally, 2% VTMO was added.
  • a reaction vessel under a nitrogen atmosphere was initially charged with 200 g of PolyU L 12000, and 5 g of a 20% DBTL solution in DINCH was added while stirring. Subsequently, 7.31 g of 3-(trimethoxysilyl)propyl isocyanate was added dropwise within 30 min. The reaction was ended after 2 h; it was no longer possible to detect any free isocyanate. The viscosity of the resultant trimethoxysilane-terminated polymer was 9100 mPa ⁇ s. Finally, 2% VTMO was added.
  • the curing characteristics of the silane-terminated polymers were tested by determining the fibre time TT and tack-free time TFT on samples of thickness 2 mm at 23° C./50% RH.
  • the samples were made up without catalyst and with TiPOSS, DBTL or with a combination of TiPOSS and DBTL and cured.
  • the triethoxysilane-terminated polymers have been obtained via the reaction of MDI prepolymer with N-(3-triethoxysilylpropyl)aminosuccinic acid diethyl ester (ESTP 1, TiPOSS-catalysed and ESTP 2, DBTL-catalysed) and via the reaction of triethoxysilylpropyl isocyanate with polyol (ESTP 3, TiPOSS-catalysed and ESTP 4, DBTL-catalysed).
  • test series 3 The curing outcome from column 3, test series 3, and column 4, test series 2, corroborates this result since there is likewise a catalyst mixture in this case of TiPOSS and DBTL.
  • the corresponding triethoxysilane-terminated polymers that cure in a particularly accelerated manner by virtue of the catalyst mixture of TiPOSS and DBTL are marked.
  • test series 1 in the case of the trimethoxysilane-terminated polymers (columns 5 to 8), that the polymers that have been prepared from the silylation using TiPOSS are much more stable with respect to curing with air humidity (test series 1, columns 5 and 7).
  • the present invention relates to the composition and to the process for preparing polyurethane prepolymers and polyurethane systems based on polyols, di- or polyisocyanates and a TiPOSS-based catalyst.
  • TiPOSS-based catalysts that are preferred in accordance with the invention are those disclosed in EP 2 989 155 B1 and EP 2 796 493 A1. The disclosure of these documents is fully incorporated with regard to the catalysts. Particular preference is given to the catalysts (metallosilsesquioxane) according to embodiment 5 of EP 2 989 155 B1.
  • TiPOSS heptaisobutyl POSS-titanium(IV) ethoxide
  • the studies have been conducted under the assumption that a complete stoichiometric reaction (index 100) can take place between isocyanate and polyol. In principle, the studies are also applicable to the preparation of prepolymers.
  • the polyol A component consisted of a polypropylene diol and the TiPOSS catalyst in the form of a 20% solution in diisononyl phthalate (DINP).
  • DINP diisononyl phthalate
  • the amount of catalyst was 0.2 percent by weight in each case (neglecting the amount of solvent).
  • the molecular weight was additionally varied from low (MW ⁇ 2000) to high (MW ⁇ 18 000), since it can be assumed that the reactivity of polypropylene polyols that are of limited reactivity in any case will decrease further with rising molecular weight, and hence differences in reactivity will be particularly readily observable.
  • the polypropylene polyols tested were accordingly those with MW ⁇ 2000 (Rokopol D2002, PCC Rokita), MW ⁇ 8000 (Rokopol LDB 8000), MW ⁇ 12 000 (Rokopol LDB 12000) and MW ⁇ 18 000 (Rokopol LDB 18000).
  • the crosslinker components used were the isocyanates P-MDI (Voranate M230, Dow), IPDI (Wanate IPDI, DKSH) and HDI trimer isocyanurates (Vestanat HT2500/100).
  • the reaction between polyol A and isocyanate B component was effected by stirring the two components at 1000 rpm with a conventional propeller stirrer for 10 s. After the stirring process had ended, the resultant reaction mixture was cast into slabs of thickness ⁇ 6 mm (10 g). The curing characteristics were determined from the cream time, fibre time and tack-free time.
  • the use of the TiPOSS catalyst is expected to lead both to a cost benefit over tin catalysts and to a product benefit.
  • the speed of fibre formation and curing in silane-terminated polyurethanes was determined on 6 mm SPUR slabs that had been produced by mixing the silane-terminated polyurethanes with 0.2 percent by weight each of TiPOSS and DBTL (each in solution, 20% in DINP). The mixing was effected with exclusion of air in an argon inert gas atmosphere with a conventional propeller stirrer. The mixed material was cured at 23° C./50% RH.
  • DINP diisononyl phthalate
  • a corresponding identical polyol A component was prepared using DBTDL.
  • the amount of catalyst was 0.2 percent by weight in each case (neglecting the DINP solvent).
  • the crosslinking component used was the isocyanate P-MDI (Voranate M230).
  • the reaction between polyol A and isocyanate B component was effected by stirring the two components at 2500 rpm with a conventional propeller stirrer for 10 s. The reaction was stoichiometric. After the stirring process had ended, the reaction mixture obtained (20 g) was poured into cups. The curing characteristics were determined from the cream time and tack-free time.
  • the polyol A component consisted of a standard polyester polyol based on Desmophen 2200 B, an amine catalyst (N,N-dimethylpiperazine and N,N-dimethylhexadecylamine), cell stabilizers, water and the TiPOSS catalyst, in the form of a 20% solution in DINP.
  • an amine catalyst N,N-dimethylpiperazine and N,N-dimethylhexadecylamine
  • cell stabilizers cell stabilizers
  • water and the TiPOSS catalyst in the form of a 20% solution in DINP.
  • a corresponding identical polyol A component was prepared using tin octoate.
  • the amount of TiPOSS and tin octoate catalyst was 0.03 percent by weight in each case.
  • the crosslinking components used were the isocyanate Desmodur T65 and a prepolymer having an NCO content of about 12%.
  • the reaction was effected in a stoichiometric ratio (index 100).
  • the reaction between polyol A and isocyanate B components was effected by stirring the two components at 1000 rpm with a Visco Jet stirrer unit for 10 s. After the stirring process had ended, the resultant reaction mixture ( ⁇ 400 g) was poured into a 2 L wooden box, and the curing characteristics were determined from the cream time and tack-free time.
  • prepolymers obtained from the reaction of KOH-based polyols and aliphatic and aromatic isocyanates can be brought about with considerably smaller amounts of TiPOSS catalyst (1 ⁇ 5 to 1/10) and/or a lower temperature ( ⁇ 80° C.) and/or a shortened reaction time. Since the formation of by-products in this preparation leads to an unwanted increase in viscosity, a distinct improvement in the reaction regime and product quality can thus be assumed.
  • TiPOSS as catalyst increases the curing rate in 2-component polyurethane clear encapsulating systems and PU varnishes.
  • the increase in molecular weight distinctly improves the mechanical properties of the varnishes and encapsulating compounds.
  • 2-component polyurethane systems for the FIPFG process based on TiPOSS-catalysed curing is particularly advantageous since the curing process is accelerated by the higher reactivity of TiPOSS compared to DBTL.
  • Polyurethane products can additionally be produced without tin compounds that are harmful to health, which is particularly important for the production of sealant materials in the medical sector, kitchen applications, etc.
  • the curing of 1-component isocyanate-terminated prepolymers can be accelerated by the use of TiPOSS. It is possible to dispense with the use of tin compounds that are harmful to health. This is of particular relevance when these prepolymers are used as adhesives for customary floor coverings, since it is thus possible to avoid possible contamination, even if only by small amounts of tin, via the skin of the foot.
  • DINP Diisononyl phthalate
  • Dibutyltin dilaurate (DBTDL or DBTL)
  • Tin(II) 2-ethylhexanoate Tin octoate
  • DMC Dimethylcyclosiloxane
  • FIPFG foam in place foam gaskets—sealant foams

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