Stable modified polymer polyol dispersions

Abstract

The present disclosure relates to new nitrogen-containing alkoxysilane-capped polyether polyols which are useful as dispersants and stabilizers for modified polymer polyol dispersions. There are also disclosed the stable modified polymer polyol dispersions of polymeric particles in a liquid polyol mixture and their method of preparation; and polyurethane materials prepared using the stabilized modified polymer polyol dispersions of the invention.

Description

Stable modified polymer polyol dispersions

[0001] .. This application claims the benefit of European Patent Application EP23383022.3 filed on October 4, 2023.

[0002] .. The present disclosure relates to new compounds useful as dispersants and stabilizers for modified polymer polyol dispersions. BACKGROUND

[0003] .. A variety of modified polymer polyols are used as raw materials for manufacturing flexible polyurethane foam and other polyurethane products. They have a continuous phase made up of one or more compounds having multiple hydroxyl groups (“base polyol”) into which another polymer is dispersed in the form of particles.

[0004] .. Thus, example of modified polymer polyols are: - Poly Harnststoff Dispersion (PHD) polyols which are modified polymer polyols which comprise in a dispersed form a polyurea which is the polycondensation reaction product of an amine or polyamine with a polyfunctional isocyanate; - Graft polyether polyols which are synthesised by in situ radical polymerisation of vinylic monomers in liquid polyethers, by batch, semi-continuous or continuous process wherein the vinylic monomer is generally selected from acrylonitrile, styrene, alpha-methyl styrene, methylmethacrylate, hydroxyalkyl acrylates and methacrylates, vinyl chloride and others; - Polyisocyanate Polyaddition (PIPA) polymer polyols which are dispersions of polyurethane and / or polyurethane-urea particles in a liquid polyether polyol, resulting from the polymerization of an alkylene glycol, and alkanolamine or an olphosphine with an organic polyisocyanate in the presence of a polyol; - and most recently described, polymer polyols comprising a polyether carbonate polyol as the base polyol, the polyether carbonate polyols (POPC) being obtainable by a process comprising copolymerizing one or more H-functional initiator substances, one or more alkylene oxides and carbon dioxide in the presence of a double metal cyanide catalyst (DMC).

[0005] .. Herein the term alkanolamine, also known as olamine, means an organic compound containing at least one hydroxyl group and at least one amino group, whether primary, secondary or tertiary amino group.

[0006] .. Herein the term olphosphine means an organic compound having at least onehydroxyl group and at least one phosphine group. While olphosphines having hydroxyl and phosphine groups attached to an aliphatic group are most suitable in the practice of the present invention, olphosphines having hydroxyl and phosphine groups attached to alicyclic, aromatic or heterocyclic nuclei or combination thereof with each other and / or aliphatic groups can also be used. Whether active hydrogens in the olphosphine are derived from both hydroxyl and phosphine groups having such hydrogens or only by hydroxyl groups, all these active hydrogens may be reactive with respect to isocyanate groups. Hydroxyalkylphosphine, hydroxyalkylphosphonium salts and hydroxyalkylphosphine oxide, and their derivatives are particular examples of olphosphines useful in the preparation of PIPA polyols.

[0007] .. In our previous patent application WO2019008140, were disclosed new modified polymer polyols comprising at least one base polyol and a stable dispersion of polymeric particles in the at least one base polyol, the modified polymer polyol being obtainable by a process comprising the preparation of the polymeric particles in the presence of the at least one base polyol by a polycondensation reaction of i. at least one compound bearing at least one basic-nitrogen atom characterized by the presence in the molecule of at least one hydrogen atom attached to a nitrogen atom; with ii. at least one compound bearing a phosphorus atom selected from the group consisting of ii1. a compound bearing a phosphorus atom which is selected from the group consisting of at least one hydroxyalkylphosphine, at least one hydroxyalkylphosphonium salt, at least one hydroxyalkylphosphine oxide and a combination thereof; or ii2. a condensation product from the mixture of compounds b.1) and at least one compound bearing at least one basic nitrogen atom.

[0008] .. Regarding the base polyol used in the preparation of these modified polymer polyols, they may be either polyether polyols, polyether carbonate polyols (POPC) or polyester polyols. Polyether polyols are manufactured commercially by polymerizing propylene oxide and or ethylene oxide in the presence of hydroxyl or amino group- containing initiators and basic catalysts. Polyester polyols are made by the polycondensation reaction of multifunctional carboxylic acids and polyhydroxyl compounds.

[0009] .. Among the polyether polyols, it is possible to differentiate between reactive and non-reactive polyether polyols. Reactive polyols are ethylene oxide (EO) capped polyether polyols, having a content of polyethylene oxide terminal blocks of 5-20 wt%; so they bear a high content of primary hydroxyl group (higher than 30%); whereas non-reactive polyols are propylene oxide (PO) capped polyether polyols, bearingmainly secondary hydroxyl groups. Secondary hydroxyl groups are less reactive than primary hydroxyl groups.

[0010] .. Different approaches to stabilise modified polymer polyols, have been proposed. Thus, introduction during the polymerisation a non-aqueous dispersant (NAD) stabiliser has been one of the proposed solutions. Stabilisation of polymeric dispersions in organic media is based on the principles of steric stabilisation, which is assured by the presence of nonaqueous dispersants (NAD) stabilisers. Thus, for example, in the case of graft polyether polyols, the NAD comprises in the same chemical structure a segment with a strong affinity for the carbocatenary vinylic polymer and a second segment with a strong affinity for the liquid polyether. The NAD is linked on the surface of solid polymeric particles with the polymeric carbocatenary segment, the polyetheric chains at the exterior part of the polymeric particles situated in the continuous polyetheric media, forming a steric hinderance which prevents the agglomeration of polymer particles.

[0011] .. It is known in the art that PIPA and PHD polymer polyols prepared using polyether polyols containing mainly secondary hydroxyl groups led to the formation of polymer particles that are not stable in the base polyol.

[0012] .. Different examples of NAD-stabilisers are known in the art, nevertheless, in view of the new developments in modified polymeric polyols and the different approaches and their different chemical and physical properties, currently there exists a need for new stabilisers for modified polymer polyols comprising at least one base polyol and a stable dispersion of polymeric particles in the at least one base polyol. More particularly there exists a need to provide new stabilisers for modified polymer polyol dispersions comprising at least one base polyol and a stable dispersion of polymeric particles in the at least one base polyol, wherein the base polyol is reactive or non-reactive polyether polyol.

[0013] .. EP3838962 discloses alcoxysilane-capped polyether polyols having from 1 to 8 hydroxyl groups per molecule and from 1 to 2 alcoxysilane groups per molecule and its use in the preparation of modified polymer polyol dispersions. SUMMARY

[0014] .. It has now been found that stable modified polymer polyol dispersions may be prepared by polymerising one or more polymeric particle precursor in the presence of a liquid polyol mixture which comprises at least one base polyol and at least one nitrogen-containing alkoxysilane-capped polyether polyol as described inthe nitrogen-containing alkoxysilane-capped polyether polyol section below and in the claims.

[0015] .. The resulting modified polymer polyol dispersion shows an improvement in its stability when compared with those modified polymer dispersions prepared in absence of the at least one nitrogen-containing alkoxysilane-capped polyether polyol, i.e. the modified polymer polyol dispersion does not settle out during storage for a longer period of time, or at least will remain in dispersion during mixing with other foam forming ingredients.

[0016] .. The new nitrogen-containing alkoxysilane-capped polyether polyols herein disclosed are useful for stabilize modified polymer polyols obtained using either a reactive polyether polyol or a non-reactive polyether polyol as the base polyol. Thus, the use of the nitrogen-containing alkoxysilane-capped polyether polyol in the liquid polyol mixture, allows to use a non-reactive base polyol for the preparation of the stable modified polymer polyol dispersions, including PIPA polymer polyol dispersions and PHD polymer polyol dispersions. Therefore, in accordance with an aspect of the present disclosure, there are provided new nitrogen-containing alkoxysilane-capped polyether polyols herein disclosed are useful for stabilize modified polymer polyols obtained using either a reactive polyether polyol or a non- reactive polyether polyol as the base polyol.

[0017] .. The new nitrogen-containing alkoxysilane-capped polyether polyols according to the present disclosure, work as non-aqueous dispersants (NAD) for modified polymer polyol dispersions and have the advantage that they are easily prepared under mild reaction conditions. Thus, the new nitrogen-containing alkoxysilane-capped polyether polyols are suitable for use as NAD stabilizers in the preparation of modified polymer polyol dispersions.

[0018] .. The new nitrogen-containing alkoxysilane-capped polyether polyols are obtainable by a process comprising: a) capping from 1 to 2 of the terminal hydroxyl groups of a polyether polyol having a functionality from 2 to 10 and a weight-average molecular weight from 2000 to 25000, determined according to the method identified in the specification, with a capping agent which is a compound having at least one alkoxysilane terminal group and at least one hydroxyl-reactive group selected from an isocyanate group, an anhydride group, and an oxirane group; wherein the reaction of the capping agent with the polyether polyol is carried out in a molar ratio from 0.05 to 2.0 mole of capping agent per mole of polyether polyol; to obtain an intermediate resulting product; b) reacting the intermediate resulting product in a) with at least one compoundcomprising an amino or -NHCONH2group and at least one alkoxysilane terminal group; to obtain the nitrogen-containing alkoxysilane-capped polyether polyol.

[0019] .. Therefore, a second aspect of the present invention relates to a method of preparation of a nitrogen-containing alkoxysilane-capped polyether polyol having from 1 to 8 hydroxyl groups per molecule and from 1 to 2 nitrogen-containing alkoxysilane-groups per molecule, wherein the method comprises: a) capping from 1 to 2 of the terminal hydroxyl groups of a polyether polyol having a functionality from 2 to 10 and a weight-average molecular weight from 2000 to 25000, determined according to the method identified in the specification, with a capping agent which is a compound having at least one alkoxysilane terminal group and at least one hydroxyl-reactive group selected from an isocyanate group, an anhydride group, and an oxirane group; wherein the reaction of the capping agent with the polyether polyol is carried out in a molar ratio from 0.05 to 2.0 mole, preferably from 0.2 to 1.8 mole, more preferably from 0.5 to 1.5 mole, being particularly preferably from 0.8 to 1.2 mole of capping agent per mole of polyether polyol; to obtain an intermediate resulting product; b) reacting the intermediate resulting product in a) with at least one compound comprising an amino or -NHCONH2group and at least one alkoxysilane terminal group; to obtain the nitrogen-containing alkoxysilane-capped polyether polyol.

[0020] .. The nitrogen-containing alkoxysilane-capped polyether polyols according to the present disclosure are useful as dispersants and stabilizers of PHD polyols, PIPA polyols, and those modified polymer polyols prepared starting from a mixture of hydroxyalkylphosphine and its derivatives (including salts, oxide and hemiacetals) as polymeric particle precursors as disclosed in WO2019008140. Therefore, a third aspect of the invention refers to the use of the nitrogen-containing alkoxysilane- capped polyether polyol of the first aspect of the invention and related embodiments, in the preparation of modified polymer polyol dispersions, more particularly as stabilizers and dispersants of modified polymer polyol dispersions.

[0021] .. A fourth aspect of the present invention relates to a method for the preparation of modified polymer polyol dispersions, wherein the method comprises the preparation of polymeric particles in the presence of a liquid polyol mixture which comprises at least one base polyol and at least one nitrogen-containing alkoxysilane- capped polyether polyol as defined in the first aspect of the invention and related embodiments.

[0022] .. A fifth aspect of the present invention refers to stable modified polymer polyol dispersions of polymeric particles in a liquid polyol mixture, the stable modified polymer polyol dispersions are obtainable by the process as defined in the fourthaspect of the invention and related embodiments.

[0023] .. Therefore, the stable modified polymer polyols according to the present invention comprise a stable dispersion of polymeric particles in a liquid polyol mixture comprising at least one base polyol and at least one nitrogen-containing alkoxysilane- capped polyether polyol as defined in the first aspect of the invention and related embodiments.

[0024] .. In a sixth aspect of the present disclosure, it is provided a process for preparing a polyurethane material wherein at least one polyisocyanate is reacted with an isocyanate-reactive component which comprises at least one stabilized modified polymer polyol dispersion as described in the fifth aspect of the invention and related embodiments, the reaction optionally being carried out in the presence of water and additives such as at least one blowing agent, at least one catalyst and tensioactive products.

[0025] .. A seventh aspect of the present disclosure refers to a polyurethane material obtainable by the process as defined in the sixth aspect of the invention and related embodiments.

[0026] .. The eight aspect of the present disclosure refers to an article of manufacture comprising the polyurethane material as defined in the seventh aspect of the invention and related embodiments.

[0027] .. The stable modified polymeric polyols of the present disclosure are useful for the preparation of polyurethane materials such as polyurethane foams, adhesives, elastomers, sealants and coatings; being preferred those polyurethane materials with flame retardant properties due to a high content of P and N of the dispersed polymeric particles.

[0028] .. In accordance with some embodiments, optionally in combination with one or more features of the various embodiments described above or below, the nitrogen- containing alkoxysilane-capped polyether polyols having from 1 to 8 hydroxyl groups per molecule and from 1 to 2 nitrogen-containing alkoxysilane groups per molecule are obtainable by a process comprising: A) capping from 1 to 2 of the terminal hydroxyl groups of a polyether polyol having a functionality from 2 to 10 and a weight-average molecular weight from 2000 to 25000, determined according to the method identified in the specification, with a capping agent which is a compound having at least one alkoxysilane terminal groupand at least one hydroxyl-reactive group selected from an isocyanate group, an anhydride group, and an oxirane group; wherein the reaction of the capping agent with the polyether polyol is carried out in a molar ratio from 0.05 to 2.0 mole, preferably from 0.2 to 1.8 mole, more preferably from 0.5 to 1.5 mole, being particularly preferably from 0.8 to 1.2 mole of capping agent per mole of polyether polyol; to obtain an intermediate resulting product; b) reacting the intermediate resulting product in a) with at least one compound comprising an amino or -NHCONH2group and at least one alkoxysilane terminal group, to obtain the nitrogen-containing alkoxysilane-capped polyether polyol; wherein the capping agent is a compound of formula (I):wherein R1, R2and R3are each independently selected from linear or branched (C1-C6)alkyl radical, linear or branched (C1-C6)alkoxyl radical and tri(C1-C3)alkylsilyloxyl radical; with the proviso that at least one of R1, R2or R3is a (C1-C6)alkoxyl radical; and wherein A is a radical selected from the group consisting of (II), (III), (IV), (V) and (VI)wherein the asterisk means the point of attachment to the Si atom in formula (I);m, n, p, r, t and w are independently an integer selected from 1 to 6; q, s and v are independently an integer selected from 1 to 4; R4is a radical selected from -NCO,wherein the asterisk indicates the point of attachment to the rest of the group; X is selected from -O- and -N(R5)-; wherein R5is a radical selected from H, linear or branched (C1-C6)alkyl,wherein the asterisk indicates the point of attachment to the N atom; x and z are independently an integer selected from 1 to 6; and R8, R9and R10are each independently selected from linear or branched (C1-C6)alkyl radical, linear or branched (C1-C6)alkoxyl radical and tri(C1-C3)alkylsilyloxyl radical; with the proviso that at least one of R8, R9or R10is a (C1-C6)alkoxyl radical or a tri(C1-C3)alkylsilyloxyl radical; wherein the reaction of the at least one polyether polyol with the compound of formula (I) is carried out in a molar ratio from 0.05 to 2.0 mole of compound of formula (I) per mole of polyether polyol; the at least one compound comprising an amino or -NHCONH2group and at least one alkoxysilane terminal group is a compound of formula (Ia)wherein R1’, R2’ and R3’ are each independently selected from linear or branched (C1-C6)alkyl radical, linear or branched (C1-C6)alkoxyl radical, and tri(C1-C3)alkylsilyloxyl radical;with the proviso that at least one of R1’, R2’ or R3’ is a (C1-C6)alkoxyl radical; and wherein A’ is selected from -(C1-C6)alkylNH2, -(C1-C6)alkylNH-(C1-C6)alkylNH2, -(C1-C6)alkylNH-(C1-C6)alkylNH-(C1-C6)alkylNH2, -(C1-C6)alkyl-NH-CO-NH2, -(C1-C6)a lkylNH-(C1-C6)alkylNH-CO-NH2, and -(C1-C6)alkylNH-(C1-C6)alkylNH-(C1-C6)alkylNH- CO-NH2.

[0029] .. In accordance with some embodiments, optionally in combination with one or more features of the various embodiments described above or below, thefunctional group reactable with the hydroxyl groups on the polyether polyol, being the terminal functional group reactable with the hydroxyl groups selected from -NCO, an anhydride group, and oxirane.

[0032] .. In accordance with certain embodiments, optionally in combination with one or more features of the various embodiments described above or below, the compound of formula (I) is selected from those wherein radical A is selected from the group consisting of those compounds of formula (II), (III), (IV), (V) and (VI)wherein the asterisk means the point of attachment to the Si atom in formula (I); m, n, p, r, t and w are independently an integer selected from 1 to 6; preferably 1, 2, 3, 4, 5 or 6; q, s and v are independently an integer selected from 1 to 4; preferably 1, 2, 3, or 4; R4 is a radical selected from -NCO,wherein the asterisk indicates the point of attachment to the rest of the group; X is selected from -O- and -N(R5)-; wherein R5 is a radical selected from H, linear or branched (C1-C6)alkyl,wherein the asterisk indicates the point of attachment to the N atom; x and z are independently an integer selected from 1 to 6; preferably 1, 2, 3, 4, 5 or 6; and R8, R9and R10are each independently selected from linear or branched (C1-C6)alkyl radical, linear or branched (C1-C6)alkoxyl radical and tri(C1-C3)alkylsilyloxyl radical; with the proviso that at least one of R8, R9or R10is a (C1-C6)alkoxyl radical or a tri(C1-C3)alkylsilyloxyl radical; preferably R8, R9and R10are each independently selected from -CH3, -CH2CH3, -OCH3, -OCH2CH3, -O-Si(CH3)3, and -O-Si(CH2CH3)3.

[0033] .. In certain embodiments, optionally in combination with one or more features of the various embodiments described above or below, the radical A is selected from those compounds of formula (II) wherein m is an integer from 1 to 6; particularly 1, 2, 3, 4, 5 or 6; more particularly 2 or 3; and R4 is –NCO,wherein the asterisk indicates the point of attachment to the rest of group.

[0034] .. In accordance with a particular embodiment, optionally in combination with one or more features of the various embodiments described above or below, the compound of formula (I) is selected from (3-isocyanatopropyl)trimethoxysilane (also known as 3-(trimethoxysilyl)propyl isocyanate), (3-isocyanatopropyl)dimethoxy(methyl)silane, (3-isocyanatopropyl)(methoxy)dimethylsilane, (3-isocyanatopropyl)dimethoxy ethylsilane, diethyl(3-isocyanatopropyl)methoxysilane, (3-isocyanatopropyl)triethoxysilane (also known as 3-(triethoxysilyl)propyl isocyanate), diethoxy(3-isocyanatopropyl)methylsilane, ethoxy(3- isocyanatopropyl)dimethylsilane, (3-isocyanatopropyl)diethoxy(ethyl)silane, ethoxydiethyl(3-isocyanatopropyl)silane, trimethoxy(2-isocyanatoethyl)silane, (2- isocyanatoethyl)dimethoxy(methyl)silane, (2-isocyanatoethyl)(methoxy)dimethylsilane, ethyl(2-isocyanatoethyl)dimethoxysilane, diethyl(2-isocyanatoethyl)methoxysilane, triethoxy(2-isocyanatoethyl)silane, diethoxy(2-isocyanatoethyl)methylsilane, ethoxy(2-isocyanatoethyl)dimethylsilane, diethoxy(ethyl)(2-isocyanatoethyl)silane, ethoxydiethyl(2-isocyanatoethyl)silane, triethoxy(isocyanatomethyl)silane, (isocyanatomethyl)trimethoxysilane, trimethoxy({7-oxabicyclo[4.1.0]heptan-3-yl}methyl)silane, triethoxy({7-oxabicyclo[4.1.0]heptan-3-yl}methyl)silane,trimethoxy(2-{7-oxabicyclo[4.1.0]heptan-3-yl}ethyl)silane, diethoxy(methyl)(2-{7- oxabicyclo[4.1.0]heptan-3-yl}ethyl)silane, triethoxy(2-{7-oxabicyclo[4.1.0]heptan-3- yl}ethyl)silane, triethoxy(3-{7-oxabicyclo[4.1.0]heptan-3-yl}propyl)silane, trimethoxy(3-{7-oxabicyclo[4.1.0]heptan-3-yl}propyl)silane, triethoxy(4-{7-oxabicyclo[4.1.0]heptan-3-yl}butyl)silane, and trimethoxy(4-{7-oxabicyclo[4.1.0]heptan-3-yl}butyl)silane.

[0035] .. In certain embodiments, optionally in combination with one or more features of the various embodiments described above or below, the radical A is selected from those compounds of formula (III) as described above. In one embodiment, optionally in combination with one or more features of the various embodiments described above or below, the radical A is selected from those compounds of formula (III) wherein n and p are independently an integer selected from 1 to 6; particularly 1, 2, 3, 4, 5 or 6; more particularly 1, 2, 3 or 4; and q is an integer selected from 1 to 4; particularly 1, 2, 3 or 4, more particularly 1 or 3; X is selected from -O- and -N(R5)-; wherein R5is a radical selected from H, linear or branched (C1-C6)alkyl,wherein the asterisk indicates the point of attachment to the N atom; x and z are independently an integer selected from 1 to 6; particularly 1, 2, 3, 4, 5, or 6; and R8, R9and R10are each independently selected from -CH3, -CH2CH3, -OCH3, -OCH2CH3, -O-Si(CH3)3, and -O-Si(CH2CH3)3.

[0036] .. In accordance with a particular embodiment, optionally in combination with one or more features of the various embodiments described above or below, the compound of formula (I) is selected from trimethoxy({3-[(oxiran-2- yl)methoxy]propyl})silane (also known as glycidoxypropyl-trimethoxysilane), dimethoxy(methyl){3-[(oxiran-2-yl)methoxy]propyl}silane, methoxydimethyl{3-[(oxiran- 2-yl)methoxy]propyl}silane, dimethoxy(ethyl){3-[(oxiran-2-yl)methoxy]propyl}silane, diethyl(methoxy){3-[(oxiran-2-yl)methoxy]propyl}silane, triethoxy({3-[(oxiran-2-yl)methoxy]propyl})silane (also known as glycidoxypropyl- triethoxysilane), diethoxy(methyl){3-[(oxiran-2-yl)methoxy]propyl}silane,ethoxydimethyl{3-[(oxiran-2-yl)methoxy]propyl}silane, diethoxy-ethyl-[3-(oxiran-2- ylmethoxy)propyl]silane, ethoxydiethyl{3-[(oxiran-2-yl)methoxy]propyl}silane, trimethoxy({2-[(oxiran-2-yl)methoxy]ethyl})silane, dimethoxy(methyl){2-[(oxiran-2- yl)methoxy]ethyl}silane, methoxydimethyl{2-[(oxiran-2-yl)methoxy]ethyl}silane, ethyldimethoxy{2-[(oxiran-2-yl)methoxy]ethyl}silane, diethyl(methoxy){2-[(oxiran-2- yl)methoxy]ethyl}silane, triethoxy({2-[(oxiran-2-yl)methoxy]ethyl})silane, diethoxy(methyl){2-[(oxiran-2-yl)methoxy]ethyl}silane, ethoxydimethyl{2-[(oxiran-2- yl)methoxy]ethyl}silane, diethoxy(ethyl){2-[(oxiran-2-yl)methoxy]ethyl}silane, diethoxy(ethyl){2-[(oxiran-2-yl)methoxy]ethyl}silane, trimethoxy({[(oxiran-2-yl)methoxy]methyl})silane, dimethoxy(methyl){[(oxiran-2- yl)methoxy]methyl}silane, methoxydimethyl{[(oxiran-2-yl)methoxy]methyl}silane, ethyldimethoxy{[(oxiran-2-yl)methoxy]methyl}silane, diethyl(methoxy){[(oxiran-2- yl)methoxy]methyl}silane, triethoxy({[(oxiran-2-yl)methoxy]methyl})silane, diethoxy(methyl){[(oxiran-2-yl)methoxy]methyl}silane, ethoxydimethyl{[(oxiran-2- yl)methoxy]methyl}silane, diethoxy(ethyl){[(oxiran-2-yl)methoxy]methyl}silane, ethoxydiethyl{[(oxiran-2-yl)methoxy]methyl}silane, butyl[(oxiran-2-yl)methyl][3-(trimethoxysilyl)propyl]amine, butyl[(oxiran-2-yl)methyl][3-(triethoxysilyl)propyl]amine, ethyl[(oxiran-2-yl)methyl][3- (trimethoxysilyl)propyl]amine, ethyl[(oxiran-2-yl)methyl][3-(triethoxysilyl)propyl]amine, methyl[(oxiran-2-yl)methyl][3-(trimethoxysilyl)propyl]amine, methyl[(oxiran-2-yl)methyl][3-(triethoxysilyl)propyl]amine, N-[(oxiran-2-yl)methyl]-N-[3- (trimethoxysilyl)propyl]aniline, N-[(oxiran-2-yl)methyl]-N-[3- (triethoxysilyl)propyl]aniline, N-[(oxiran-2-yl)methyl]-N-[(trimethoxysilyl)methyl]aniline, N-[(oxiran-2-yl)methyl]-N-[(triethoxysilyl)methyl]aniline, methyl[(oxiran-2-yl)methyl][(trimethoxysilyl)methyl]amine, methyl[(oxiran-2-yl)methyl][(triethoxysilyl)methyl]amine 3-(trimethoxysilyl)-N-(3- (trimethoxysilyl)propyl)-N-((oxiran-2-yl)methyl)propan-1-amine, 3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)-N-((oxiran-2-yl)methyl)propan-1-amine and N,N-bis((trimethoxysilyl)methyl)(oxiran-2-yl)methanamine, and N,N-bis((triethoxysilyl)methyl)(oxiran-2-yl)methanamine.

[0037] .. In certain embodiments, optionally in combination with one or more features of the various embodiments described above or below, the radical A is selected from those compounds of formula (IV) or (V) as described above. In one embodiment, optionally in combination with one or more features of the various embodiments described above or below, the radical A is selected from those compounds of formula (IV) or (V) wherein r and t are independently an integer selected from 1, 2, 3, or 4; ands is an integer selected from 1, 2 or 3.

[0038] .. In accordance with a particular embodiment, optionally in combination with one or more features of the various embodiments described above or below, the compound of formula (I) is selected from (oxiran-2-yl)methyl N-[3- (trimethoxysilyl)propyl]carbamate, (oxiran-2-yl)methyl-N-[3- (triethoxysilyl)propyl]carbamate, (oxiran-2-yl)methyl-N-[4-(trimethoxysilyl)butyl]carbamate, (oxiran-2-yl)methyl-N-[4-(triethoxysilyl)butyl]carbamate, (oxiran-2-yl)methyl-N-[2-(trimethoxysilyl)ethyl]carbamate, (oxiran-2-yl)methyl-N-[2- (triethoxysilyl)ethyl]carbamate, (oxiran-2-yl)methyl-N-[(trimethoxysilyl)methyl]carbamate, (oxiran-2-yl)methyl-N--[(triethoxysilyl)methyl]carbamate, 3-trimethoxysilylpropylcarbamoyl oxirane-2-carboxylate, 3-triethoxysilylpropylcarbamoyl oxirane-2-carboxylate, oxirane-2-carbonyl-N- [(trimethoxysilyl)methyl]carbamate, oxirane-2-carbonyl-N- [(triethoxysilyl)methyl]carbamate, oxirane-2-carbonyl-N-[4-(trimethoxysilyl)butyl]carbamate and oxirane-2-carbonyl-N-[4-(triethoxysilyl)butyl]carbamate.

[0039] .. In certain embodiments, optionally in combination with one or more features of the various embodiments described above or below, the radical A is selected from those compounds of formula (VI) as described above.

[0040] .. In one embodiment, optionally in combination with one or more features of the various embodiments described above or below, the radical A is selected from those compounds of formula (VI) wherein w is an integer selected from 1, 2, 3, or 4; particularly 2, 3 or 4.

[0041] .. In accordance with a particular embodiment, optionally in combination with one or more features of the various embodiments described above or below, the compound of formula (I) is selected from 3-[3-(triethoxysilyl)propyl]oxolane-2,5-dione and 3-[3-(trimethoxysilyl)propyl]oxolane-2,5-dione.

[0042] .. In accordance with some particular embodiment, optionally in combination with one or more features of the various embodiments described above or below, the reaction of the capping agent with the polyether polyol is carried out in a molar ratio from 0.05 to 2.0 mole, preferably from 0.2 to 1.8 mole, more preferably from 0.50 to 1.5 mole, being particularly preferably from 0.8 to 1.2 mole of capping agent per mole of polyether polyol.

[0043] .. Thus, in accordance with certain embodiments, optionally in combination with one or more features of the various embodiments described above or below, thenitrogen-containing alkoxysilane-capped polyether polyol contains from 1 to 8 hydroxyl groups per molecule, preferably from 2 to 7, more preferably from 3 to 6 and still more preferably from 4 to 5 hydroxyl groups per molecule and from 1 to 2, preferably 1 nitrogen-containing alkoxysilane groups per molecule.

[0044] .. As mentioned above, the nitrogen-containing alkoxysilane-capped polyether polyol is obtained by capping from 1 to 2 of the terminal hydroxyl groups of a polyether polyol (polyether polyol raw material) having a functionality from 2 to 10 and a weight-average molecular weight from 2000 to 25000 with a capping agent to obtain an intermediate resulting product (first capping step); and then reacting the intermediate resulting product with a compound comprising an amino or -NHCONH2group and at least one alkoxysilane terminal group, to obtain the nitrogen-containing alkoxysilane-capped polyether polyol.

[0045] .. In accordance with particular embodiments, optionally in combination with one or more features of the various embodiments described above or below, the polyether polyol, used as raw material in the first capping step, has a OH functionality from 2-10, preferably from 2-8, more preferably from 3-7; and still more preferably from 3-6. In some particular embodiments the OH functionality is 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0046] .. In accordance with particular embodiments, optionally in combination with one or more features of the various embodiments described above or below, such polyether polyol has a weight-average molecular weight from 2000 to 25000, preferably from 2000 to 20000, more preferably from 3000 to 20000, particularly preferred from 8000 to 15000, and still more preferably from 11000 to 14000.

[0047] .. In accordance with particular embodiments, optionally in combination with one or more features of the various embodiments described above or below, such polyether polyol has a hydroxyl number in the range 20-600 mg KOH / g, preferably 24-380 mg KOH / g, more preferably 26-80 mg KOH / g.

[0048] .. In accordance with particular embodiments, optionally in combination with one or more features of the various embodiments described above or below, such polyether polyol has a viscosity at 25 ºC from 50 to 12500 mPa s, preferably from 200 to 8000 mPa s, more preferably from 450 to 5000 mPa s and still more preferably from 500 to 2000 mPa s.

[0049] .. In accordance with certain particular embodiments, optionally in combination with one or more features of the various embodiments described above or below, the polyether polyol is a polyether polyol having a functionality between 3-6; a weight-average molecular weight from 2000 to 20000 and a viscosity at 25 ºC from 200 to 8000 mPa s.

[0050] .. In accordance with some particular embodiments of the present invention, optionally in combination with one or more features of the various embodiments described above or below, the polyether polyol does not comprise organic fillers dispersed therein. Thus, in accordance with one embodiment, the first polyol is not or does not comprise a modified polymer polyol, since it is substantially free of organic fillers dispersed therein.

[0051] .. In accordance with some particular embodiments of the present invention, optionally in combination with one or more features of the various embodiments described above or below, the polyether polyol comprises quantities of organic fillers dispersed therein; thus in some embodiments, the polyether polyol may contain from 0 wt% to 50 wt% of and organic filler dispersed therein, preferably from 0.01 wt% to 30 wt%, more preferably from 0.02 wt% to 15 wt%, and still more preferably from 0.5 wt% to 5 wt%. Example of organic fillers are polyethylene, polypropylene, and vinyl polymer particles such as particles of acrylonitrile, polystyrene, methacrylonitrile, methyl methacrylate, polyisocyanate polyaddition polymer (PIPA), polyurea (PHD), and styrene-acrylonitrile.

[0052] .. In certain embodiments, optionally in combination with one or more features of the various embodiments described above or below, the at least one polyether polyol has a functionality from 2 to 10 and a weight-average molecular weight from 2000 to 20000, and is obtainable by reacting ethylene oxide and / or propylene oxide with a polyhydric alcohol selected from glycerol, sorbitol, sucrose, trimethylolpropane, diethylene glycol, butanetriol, pentanetriol, hexanetriol erythritol and pentaerythritol.

[0053] .. In some particular embodiments of the present invention, optionally in combination with one or more features of the various embodiments described above or below, the polyether polyol is a poly(ethylene oxide and / or propylene oxide) adduct of a polyhydric alcohol selected from glycerol, sorbitol, sucrose, trimethylolpropane, diethylene glycol, butanetriol, pentanetriol, hexanetriol erythritol and pentaerythritol; wherein the polyether polyol has a functionality from 2-10, a weight-average molecular weight from 2000 to 20000.

[0054] .. In accordance with particular embodiments, optionally in combination with one or more features of the various embodiments described above or below, the polyether polyol is an ethylene oxide (EO) or propylene oxide (PO) capped polyether polyol. In a particular embodiment, optionally in combination with one or more features of the various embodiments described above or below, the polyether polyol is a reactive polyether polyol, i.e. an ethylene oxide (EO) capped polyether polyol having a content of terminal primary hydroxyl groups, as measured by RMN-13C, from 35 to 99.9 %, from 35 to 98 %, from 40 to 95 %, from 45 to 90 %, from 50 to 85%, from 75 to 99 %, from 77 to 98 % or from 78 to 95 %. In accordance with some particular embodiments, optionally in combination with one or more features of the various embodiments described above or below, the polyether polyol is a reactive polyether polyol having a content of polyethylene oxide terminal blocks of 5-20 wt%, preferably 10-19.5 wt%, preferably from 12-19 wt% and more preferably from 13-18 wt%.

[0055] .. In accordance with another particular embodiment, optionally in combination with one or more features of the various embodiments described above or below, the polyether polyol is a non-reactive polyether polyol, i.e. a propylene oxide (PO) capped polyether polyol.

[0056] .. In some particular embodiments of the present invention, optionally in combination with one or more features of the various embodiments described above or below, the at least one compound comprising an amino or -NHCONH2group and at least one alkoxysilane terminal group is a compound of formula (Ia)wherein R1’, R2’ and R3’ are each independently selected from linear or branched (C1- C6)alkyl radical, linear or branched (C1-C6)alkoxyl radical, and tri(C1-C3)alkylsilyloxyl radical; preferably a radical selected from CH3-O-, CH3CH2-O-, CH3CH2CH2-O-, (CH3)2CH-O-, CH3CH2CH2CH2-O-, (CH3)3CH-O-, (CH3)2CHCH2-O-, CH3-, CH3CH2-, CH3CH2CH2-, (CH3)2CH-, CH3CH2CH2CH2-, (CH3)3CH-, (CH3)2CHCH2-, (CH3)3Si-O-, and (CH3CH2)3Si-O-; with the proviso that at least one of R1’, R2’ or R3’ is a (C1-C6)alkoxyl radical; preferably at least one of R1’, R2’ or R3’ is CH3-O-, CH3CH2-O-, CH3CH2CH2-O-, or (CH3)2CH-O-; and wherein A’ is selected from -(C1-C6)alkylNH2, -(C1-C6)alkylNH-(C1-C6)alkylNH2, -(C1-C6)alkylNH-(C1-C6)alkylNH-(C1-C6)alkylNH2, -(C1-C6)alkyl-NH-CO-NH2, -(C1-C6)alkylNH-(C1-C6)alkylNH-CO-NH2, and -(C1-C6)alkylNH-(C1-C6)alkylNH-(C1-C6)alkylNH-CO-NH2; preferably A’ is selected from -CH2NH2, -CH2CH2NH2, -CH2CH2CH2NH2, -CH2CH(CH3)NH2, -CH2NHCH2NH2, - CH2CH2NHCH2NH2, -CH2CH2NHCH2CH2NH2, -CH2CH2CH2NHCH2NH2, CH2CH2CH2NHCH2CH2NH2, CH2CH2CH2NHCH2CH2CH2NH2,-CH2CH(CH3)NHCH(CH3)CH2NH2, -CH2NHCH2NHCH2NH2, -CH2CH2NHCH2NHCH2NH2, -CH2CH2NHCH2NHCH2CH2NH2, -CH2CH2NHCH2CH2NHCH2CH2NH2, -CH2CH2CH2NHCH2NHCH2CH2CH2NH2, -CH2CH2CH2NHCH2CH2NHCH2CH2CH2NH2, -CH2CH2CH2NHCH2CH2CH2NHCH2CH2CH2NH2, CH2CH2CH2NHCH2CH2NHCH2NH2, -CH2CH2CH2NHCH2CH2NHCH2CH2NH2, -CH2CH(CH3)NHCH(CH3)CH2NHCH(CH3)NH2, -CH2NHCONH2, -CH2CH2NHCONH2, -CH2CH2CH2NHCONH2, -CH2CH(CH3)NHCONH2, -CH2NHCH2NHCONH2, -CH2CH2NHCH2NHCONH2, -CH2CH2NHCH2CH2NHCONH2, -CH2CH2CH2NHCH2NHCONH2, CH2CH2CH2NHCH2CH2NHCONH2, CH2CH2CH2NHCH2CH2CH2NHCONH2, -CH2CH(CH3)NHCH(CH3)CH2NHCONH2.

[0057] .. In accordance with some embodiments, optionally in combination with one or more features of the various embodiments described above or below, the compound of formula (Ia) is selected from N-(2-aminoethyl)-3- aminopropyltrimethoxysilane (CAS 1760-24-3), (3-aminopropyl)triethoxysilane (CAS 919-30-2) , 3-(2-aminoethylamino)propyldimethoxymethylsilane (CAS 3069-29-2), 3- aminopropyl(diethoxy)methylsilane (CAS 3179-76-8), N1-(3- trimethoxysilylpropyl)diethylenetriamine (CAS 35141-30-1), 3- (ethoxydimethylsilyl)propylamine (CAS 18306-79-1), (3-aminopropyl)trimethoxysilane (CAS 13822-56-5), aminopropylmethyldiethoxysilane (CAS 3179-76-8), 3- aminopropylsilanetriol (CAS 58160-99-9), N-(3-triethoxysilylpropyl)ethylenediamine (CAS 5089-72-5), 3-ureidopropyltrimethoxysilan (CAS 23843-64-3), N- cyclohexylamino- methyltriethoxysilan (CAS 26495-91-0), N-cyclohexyl-3- aminopropyltrimethoxysilan (CAS 3068-78-8), bis[3-triethoxysilyl)propyl]amine (CAS 13497-18-2), bis[3-trimethoxysilyl)propyl]amine (CAS 82985-35-1), aminopropylmethyldimethoxysilane (CAS 3663-44-3), diethylaminomethyltriethoxysilane (CAS 15180-47-9), diethylaminoethyltriethoxysilane (CAS 41051-80-3), N-(N-Butyl)-3- aminopropyltrimethoxysilane (CAS 31024-56-3).

[0058] .. In some embodiments, optionally in combination with one or more features of the various embodiments described above or below, the at least one compound of formula Ia is added to the intermediate resulting product in a molar ratio with respect to the compound of formula (I) added in step (a) ranging from 0.1 to 20, from 0.5 to 10, from 0.7 to 5, from 0.9 to 5, from 0.99 to 3.5, from 1.5 to 2.75.

[0059] .. In some particular embodiments of the present invention, optionally in combination with one or more features of the various embodiments described aboveor below, the nitrogen-containing alkoxysilane-capped polyether polyols are obtained by a) capping from 1 to 2 of the terminal hydroxyl groups of i) a polyether polyol having a functionality from 2 to 10 and a weight-average molecular weight from 2000 to 20000, which is obtainable by reacting ethylene oxide and / or propylene oxide with a polyhydric alcohol selected from glycerol, sorbitol, sucrose, trimethylolpropane, diethylene glycol, butanetriol, pentanetriol, hexanetriol, erythritol and pentaerythritol; with ii) a capping agent which is a compound of formula (I); wherein the reaction of the capping agent with the polyether polyol is carried out in a molar ratio from 0.05 to 2.0 mole, preferably from 0.2 to 1.8 mole, more preferably from 0.5 to 1.5 mole, being particularly preferably from 0.8 to 1.2 mole of capping agent per mole of polyether polyol; to obtain an intermediate resulting product; and b) reacting the intermediate resulting product in a) with at least one compound of formula (Ia) comprising an amino or -NHCONH2group and at least one alkoxysilane terminal group; to obtain the nitrogen-containing alkoxysilane-capped polyether polyol; wherein the at least one capping alkoxysilane group-containing agent is a compound of formula (I), wherein the radical A is selected from ii.1) those compounds of formula (II) wherein m is an integer from 1 to 6; and R4 is selected from –NCO,wherein the asterisk indicates the point of attachment to the rest of group; ii.2) those compounds of formula (III) wherein n and p are independently an integer selected from 1 to 6, q is an integer selected from 1 to 3, X is selected from -O- and -N(R5)-, wherein R5is a radical selected from H, linear or branched (C1-C6)alkyl,wherein the asterisk indicates the point of attachment to the N atom; x and z are independently an integer selected from 1 to 6; and R8, R9and R10are each independently selected from -CH3, -CH2CH3, -OCH3, -OCH2CH3, -O-Si(CH3)3, and -O-Si(CH2CH3)3; ii.3) those compounds of formula (IV) or (V) wherein r and t are independently an integer selected from 1 to 4; and s is an integer selected from 1 to 3; or alternatively ii.4) those compounds of formula (VI), wherein w is an integer selected from 1 to 4; and wherein the at least one compound of formula (Ia) is added to the intermediate resulting product in a molar ratio with respect to the compound of formula (I) added in step (a) ranging from 0.1 to 20, preferably from 0.5 to 10, more preferably from 0.7 to 5, more preferably from 0.9 to 5, more preferably from 0.99 to 3.5, more preferably from 1.5 to 2.75.

[0060] .. In some particular embodiments of the present invention, optionally in combination with one or more features of the various embodiments described above or below, the nitrogen-containing alkoxysilane-capped polyether polyol are obtained by a) capping from 1 to 2 of the terminal hydroxyl groups of a polyether polyol having a functionality from 2 to 10 and a weight-average molecular weight from 2000 to 20000, which is obtainable by reacting ethylene oxide and / or propylene oxide with a polyhydric alcohol selected from glycerol, sorbitol, sucrose, trimethylolpropane, diethylene glycol, butanetriol, pentanetriol, hexanetriol, erythritol and pentaerythritol; with a capping agent which is a compound of formula (I); wherein the reaction of the capping agent with the polyether polyol is carried out in a molar ratio from 0.05 to 2.0 mole, preferably from 0.2 to 1.8 mole, more preferably from 0.5 to 1.5 mole, being particularly preferably from 0.8 to 1.2 mole of capping agent per mole of polyether polyol; to obtain an intermediate resulting product; andb) reacting the intermediate resulting product in a) with at least one compound of formula (Ia) comprising an amino or -NHCONH2group and at least one alkoxysilane terminal group; to obtain the nitrogen-containing alkoxysilane- capped polyether polyol; wherein, in the compound of formula (I) the radical A is selected from: i) those compounds of formula (II) wherein m is an integer selected from 1, 2, 3, 4, 5 and 6; and R4 is selected from –NCO,wherein the asterisk indicates the point of attachment to the rest of group; ii) those compounds of formula (III) wherein n and p are independently an integer selected from 1.2.3.4.5. And 6, q is an integer selected from 1, 2 and 3, X is selected from -O- and -N(R5)-, wherein R5 is a radical selected from H, linear or branched (C1-C6)alkyl,wherein the asterisk indicates the point of attachment to the N atom; x and z are independently an integer selected from 1, 2, 3, 4, 5 and 6; and R8, R9 and R10 are each independently selected from -CH3, -CH2CH3, -OCH3, -OCH2CH3, -O-Si(CH3)3, and -O-Si(CH2CH3)3; iii) those compounds of formula (IV) or (V) wherein r and t are independently an integer selected from 1, 2, 3, and 4; and s is an integer selected from 1, 2, and 3; or alternatively iv) those compounds of formula (VI), wherein w is an integer selected from 1, 2, 3 and 4, such as 3-[3-(triethoxysilyl)propyl]oxolane-2,5-dione and 3-[3-(trimethoxysilyl)propyl]oxolane-2,5-dione wherein in the compound of formula (Ia), R1’, R2’ and R3’ are each independently selected from linear or branched (C1-C6)alkyl radical, linear or branched (C1-C6)alkoxyl radical, and tri(C1-C3)alkylsilyloxyl radical; preferably a radical selected from CH3-O-, CH3CH2-O-, CH3CH2CH2-O-, (CH3)2CH-O-, CH3CH2CH2CH2-O-, (CH3)3CH-O-, (CH3)2CHCH2-O-, CH3-, CH3CH2-, CH3CH2CH2-, (CH3)2CH-, CH3CH2CH2CH2-, (CH3)3CH-, (CH3)2CHCH2-, (CH3)3Si-O-, and (CH3CH2)3Si-O-; with the proviso that at least one of R1’, R2’ or R3’ is a (C1-C6)alkoxyl radical; preferably at least one of R1’, R2’ or R3’ is CH3-O-, CH3CH2-O-, CH3CH2CH2-O-, (CH3)2CH-O-; wherein A’ is selected from –(C1-C6)alkylNH2, -(C1-C6)alkylNH-(C1-C6)alkylNH2, -(C1-C6)alkylNH-(C1-C6)alkylNH-(C1-C6)alkylNH2, -(C1-C6)alkyl-NH-CO-NH2, -(C1-C6)alkylNH-(C1-C6)alkylNH-CO-NH2, and -(C1-C6)alkylNH-(C1-C6)alkylNH-(C1-C6)alkylNH-CO-NH2; preferably A’ is selected from -CH2NH2, -CH2CH2NH2, -CH2CH2CH2NH2, -CH2CH(CH3)NH2, -CH2NHCH2NH2, - CH2CH2NHCH2NH2, -CH2CH2NHCH2CH2NH2, -CH2CH2CH2NHCH2NH2, CH2CH2CH2NHCH2CH2NH2, CH2CH2CH2NHCH2CH2CH2NH2, -CH2CH(CH3)NHCH(CH3)CH2NH2, -CH2NHCH2NHCH2NH2, -CH2CH2NHCH2NHCH2NH2, -CH2CH2NHCH2NHCH2CH2NH2, -CH2CH2NHCH2CH2NHCH2CH2NH2, -CH2CH2CH2NHCH2NHCH2CH2CH2NH2, -CH2CH2CH2NHCH2CH2NHCH2CH2CH2NH2, -CH2CH2CH2NHCH2CH2CH2NHCH2CH2CH2NH2, CH2CH2CH2NHCH2CH2NHCH2NH2, CH2CH2CH2NHCH2CH2NHCH2CH2NH2, -CH2CH(CH3)NHCH(CH3)CH2NHCH(CH3)NH2, -CH2NHCONH2, -CH2CH2NHCONH2, -CH2CH2CH2NHCONH2, -CH2CH(CH3)NHCONH2, -CH2NHCH2NHCONH2, -CH2CH2NHCH2NHCONH2, -CH2CH2NHCH2CH2NHCONH2, -CH2CH2CH2NHCH2NHCONH2, CH2CH2CH2NHCH2CH2NHCONH2, CH2CH2CH2NHCH2CH2CH2NHCONH2, -CH2CH(CH3)NHCH(CH3)CH2NHCONH2; and wherein the compound of formula (Ia) is added to the intermediate resulting product in a molar ratio with respect to the compound of formula (I) added in step (a) ranging from 0.1 to 20, preferably from 0.5 to 10, more preferably from 0.7 to 5, more preferably from 0.9 to 5, more preferably from 0.99 to 3.5, more preferably from 1.5 to 2.75

[0061] .. In some particular embodiments of the present invention, optionally in combination with one or more features of the various embodiments described above or below, the nitrogen-containing alkoxysilane-capped polyether polyols are obtainable by a) capping from 1 to 2 of the terminal hydroxyl groups ofat least one polyether polyol having a functionality from 2 to 10 and a weight-average molecular weight from 2000 to 20000, which is obtainable by reacting ethylene oxide and / or propylene oxide with a polyhydric alcohol selected from glycerol, sorbitol, sucrose, trimethylolpropane, diethylene glycol, butanetriol, pentanetriol, hexanetriol, erythritol and pentaerythritol; with at least a capping alkoxysilane group-containing agent of formula (I) which is selected from (3-isocyanatopropyl)trimethoxysilane, (3-isocyanatopropyl)dimethoxy(methyl)silane, (3-isocyanatopropyl)(methoxy)dimethylsilane, (3-isocyanatopropyl)dimethoxy-ethylsilane, 3-isocyanatopropyltriethoxysilane, (3-isocyanatopropyl)diethoxy(ethyl)silane, triethoxy(2-isocyanatoethyl)silane, triethoxy(isocyanatomethyl)silane, trimethoxy({3-[(oxiran-2-yl)methoxy]propyl})silane, dimethoxy(methyl){3-[(oxiran-2-yl)methoxy]propyl}silane, methoxydimethyl{3-[(oxiran- 2-yl)methoxy]propyl}silane, dimethoxy(ethyl){3-[(oxiran-2-yl)methoxy]propyl}silane, triethoxy({3-[(oxiran-2-yl)methoxy]propyl})silane, diethoxy-ethyl-[3-(oxiran-2-ylmethoxy)propyl]silane, 3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)-N-((oxiran-2-yl)methyl)propan-1- amine, 3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)-N-((oxiran-2-yl)methyl)propan-1- amine, N,N-bis((trimethoxysilyl)methyl)(oxiran-2-yl)methanamine, 3-trimethoxysilylpropylcarbamoyl oxirane-2-carboxylate, 3-triethoxysilylpropylcarbamoyl oxirane-2-carboxylate, 3-trimethoxysilylethylcarbamoyl oxirane-2-carboxylate, and 3-triethoxysilylethylcarbamoyl oxirane-2-carboxylate; wherein the reaction of the capping agent with the polyether polyol is carried out in a molar ratio from 0.05 to 2.0 mole, preferably from 0.2 to 1.8 mole, more preferably from 0.50 to 1.5 mole, being particularly preferably from 0.8 to 1.2 mole of capping agent per mole of polyether polyol; b) reacting the intermediate resulting compound in a) with at least one compound of formula (Ia) which is selected from N-(2-aminoethyl)-3- aminopropyltrimethoxysilane (CAS 1760-24-3), (3-aminopropyl)triethoxysilane (CAS 919-30-2) , 3-(2-aminoethylamino)propyldimethoxymethylsilane (CAS 3069-29-2), 3- aminopropyl(diethoxy)methylsilane (CAS 3179-76-8), N1-(3- trimethoxysilylpropyl)diethylenetriamine (CAS 35141-30-1), 3- (ethoxydimethylsilyl)propylamine (CAS 18306-79-1), (3-aminopropyl)trimethoxysilane (CAS 13822-56-5), aminopropylmethyldiethoxysilane (CAS 3179-76-8), 3- aminopropylsilanetriol (CAS 58160-99-9), N-(3-triethoxysilylpropyl)ethylenediamine (CAS 5089-72-5), 3-ureidopropyltrimethoxysilan (CAS 23843-64-3), N-cyclohexylamino- methyltriethoxysilan (CAS 26495-91-0), N-cyclohexyl-3- aminopropyltrimethoxysilan (CAS 3068-78-8), bis[3-triethoxysilyl)propyl]amine (CAS 13497-18-2), bis[3-trimethoxysilyl)propyl]amine (CAS 82985-35-1), aminopropylmethyldimethoxysilane (CAS 3663-44-3), diethylaminomethyltriethoxysilane (CAS 15180-47-9), diethylaminoethyltriethoxysilane (CAS 41051-80-3), N-(N-Butyl)-3- aminopropyltrimethoxysilane (CAS 31024-56-3).

[0062] .. Thus, since the intermediate resulting product in step a) are obtainable by reaction of at least a polyether polyol as defined above with the at least one compound of formula (I), the intermediate resulting products may be described as alkoxysilane-capped polyether polyols wherein from 1 to 2, preferably 1 hydroxyl groups of the polyether polyol are reacted with the hydroxyl-reactive group present in the capping alkoxysilane group-containing agent. Thus, for example, when a polyether polyol having a functionality of 6, i.e. the number of OH groups in the molecule is 6, reacts with the compound of formula (I) in a molar ratio from 0.8 to 1.2 mole of compound of formula (I) per mole of polyether polyol, the alkoxysilane group- modified compound thus obtained is a polyether polyol wherein 1 hydroxyl groups have reacted with the hydroxyl-reactive group present in the capping alkoxysilane group -containing agent of formula (I), leaving the other hydroxyl groups free.

[0063] .. In accordance with one embodiment, optionally in combination with one or more features of the various embodiments described above or below, the reaction between the polyether polyol and the compound of formula (I) is carried out in a temperature range from 0 ºC to 160 ºC, preferably from 10 ºC to 120 ºC, particularly preferred from 20 ºC to 80 ºC.

[0064] .. This reaction may be carried out in the presence of a catalyst. The skilled person in the art may identify any suitable catalyst depending on the reactants.

[0065] .. In some embodiments, optionally in combination with one or more features of the various embodiments described above or below, the reaction may be carried out in the presence of urethanization catalysts known to experts per se, such as potassium-based catalyts, organotin compounds or amine catalysts. Other catalysts such as Zinc based catalysts may be used. In some particular embodiments, optionally in combination with one or more features of the various embodiments described above or below, the potassium-based catalyst is selected from potassium acetate and potassium octoate; the organitin catalyst is selected from dibutyl tin diacetate, dibutyl tin dilaurate, dioctyl tin dilaurate, dibutyl tin bis acetoacetonate, tin carboxylates such as tin octoate, tin ricinoleate, tin neodecanoate; whereas the amine catalysts is selected from tertiary amines. In some embodiments, the reactionis carried out in the presence of at least one tin catalyst or at least one amino catalyst.

[0066] .. In another embodiments, optionally in combination with one or more features of the various embodiments described above or below, particularly when the compound of formula (I) have an epoxide group as the hydroxyl-reactive group, the reaction may be carried out in the presence of a catalyst selected from Lewis acids and Brönsted superacids such as BF3, PF5, SbF5, HPF6, HBF4, HSbF6, CF3SO3H, Al(CF3SO3)3, Y(CF3SO3)3, Nd(CF3SO3)3; anionic catalyst such as NaOH, KOH, CsOH, Sr(OH)2, Ba(OH)2, calcium naphthenates, calcium octanoates, phosphazenium compounds; co-ordinative catalysts such as aluminium and zinc alkyls and alcoholates [Al(OR)3, Zn(OR)2], aluminium and zinc tetraphenyl porphirinates, titanium alcoholates [Ti(OR)4], dimetallic catalysts (DMC) based on Zn3[Co(CN)6]3.

[0067] .. The reaction may be carried out continuously, e.g. in a static mixer or in a extruder, or discontinuously, e.g. in a stirred reactor.

[0068] .. Step b) in the preparation of the nitrogen-containing alkoxysilane-capped polyether polyol comprises the reaction of the intermediate resulting product in step a), i.e. the alkoxysilane-capped polyether polyol (intermediate resulting product), with a compound of formula Ia to obtain the nitrogen-containing alkoxysilane-capped polyether polyol. In a first step, the alkoxysilane-capped polyether polyol (intermediate resulting product) undergoes an hydrolysis reaction to afford a silanol group, obtaining the corresponding hydrolysed alkoxysilane-capped polyether polyol derivative; then, the alkoxysilane moiety present in the compound of formula Ia, or its corresponding hydrolysed derivative, reacts with the silanol moiety present in the hydrolysed alkoxysilane-capped polyether polyol derivative to afford the nitrogen- containing alkoxysilane-capped polyether polyol.

[0069] .. The hydrolysis reaction takes place in the presence of water, which may be added intentionally to the reaction media, or it may be the water which accompanies to the reactants which may be supplied as a water solution thereof. The amount of water present in the reaction media should be the necessary to carry out the hydrolysis of the intermediate resulting product to afford the corresponding silanol group containing derivative (i.e. hydrolysed alkoxysilane-capped polyether polyol derivative). Modified polymer polyol dispersions

[0070] .. The present invention also relates to new stable modified polymer polyol dispersions obtainable by polymerising one or more polymeric particle precursors in aliquid polyol mixture under polymerisation conditions characterised in that the liquid polyol mixture comprises at least one base polyol and at least one nitrogen- containing alkoxysilane-capped polyether polyol as defined herein.

[0071] .. With regard to the base polyol used in the preparation of the modified polymer polyol dispersions and / or the polyurethane foams according to the present invention, this base polyol may be of any suitable kind known in the art.

[0072] .. Representative base polyols useful in the preparation of the modified polymer polyol in accordance with the present disclosure may include polyether polyols, polyester polyols, polymer polyols, polyhydroxy-terminated acetal resins, hydroxyl-terminated amines, polyalkylene carbonate-based polyols, acrylic polyols, polyphosphate-based polyols, and polyols comprising a polyether carbonate polyol (POPC). Suitable polymer polyols include PDH polyols, PIPA polyols, SAN polyols, copolymer polyols and polymer polyols comprising a polyether carbonate polyol (POPC) as the base polyol. All types of other polyols like polyols derived from renewable resources (so called natural oil polyols or NOP's) can also be used pure or in mixtures as long as they have the right physico - chemical features.

[0073] .. In accordance with an embodiment, optionally in combination with one or more features of the various embodiments described above or below, preferred base polyols are selected from polyether polyols, polyester polyols, PDH polyols, PIPA polyols, SAN polyols, and polyols comprising a polyether carbonate polyol (POPC). Some particularly preferred base polyols are selected from polyether carbonate polyols (POPC) and polyether polyols.

[0074] .. In one preferred embodiment, optionally in combination with one or more features of the various embodiments described above or below, the base polyol comprises at least one ethylene oxide (EO) or propylene oxide (PO) capped polyether polyol.

[0075] .. In accordance with one particular embodiment, optionally in combination with one or more features of the various embodiments described above or below, suitable base polyols may have an OH functionality from 2 to 10, in other particular embodiments the OH functionality is from 2 to 8, more particularly from 2 to 6, even more particularly from 3 to 6. In some particular embodiments the OH functionality is 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0076] .. In accordance with one particular embodiment, optionally in combination with one or more features of the various embodiments described above or below, suitable base polyols are reactive polyether polyols, i.e. ethylene oxide (EO) capped polyether polyol having a content of terminal primary hydroxyl groups between 35- 99.9 %, as measured by RMN-13C,from 35 to 99.9 %, from 35 to 98 %, from 40 to 95%, from 45 to 90 %, from 50 to 85 %, from 75 to 99 %, from 77 to 98 % or from 78 to 95 %. In accordance with some particular embodiments, optionally in combination with one or more features of the various embodiments described above or below, the base polyol is a reactive polyether polyol having a content of polyethylene oxide terminal blocks of 5-20 wt%, preferably 10-19.5 wt%, preferably from 12-19 wt% and more preferably from 13-18 wt%.

[0077] .. Nevertheless, as explained above, the new nitrogen-containing alkoxysilane-capped polyether polyols allows to use a non-reactive base polyol for the preparation of the stable modified polymer polyol dispersions, including PIPA polymer polyol dispersions and PHD polymer polyol dispersions. Therefore, in accordance with another particular embodiment, optionally in combination with one or more features of the various embodiments described above or below, the base polyol is a non-reactive polyether polyol. Preferably the base polyol is a non-reactive propylene oxide (PO) capped polyether polyol having a content of terminal primary hydroxyl groups between 0-40 %, as measured by RMN-13C, from 0.1 to 35 %, from 0.2 to 30 %, from 0.3 to 25 %, from 0.4 to 20 %, from 0.5 to 15 %; preferably the base polyol is a non-reactive propylene oxide (PO) capped polyether polyol having a content of terminal primary hydroxyl groups between 0 to 10 %.

[0078] .. In some embodiments, optionally in combination with one or more features of the various embodiments described above or below, the base polyols have a molecular weight (MW) in the range of 150 to 16000; preferably 200 to 12500 and more preferably from 250 to 12000. Some base polyols according to the invention have a molecular weight (MW) in the range from 300 to 6500, particularly from 350 to 4800, more particularly from 400 to 3500. In other particular embodiments, optionally in combination with one or more features of the various embodiments described above or below, the base polyols may have a MW in the range from 3000 to 12000, particularly in the range from 4500 to 12000, more particularly from 4600 to 10000, or even more particularly from 5000 to 9000. Some particular embodiments, optionally in combination with one or more features of the various embodiments described above or below, refer to base polyols having a molecular weight (MW) in the range from 400 to 3000; alternatively in certain particular embodiments the base polyols have a molecular weight in the range from 4500 to 12000.

[0079] .. In some embodiments, optionally in combination with one or more features of the various embodiments described above or below, the base polyols have a viscosity at 25 ºC from 50 to 25000 mPa s, preferably from 65 to 9500 and more preferably from 150 to 8000 mPa s. In some embodiments, optionally in combination with one or more features of the various embodiments described above or below, thebase polyols have a viscosity at 25 ºC from 250 to 6500 mPa s, particularly from 400 to 2000 mPa s, from 420 to 1800 mPa s, from 450 to 1600 mPa s, from 470 to 1500 mPa s.

[0080] .. In certain embodiments, optionally in combination with one or more features of the various embodiments described above or below, the hydroxyl number (iOH) of the base polyols ranges from 5 to 1800 mg KOH / g, from 5 to 1500 mg KOH / g, from 7 to 1400 mg KOH / g, from 8 to 1300 mg KOH / g, from 9 to 1200 mg KOH / g, or from 10 to 1100 mg KOH / g. In other embodiments the iOH of the base polyols ranges from 5 to 800 mg KOH / g, from 10 to 600 mg KOH / g, from 15 to 500 mg KOH / g, from 25 to 460 mg KOH / g. In certain particular embodiments the iOH of the base polyols ranges from 20 to 80 mg KOH / g, from 25 to 70 mg KOH / g, from 26 to 65 mg KOH / g or 26 to 58 mg KOH / g. Whereas in certain embodiments, the iOH of the base polyols ranges from 80 to 700 mg KOH / g, from 81 to 650 mg KOH / g, from 90 to 550 mg KOH / g, from 120 to 520 mg KOH / g. In some examples the iOH of the base polyols ranges from 28-280 mg KOH / g; in accordance with additional examples the iOH ranges from 28- 56 mg KOH / g and in further examples the iOH ranges from 160-490 mg KOH / g.

[0081] .. It is well known in the art to use mixed polyols to vary the reactivity of the system or impart desired properties to the resulting polyurethanes. Therefore, in accordance with an embodiment of the present disclosure, optionally in combination with one or more features of the various embodiments described above or below, mixtures of base polyols, mixtures of polymer polyols or mixtures of base and polymer polyols may also be used.

[0082] .. In accordance with an embodiment of the present invention, optionally in combination with one or more features of the various embodiments described above or below, the stable modified polymer polyol dispersion is a polyisocyanate polyaddition polymer polyol dispersion (PIPA polyol), and the base polyol is a non- reactive polyol.

[0083] .. In accordance with an embodiment of the present disclosure, optionally in combination with one or more features of the various embodiments described above or below, the method of preparation of the modified polymer polyol dispersions comprises the preparation of polymeric particles, in the presence of the liquid polyol mixture, by a. reacting, in the liquid polyol mixture and under polymerisation conditions a.1) at least one compound bearing at least one basic-nitrogen atom characterized by the presence in the molecule of at least one hydrogen atom attached to a nitrogen atom; with either a.2) or a.3), whereina.2) is at least one compound or a mixture of compounds bearing a phosphorus atom selected from the group consisting of [bis(hydroxymethyl)phosphanyl]metanol (THP), tetrakis(hydroxymethyl) phosphonium salt (THPX), [bis(hydroxymethyl)phosphoryl]methanol (THPO), ({[bis(hydroxymethyl)phosphanyl]methoxy}methanol (mTHP), {bis[(hydroxymethoxy)methyl]phosphanyl}methanol (dTHP), {bis[(hydroxymethoxy)methyl]phosphanyl}methoxy)methanol (tTHP), {[bis(hydroxymethyl)phosphoryl]methoxy}methanol (mTHPO), {bis[(hydroxymethoxy)methyl]phosphoryl}methanol (dTHPO), ({bis[(hydroxymethoxy)methyl]phosphoryl}methoxy)methanol (tTHPO) and mixtures thereof; and a.3) is a mixture of condensation products resulting from the reaction of the at least one compound or mixture of compounds bearing a phosphorus atom a.2) as described above and the at least one compound bearing at least one basic nitrogen atom a.1); wherein the compound bearing at least one basic-nitrogen atom a.1) is selected from a.1i) melamine, trimethylol melamine, diethylenetriamine, tertiary octylamine, dimethylaminopropylamine, polyethyleneimines; a.1ii) those compounds of formula (VII) or formula (VIII); and a.1iii) mixtures thereof; wherein the compounds of formula (VII) are as follows R11-NH2(VII) wherein R11is selected from –H, -(C1-C3)Alkyl, (C1-C3)Alkyl-CO-, NH2-CO-, -(CH2)n-NH2, -CN, -NH2, -SO2NH2, cyclohexyl, phenyl, -SO2OH and -NHCONHNH2; wherein n is an integer from 1-18; and the compounds of formula (VIII) are as follows:wherein R12is selected from NH=C<, O=C< and S=C<; and R13is selectedfrom H, -CN, -NH2, -CONH2, -CONHCONH2, and -CONHCONHCONH2; or alternatively b. reacting, in the liquid polyol mixture and under polymerisation conditions, optionally in the presence of a catalyst, b.1) at least one co-reactant selected from b.1.i) an amine, an alkanolamine or a diol having an equivalent weight of up to 400 and at least one active hydrogen attached to a nitrogen or oxygen atom; b.1.ii) an olphosphine; with b.2) at least one polyisocyanate; wherein the liquid polyol mixture comprises at least one base polyol and at least one nitrogen-containing alkoxysilane-capped polyether polyol as defined according to the first aspect of the present invention and related embodiments.

[0084] .. In the context of the present invention, the term “equivalent weight”, when referring to the co-reactant, refers to the molecular weight per isocyanate reactive hydrogen atom in the molecule.

[0085] .. In accordance with some embodiments, optionally in combination with one or more features of the various embodiments described above or below, the modified polymer polyol dispersions are obtained using as polymeric particle precursors at least one co-reactant selected from b.1.i) an amine, an alkanolamine or a diol having an equivalent weight of up to 400 and at least one active hydrogen attached to a nitrogen or oxygen atom; and b.1.ii) an olphosphine.

[0086] .. In those embodiments wherein the polymeric particle precursor is as defined in b.1), then the modified polymer polyol dispersion thus obtained is a PIPA polyol or a PHD polyol.

[0087] .. If a PHD polymer polyol is desired, the PHD forming co-reactants may include amines, such as ammonia, anilines and substituted anilines, fatty amines and mixtures thereof. The PHD forming co-reactants may also include diamines, such as ethylenediamine and 1,6-hexamethylenediamine; alkanolamines; hydrazine, 2,6- diaminotoluene, 2,4-diaminotoluene, 4,4'-methylenedianiline, and mixtures thereof.

[0088] .. Particularly preferred co-reactants are those aromatic diamines such as 2,6- diaminotoluene, 2,4-diaminotoluene, and 4,4'-methylenedianiline, which may optionally be obtained as polyurethane recycling materials.

[0089] .. If a PIPA polymer polyol is desired, the PIPA forming co-reactants may include alkylene glycols, alkanolamines and olphosphines. In some embodiments, thePIPA forming co-reactants may include diols, such as diethylene glycol, triethylene glycol, and polyethyelene glycol; olphosphines, such as hydroxyalkylphosphines, hydroxyalkylphosphonium salts and hydroxyalkylphosphine oxides, and their derivatives; and alkanolamines, such as monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, 2-(2-aminoethoxyethanol), hydroxyethylpiperazine, monoisopropanolamine, diisopropanolamine and mixtures thereof. Other alkanolamines which may be considered include N-methylethanolamine, phenylethanolamine, glycol amine, and mixtures thereof.

[0090] .. It is also possible to provide a mixture of PHD and PIPA forming co- reactants to form hybrid PHD-PIPA particles.

[0091] .. The at least one PHD and / or PIPA polymer forming co-reactants are added to the blend in a concentration of between about 2 wt.% and about 80 wt.% of the total polyol blend weight, preferably between about 5 wt.% and about 60 wt.%. All individual values and subranges between about 2 wt.% and about 80 wt.% are included herein and disclosed herein.

[0092] .. In accordance with some embodiments catalytic quantities of organometallics may be used. Organometallic compounds useful as catalysts include those of bismuth, lead, tin, titanium, iron, antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel, cerium, molybdenum, vanadium, copper, manganese, zirconium, chromium, etc. Some examples of these metal catalysts include tin neodecanoate, bismuth nitrate, bismuth neodecanoate, lead 2- ethylhexoate, lead benzoate, lead oleate, dibutyltin dilaurate, tributyltin, butyltin trichloride, dimethyltin, dimethyltin dineodecanoate, stannic chloride, stannous octoate, stannous oleate, stannous riconoleate, dibutyltin di(2-ethylhexoate), zinc octoate, zinc riconoleate ferric chloride, antimony trichloride, antimony glycolate, tin glycolates, iron acetyl acetonate etc. The catalyst may accelerate the reaction of diisocyanate with the primary hydroxyl groups of the alkanolamines.

[0093] .. Therefore, in accordance with some embodiments, optionally in combination with one or more features of the various embodiments described above or below, the method of preparation of the modified polymer polyols comprises: i. mixing the at least one base polyol with the at least one nitrogen-containing alcoxysilane-capped polyether polyol as defined according to the first aspect of the present invention and related embodiments, thus obtaining a liquid polyol mixture; and ii. adding to the liquid polyol mixture obtained in i) simultaneously or sequentially, in any order, optionally in the presence of a catalyst, and under polymerisation conditions,b.1) at least one co-reactant selected from b.1.i) an amine, an alkanolamine or a diol having an equivalent weight of up to 400 and at least one active hydrogen attached to a nitrogen or oxygen atom, and b.1.ii) an olphosphine; b.2) at least one polyisocyanate; wherein the at least one co-reactant b.1) is selected from ammonia, aniline, (C1-C3)alkyl substituted aniline, fatty amines, ethylenediamine, 1,6- hexamethylenediamine, hydrazine, 2,6-diaminotoluene, 2,4-diaminotoluene, 4,4'- methylenedianiline, diethylene glycol, triethylene glycol, and polyethyelene glycol; olphosphines, such as hydroxyalkylphosphines, hydroxyalkylphosphonium salts, hydroxyalkylphosphine oxides and their derivatives; and alkanolamines, such as monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, 2-(2- aminoethoxyethanol), hydroxyethylpiperazine, monoisopropanolamine, diisopropanolamine, N-methylethanolamine, phenylethanolamine, glycol amine, and mixtures thereof.

[0094] .. In accordance with certain embodiments, optionally in combination with one or more features of the various embodiments described above or below, the method of preparation of the modified polymer polyols comprises: i. mixing the at least one base polyol with the at least one nitrogen-containing alkoxysilane-capped polyether polyol as defined according to the first aspect of the present invention and related embodiments, thus obtaining a liquid polyol mixture; ii. adding to the liquid polyol mixture obtained in i) simultaneously or sequentially, in any order a.1) the at least one compound bearing at least one basic-nitrogen atom characterized by the presence in the molecule of at least one hydrogen atom attached to a nitrogen atom; and either a.2) or a.3), wherein a.2) is at least one compound or a mixture of compounds bearing a phosphorus atom selected from I. [bis(hydroxymethyl)phosphanyl]methanol (THP) in a concentration from 0-100 mol%, from 0-99.9 mol%, from 20-95 mol%, from 30-90 mol%; from 35-85 mol%, from 50-75 mol% or from 60-72 mol%; II. a tetrakis(hydroxymethyl) phosphonium salt (THPX) in a concentration from 0-100 mol%, from 0-99.9 mol%, from 0-90.0 mol%, from 0.05 to 75 mol%, from 0.05-50 mol%, from 0.1-40 mol%, from 0.1-25 mol%,from 0.2-15 mol%, or from 0,5-10 mol % THPX; III. [bis(hydroxymethyl)phosphoryl]methanol (THPO) in a concentration from 0-100 mol%, from 0-99.9 mol%, from 0-40 mol%, from 1-15 mol%, from 2-12 mol%, or from 2-7 mol% THPO; IV. {[bis(hydroxymethyl)phosphanyl]methoxy}methanol (mTHP) in a concentration from 0-80 mol%, from 0.1-60 mol%, from 0.2-45 mol%, from 0.4-40 mol%, from 0.5-30 mol%, or from 1-25 mol% mTHP; V. {bis[(hydroxymethoxy)methyl]phosphanyl}methanol (dTHP) in a concentration from 0-30 mol%, from 0.1-20 mol%, from 0.2-15 mol% or from 0.25-10 mol% dTHP; VI. ({bis[(hydroxymethoxy)methyl]phosphanyl}methoxy)methanol (tTHP) in a concentration from 0-15 mol%, from 0.05-5 mol%, from 0.075-2 mol%, or from 0.1-1 mol% tTHP; VII. {[bis(hydroxymethyl)phosphoryl]methoxy}methanol (mTHPO) in a concentration from 0-20 mol%, from 0.05-10 mol%, from 0.1-6.5 mol%, from 0-6.1 mol% mTHPO; VIII. {bis[(hydroxymethoxy)methyl]phosphoryl}methanol (dTHPO) in a concentration from 0-10 mol%, from 0.05-5 mol%, from 0.1-1 mol% dTHPO; and IX. ({bis[(hydroxymethoxy)methyl]phosphoryl}methoxy)methanol (tTHPO) in a concentration from 0-4 mol %, from 0.01-1 mol%, from 0.05-0.2 mol%, from 0-0.5 mol% tTHPO; being the sum total of compounds bearing a phosphorus atom in the mixture 100 mol%. and a.3) is a mixture of condensation products resulting from the reaction of the at least one compound or a mixture of compounds a.2) as described above and at least one compound bearing at least one basic nitrogen atom a.1); wherein the compound bearing at least one basic-nitrogen atom a.1) is selected from - melamine, trimethylol melamine, diethylenetriamine, tertiary octylamine, dimethylaminopropylamine, polyethyleneimines; - those compounds of formula (VII) or formula (VIII); and - mixtures thereof.

[0095] .. Particular examples of compounds bearing at least one basic-nitrogen atom characterized by the presence in the molecule of at least one hydrogen atom attached to a nitrogen atom are NH3, primary aliphatic and alicyclic amines, aliphaticand alicyclic primary and secondary polyamines and aromatic primary, secondary and tertiary amines and polyamines, for example, cyanamide, guanidine, 2- cyanoguanidine, methylamine, ethylene diamine, diethylenetriamine, hexamethylendiamine, hydrazine, tertiary octylamine, dimethylaminopropylamine, cyclohexylamine, trimethylol melamine, urea, tiourea, aniline, and polyethyleneimines. NH3, cyanamide, melamine, urea, thiourea, diethylentriamine, hydrazine and ethylene diamine are particular preferred examples.

[0096] .. The skilled person in the art may know the method and the suitable media in order to solubilize, if necessary, the compound bearing at least one basic-nitrogen atom.

[0097] .. In accordance with a particularly preferred embodiment, the modified polymer polyol dispersions are those obtained using a mixture of hydroxyalkylphosphine (e.g. [bis(hydroxymethyl)phosphanyl]methanol (THP)) and its derivatives (including salts, oxides and hemiacetals) as polymeric particle precursors.

[0098] .. It is known that when a tetrakis(hydroxymethyl)phosphonium salt (THPX) is reacted with a base (e.g. KOH), then it may be obtained a mixture of THP, formaldehyde, the salt KX and water; additionally, depending on the basic conditions used, [bis(hydroxymethyl)phosphoryl]methanol (THPO, also known as tris(hydroxymethyl) phosphine oxide) may also be obtained as co-product together with THP; besides, THP and THPO may react with formaldehyde forming the corresponding hemiformals (mono-, di- and tri-substituted hemiformals of THP and THPO can be found as reaction products). In some cases, it is possible to perform the reaction with defect of base, in that case, non-reacted THPX may be present in the reaction media in combination with the obtained products. The quantity of THPO formed depends on the reaction conditions. Basic pH favours the concentration of THPO. Therefore, the product of the reaction between THPX and a base, depending on the conditions used, may be a complex mixture of phosphorus compounds (THP, THPO, their corresponding hemiformals and unreacted THPX), water, the corresponding salt and formaldehyde.

[0099] .. In accordance with some embodiments, optionally in combination with one or more features of the various embodiments described above or below, the mixture of compounds bearing a phosphorus atom comprises a tetrakis(hydroxymethyl)phosphonium salt (THPX) in a concentration from 0-100 mol%; wherein the counter-cation (X) of the salt is a monovalent, bivalent or trivalent ligand selected from chloride, bromide, iodide, sulphate, phosphate, hydrogen phosphate, dihydrogen phosphate, hydroxide, acetate, oxalate and citrate. [000100].. In certain embodiments, optionally in combination with one or morefeatures of the various embodiments described above or below, the hydroxyalkylphosphonium salt is selected from: tetrakis(hydroxymethyl) phosphonium chloride (THPC), bis[tetrakis(hydroxymethyl) phosphonium] sulphate (THPS), tetrakis(hydroxymethyl) phosphonium phosphate (THPP (3:1)), tetrakis(Hydroxymethyl)phosphonium monohydrogen phosphate (THPP (2:1)), tetrakis(Hydroxymethyl)phosphonium dihydrogen phosphate (THPP (1:1)), tetrakis(hydroxymethyl) phosphonium hydroxide (THPOH), tetrakis(hydroxymethyl) phosphonium oxalate (THPOx) and tetrakis(hydroxymethyl) phosphonium acetate (THPA). [000101].. Particular examples of hydroxyalkylphosphonium salts are tetrakis(hydroxymethyl) phosphonium chloride (THPC) and bis[tetrakis(hydroxymethyl) phosphonium] sulphate (THPS). [000102].. In the event that a hydroxyalkylphasphonium salt is used, it may be treated with a base in order to obtain the corresponding hydroxyalkylphosphine. The base may be an organic or an inorganic base; preferably selected from KOH, NaOH, Ca(OH)2, Mg(OH)2, Ba(OH)2, triethylamine (Net3), tributylamine (Nbu3). Alternatively, the hydroxyalkylphosphonium salt may be treated with a basic ion-exchange resin. Both, strong and weak ion exchange resins are suitable for the process. Examples of strong bases would be Amberlite®IRN78 or Amberlist®A26. Examples of weak bases would be Amberlite®IRA 67, Lewatit®MP-62 and Lewatit®VP OC1065. [000103].. As mentioned above, when the hydroxyalkylphosphonium salt is reacted with a base, there may be obtained the corresponding hydroxyalkylphosphine, the corresponding salt, the corresponding aldehyde and water, whereas other phosphorus compounds may appear as reaction products. THPO is usually obtained as co-product together with THP. Besides, THP and THPO may react with formaldehyde forming the corresponding hemiformals. Mono, di and tri-substituted hemiformals of THP and THPO may be found as reaction products. [000104].. In accordance with some embodiments, optionally in combination with one or more features of the various embodiments described above or below, the preparation of the modified polymer polyols comprises: i. mixing at least one tetrakis(hydroxymethyl) phosphonium salt (THPX) with an aqueous or alcoholic solution of a base, preferably at a temperature ranging from 0 ºC to 60 ºC; ii. optionally filtering out the resulting solution; iii. distilling off the solvent and volatiles, in particular formaldehyde, thus obtaining at least one compound or mixture of compounds bearing a phosphorus atom a.2) selected from the group consisting of[bis(hydroxymethyl)phosphanyl]metanol (THP), tetrakis(hydroxymethyl) phosphonium salt (THPX), [bis(hydroxymethyl)phosphoryl]methanol (THPO), ({[bis(hydroxymethyl)phosphanyl]methoxy}methanol (mTHP), {bis[(hydroxymethoxy)methyl]phosphanyl}methanol (dTHP), {bis[(hydroxymethoxy)methyl]phosphanyl}methoxy)methanol (tTHP), {[bis(hydroxymethyl)phosphoryl]methoxy}methanol (mTHPO), {bis[(hydroxymethoxy)methyl]phosphoryl}methanol (dTHPO), ({bis[(hydroxymethoxy)methyl]phosphoryl}methoxy)methanol (tTHPO) and mixtures thereof; iv. optionally filtering out the resulting solution, v. optionally oxydizing the product obtained in iii or the solution obtained in iv, wherein the oxidation may be done by simply thermal treatment in air atmosphere or by the use of oxidants as, for example, water peroxide, thus obtaining the mixture a.2) with a high content of oxydized components; vi. mixing the at least one base polyol with the at least one alkoxysilane group-modified compound as defined above, thus obtaining the liquid polyol mixture; vii. preparing the polymeric particles in the presence of the liquid polyol mixture obtained in vi by the reaction resulting from adding to the liquid polyol mixture obtained in vi simultaneously or sequentially in any order o the at least one compound bearing at least one basic-nitrogen atom a.1) characterized by the presence in the molecule of at least one hydrogen atom attached to a nitrogen atom and is selected from melamine, trimethylol melamine, diethylenetriamine, tertiary octylamine, dimethylaminopropylamine, polyethyleneimines, those compounds of formula (VII) or formula (VIII) as defined above, and mixtures thereof; and o the at least one compound or mixture of compounds bearing a phosphorus atom a.2) obtained in iii, the filtered solution obtained in iv, or mixtures thereof. [000105].. In accordance with certain embodiments, optionally in combination with one or more features of the various embodiments described above or below, the aqueous or alcoholic solution of a base used in step i. above may be selected from KOH, NaOH, Ca(OH)2, Mg(OH)2, Ba(OH)2, triethylamine (Net3), tributylamine (Nbu3). Alternatively, the hydroxyalkylphosphonium salt may be treated with a basic ion- exchange resin. Both, strong and weak ion exchange resins are suitable for theprocess. Examples of strong bases would be Amberlite® IRN78 or Amberlist® A26. Examples of weak bases would be Amberlite® IRA 67, Lewatit® MP-62 and Lewatit® VP OC1065. [000106].. In accordance with certain embodiments, optionally in combination with one or more features of the various embodiments described above or below, the distilling off step is performed under vacuum and at a temperature ranging from 25- 99ºC, preferably from 40-90ºC and more preferably from 60-80ºC. [000107].. Molar ratios to be used between the phosphorus bearing compound and the compound bearing at least one basic-nitrogen atom depend on the functionality of the compound bearing at least one basic-nitrogen atom. The skilled person would know how to adjust the molar ratios in the light of the description and examples of the present invention in order to obtain a solid product. [000108].. The compound bearing at least one basic nitrogen atom may be added to the reactor as a solid, or dissolved in a suitable solvent. Aqueous solutions of amines are preferred. [000109].. The reaction can be carried out at atmospheric pressure, vacuum or under pressure. Besides, the reaction can be carried out under inert (nitrogen, argon) or oxidant atmosphere (air). [000110].. Stirring must be vigorous in order to guarantee the formation of particles and to avoid agglomeration of the products. [000111].. With regard to the specific conditions for carrying out the process of the invention, the skilled person would know how to adjust the parameters of each of the steps indicated above in the light of the description and examples of the present invention. [000112].. In certain embodiments, optionally in combination with one or more features of the various embodiments described above or below, the process for the preparation of the modified polymer polyol dispersions comprises: i) mixing at least one base polyol with the at least one alkoxysilane group-modified compound as defined above, thus obtaining a liquid polyol mixture; ii) adding to the liquid polyol mixture obtained in i. simultaneously or sequentially, in any order ^ the at least one compound bearing at least one basic-nitrogen atom a.1) characterized by the presence in the molecule of at least one hydrogen atom attached to a nitrogen atom as defined above; and ^ the mixture of condensation products a.3) as defined above. [000113].. The condensation products a.3) resulting from the reaction of the at least one compound or mixture of compounds a.2) and at least one compound bearing atleast one basic nitrogen atom a.1); wherein the condensation rection is carried out at a temperature ranging from 2-140ºC, preferably from 25-120ºC, more preferably from 40-100ºC, being particularly preferably from 60-90ºC. The skilled person in the art may know how to adjust the temperature conditions in view of the compound a.1) used in the method. [000114].. In accordance with certain particular embodiments, optionally in combination with one or more features of the various embodiments described above or below, the preparation of the modified polymer polyols comprises: i) mixing at least one base polyol with the at least one alkoxysilane group-modified compound as defined above, thus obtaining a liquid polyol mixture; ii) adding to the liquid polyol mixture obtained in i) simultaneously or sequentially, in any order ^ the at least one compound bearing at least one basic-nitrogen atom a.1) which is selected from: - melamine, trimethylol melamine, diethylenetriamine, tertiary octylamine, dimethylaminopropylamine, polyethyleneimines; - those compounds of formula (VII) wherein R11is selected from H, methyl, - CN, CH₃ CO-, NH2-CO-; - those compounds of formula (VIII) wherein R12is selected from O=C<; S=C<; and R13es H; and - mixtures thereof and ^ the mixture of condensation products a.3) obtainable at a temperature ranging from 2-140ºC, preferably from 25-120ºC, more preferably from 40-100ºC, being particularly preferably from 60-90ºC. [000115].. In accordance with some embodiments, optionally in combination with one or more features of the various embodiments described above or below, the preparation of the modified polymer polyols comprises: i) mixing at least one tetrakis(hydroxymethyl) phosphonium salt (THPX) with an aqueous or alcoholic solution of a base, preferably at a temperature ranging from 0 ºC to 60 ºC; ii) optionally filtering out the resulting solution; iii) distilling off the solvent and volatiles, thus obtaining the at least one compound or mixture of compounds a.2) of compounds bearing a phosphorus atom as defined above, iv) optionally filtering out the resulting solution; v) optionally oxidizing the product obtained in iii or the solution obtainedin iv, wherein the oxidation may be performed by simple by thermal treatment in air atmosphere or by the use of oxidants as, for example, water peroxide, thus obtaining the at least one compound or mixture of compounds a.2) with a high content of oxydized components; vi) reacting the at least one compound or mixture of compounds a.2) as obtained in iii), the filtered solution obtained in iv), the oxidized mixture as obtained in v) or mixtures thereof with at least one compound bearing at least one basic-nitrogen atom a.1) characterized by the presence in the molecule of at least one hydrogen atom attached to a nitrogen atom and is selected from melamine, trimethylol melamine, diethylenetriamine, tertiary octylamine, dimethylaminopropylamine, polyethyleneimines, those compounds of formula (VII) or formula (VIII) as defined above, and mixtures thereof; preferably at a temperature ranging from 2 to 140 ºC, preferably from 25 to 120 ºC, more preferably from 40 to 100 ºC, and most preferably from 60 to 90 ºC thus obtaining a mixture of condensation products a.3); vii) mixing the at least one base polyol with the at least one alkoxysilane group-modified compound as defined above, thus obtaining a liquid polyol mixture; viii) preparing the polymeric particles in the presence of the liquid polyol mixture obtained in vii) by the reaction resulting from adding to the liquid polyol mixture obtained in vii), simultaneously or sequentially in any order o the at least one compound bearing at least one basic-nitrogen atom a.1) characterized by the presence in the molecule of at least one hydrogen atom attached to a nitrogen atom which is selected from melamine, trimethylol melamine, diethylenetriamine, tertiary octylamine, dimethylaminopropylamine, polyethyleneimines, those compounds of formula (VII) or formula (VIII) as defined above, and mixtures thereof; and o the mixture of condensation products a.3) obtained in vi). [000116].. In accordance with some particular embodiments, optionally in combination with one or more features of the various embodiments described above or below, the aqueous or alcoholic solution of a base used in step i) above is selected from KOH, NaOH, Ca(OH)2, Mg(OH)2, Ba(OH)2, triethylamine (Net3), tributylamine (Nbu3). Alternatively, the hydroxyalkylphosphonium salt may be treated with a basic ion-exchange resin. Both, strong and weak ion exchange resins are suitable for theprocess. Examples of strong bases would be Amberlite®IRN78 or Amberlist®A26. Examples of weak bases would be Amberlite®IRA 67, Lewatit®MP-62 and Lewatit®VP OC1065. [000117].. In accordance with certain particular embodiments, optionally in combination with one or more features of the various embodiments described above or below, the condensation products resulting from the reaction of the at least one compound or mixture of compounds a.2) as obtained in step iii), the filtered solution obtained in iv), the oxydized mixture as obtained in step v or mixtures thereof, and the at least one compound bearing at least one basic nitrogen atom a.1) which is selected from melamine, trimethylol melamine, diethylenetriamine, tertiary octylamine, dimethylaminopropylamine, polyethyleneimines, those compounds of formula (VII) or formula (VIII) as described above, and mixtures thereof, are obtainable at a temperature ranging from 2 to 140 ºC, preferably from 25 to 120 ºC, more preferably from 40 to 100 ºC, and most preferably from 60 to 90 ºC. The skilled person in the art would know how to adjust the temperature and reaction time in the light of the description and examples herein described in order to complete the condensation reaction. [000118].. In some embodiments, optionally in combination with one or more features of the embodiments described above or below, the modified polymer polyol dispersion obtained as described herein, may be purified by stripping under reduced pressure; removing a solid comprising a complex mixture of compounds comprising the unreacted compounds bearing at least one basic-nitrogen atom and reaction sub- products; and recovering a purified modified polymer polyol dispersion. The resulting purified modified polymer polyol dispersion may be used in the preparation of polyurethane foams which show an improvement in porosity and wet compression set; as well as polyisocyanurate foams which show an improvement in reaction to fire according to DIN 4102-1. [000119].. Thus, according to some embodiments, optionally in combination with one or more features of the embodiments described above or below, the method for the preparation of the modified polymer polyol dispersion obtained as described above, further comprises: i) purifying the crude modified polymer polyol obtained in (1) by stripping under reduced pressure, removing a solid comprising a complex mixture of compounds comprising the unreacted compounds bearing at least one basic- nitrogen atom and reaction sub-products; and ii) recovering the purified modified polymer polyol dispersion.[000120].. Without being bounded by theory, the solid removed comprises a complex mixture of compounds comprising the unreacted compounds bearing at least one basic-nitrogen atom and reaction byproducts, such as formaldehyde and different oligomers formed as a reaction sub-products. [000121].. In accordance with a particular embodiment, the stripping step may be carried out by bubbling and inert gas, stream, or air into the reactor chamber or into the stripping column wherein the crude modified polymer polyol has been transferred, removing the solid captured in a cold trap, and recovering the purified modified polymer polyol. [000122].. Alternative known methods, as for example thin film or falling film evaporation, of removing such solid comprising a complex mixture of compounds comprising the unreacted compounds bearing at least one basic-nitrogen atom and reaction sub-products may also be applied instead of a stripping process. Additional examples of alternative methods are known by the skilled in the art. [000123].. The stable modified polymer polyol dispersion obtained according to the above-mentioned methods, is a polyol which has finely dispersed particles of a polymer with high content of nitrogen and phosphorus. [000124].. In some embodiments, optionally in combination with one or more features of the various embodiments described above or below, the stable modified polymer polyol dispersion comprises from 5 wt% to 95 wt%, from 10 wt% to 90 wt%, from 15 wt% to 80 wt%, from 20 wt% to 70 wt% of dispersed polymeric particles. [000125].. Accordingly, the polymeric particles dispersed in the at least one polyol have a phosphorus content from 0,1 to 50 wt%; preferably from 5 to 40 wt% and most preferably from 13 to 35 wt%. The polymeric particles dispersed in the at least one polyol have a nitrogen content from 0,1 to 40 wt%; preferably from 5 to 40 wt% and most preferably from 7 to 30 wt%. In conjunction the sum of the content of nitrogen and phosphorus is from 0,1 to 90 wt %; preferably from 10 to 70 wt% and most preferably from 20 to 60 wt%. [000126].. In accordance with a particular embodiment of the present disclosure, the polymeric particles dispersed in the at least one base polyol, may be further oxidized using suitable oxidizing agents such as manganate, permanganate, peroxides and molecular oxygen; preferably the oxidizing agent is molecular oxygen and / or hydrogen peroxide. [000127].. The oxidation step is performed by introducing at least one oxidizing agent in the media once the polycondensation reaction has occurred. If hydrogen peroxide is used as oxidating agent, this one may be added in aqueous solution to the modified polymer polyol containing the stable dispersion of polymeric particles in thebase polyol. If molecular oxygen is used as the oxidant, the oxidation may be done bubbling air or oxygen into the system once the polymeric particles are formed. [000128].. The polyol composition according to the present invention comprises polymeric particles of which at least 90 % by volume has a particle size of 30 µm or less, preferably from 0.5 µm to 20 µm, more preferably from 0.6 µm to 15 µm, still more preferably from 0.8 µm to 10 µm (particle size is measured using a mastersizer 3000, from Malvern Instruments, with a hydro SM dispersion, using ethanol as eluent). [000129].. The particle size distribution may be trimodal, bimodal, monomodal and also different independent distributions may be found. [000130].. The polymeric modified polyols of the present disclosure are useful for the preparation of polyurethane materials such as polyurethane foams, adhesives, elastomers, sealants and coatings; being preferred those with flame retardant properties. [000131].. With regard to the specific conditions for carrying out the processes of the invention, the skilled person would know how to adjust the parameters of each of the steps indicated above in the light of the description and examples of the present invention. Polyurethane material [000132].. It is also an object of the present invention a process for the preparation of polyurethane material, wherein the process comprises reacting at least one polyisocyanate with an isocyanate-reactive component which comprises at least one stabilized modified polymer polyol dispersion as defined in the corresponding aspect of the invention and related embodiments, in the presence of at least one catalyst and optionally additives. [000133].. It is also an object of the present invention, the polyurethane material obtainable by the process as defined herein. [000134].. The at least one polyisocyanate which may be used in the present invention include aliphatic, cycloaliphatic, arylaliphatic and aromatic isocyanates. Examples of suitable aromatic polyisocyanates include the 4,4’-, 2,4’ and 2,2’- isomers of diphenylmethane diisocyante (MDI), blends thereof and polymeric and monomeric MDI blends, toluene-2,4- and 2,6-diisocyanates (TDI), m- and p- phenylenediisocyanate, chlorophenylene-2,4-diisocyanate, diphenylene-4,4’- diisocyanate, 4,4’-diisocyanate3,3’-dimehtyldiphenyl, 3-methyldiphenyl-methane-4,4’- diisocyanate and diphenyletherdiisocyanate and 2,4,6-triisocyanatotoluene and 2,4,4’-triisocyanatodiphenylether. Mixtures of polyisocyanates may be used, such asthe commercially available mixtures of 2,4- and 2,6-isomers of toluene diisocyanates. A crude polyisocyanate may also be used in the practice of this invention, such as crude toluene diisocyanate obtained by the phosgenation of a mixture of toluene diamine or the crude diphenylmethane diisocyanate obtained by the phosgenation of crude methylene diphenylamine. TDI / MDI blends may also be used. Examples of aliphatic polyisocyanates include ethylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane 1,4-diisocyanate, 4,4’- dicyclohexylmethane diisocyanate, saturated analogues of the above mentioned aromatic polyisocyanates and mixtures thereof. [000135].. The polyisocyanate may be used at an isocyanate index of from 60 to 140, preferably from 80 to 120 and most preferably from 90 to 110. The isocyanate index is defined as the ratio of isocyanate-groups over isocyanate-reactive hydrogen atoms present in a polyurethane formulation. Thus, the isocyanate index expresses the percentage of isocyanate actually used in a formulation with respect to the amount of isocyanate theoretically required for reacting with the amount of isocyanate-reactive hydrogen used in a formulation. [000136].. In the preparation of polyurethane foams, polyisocyanates, water and additives conventionally used in the manufacture of polyurethane foams may be used in combination with the modified polymer polyols of the present disclosure, in amounts and under reaction conditions which will vary depending on the type and desired properties of the polyurethane foam to be prepared. The skilled person knows different types of reactants, catalysts and conditions necessary to prepare polyurethane foams. [000137].. In the preparation of polyurethane foams, polyisocyanates, water and additives conventionally used in the manufacture of polyurethane foams may be used in combination with the modified polymer polyols of the present disclosure, in amounts and under reaction conditions which will vary depending on the type and desired properties of the polyurethane foam to be prepared. The skilled person knows different types of reactants, catalysts and conditions necessary to prepare polyurethane foams. [000138].. The blowing agent may be selected from any blowing agent commonly known in the art. The main blowing agent is the carbon dioxide generated by the decarboxylation of the carbamic acid generated by the reaction of water with the isocyanate. Alternative blowing agents (ABA) such as liquid carbon dioxide, methylene chloride, HCFC, pentane, etc. may be used according to legislation and targeted foam properties. [000139].. The blowing agent concentration in a expandable polymer composition ispreferably comprised from 0 % w / w to 120 % w / w relative to total expandable polymeric mixture weight; more preferably from 0 % w / w to 40 % w / w; yet more preferably from 0 % w / w to 10 % w / w. [000140].. Any known catalyst may be used, including aminic compounds, such as triethylenediamine, N-methylmorpholine, N,N-dimethylcyclohexylamine, pentamethyldiethylenetriamine, tetramethylethylenediamine, bis(dimethylaminoethyl)ether, 1 -methyl-4-dimethylaminoethyl-piperazine, 3-methoxy- N- dimethylpropylamine, N-ethylmorpholine, dimethylethanolamine, N- cocomorpholine, N,N-dimethyl-N’,N’-dimethyl isopropylpropylenediamine, N,N- diethyl-3-diethylamino- propylamine and dimethylbenzylamine. Metal catalyst based on tin, zinc, bismuth and other metals may be used in the foam formulations such as for example tin octoate, tin dibutyldilaurate, zinc octoate, and other similar compounds. [000141].. The amount of catalysts may vary from 0 to 4% in the formulation; preferably in the range 0 to 2%, most preferably from 0 to 1%. Another option is the use of autocatalytic polyols, based on tertiary amine initiatiors, replacing the amine catalysts, hence reducing volatile organic compounds in the foam. [000142].. Among the additional additives which may be employed in preparing polyurethane polymers are fillers (for example, talc, silica, titania, magnesia, calcium carbonate, carbon black, graphite, magnesium silicate or clays such as kaolinite and montmorillonite); flame retardants (for example, halogenated flame retardants, such as hexabromocyclododecane and brominated polymers, or phosphorus flame retardants such as triphenylphosphate, dimethyl methylphosphonate, red phosphorus or aluminium diethyl phosphinate); acid scavengers (for example, calcium stearate, magnesium oxide, zinc oxide, tetrasodium pyrophosphate or hydrotalcite); antioxidants (for example, sterically hindered phenols, phosphites and mixtures thereof ); and pigments and blowing agent stabilizers. A silicone surfactant may be necessary to stabilize the foam formulation, those products are available from the main actors of the market such as EVONIK, MOMENTIVE, AIR PRODUCTS, STRUKSILON, etc. [000143].. The polyurethane foam may be prepared by any known method. Thus, for example, the polyurethane foam may be formed by the so-called prepolymer method, in which a stoichiometric excess of the polyisocyanate is first reacted with the high equivalent weight polyol to form a prepolymer, which is in a second step reacted with a chain extender and / or water to form the desired foam. Frothing methods may also be suitable. The so-called one-shot methods may also be used. In such one-shot methods, the polyisocyanate and all isocyanate-reactive components aresimultaneously brought together and caused to react. Three widely used one-shot methods which are suitable for use herein include slabstock foam processes, high resiliency slabstock foam processes, molded foam methods and box foam methods. [000144].. Polyurethane foams prepared from the stable modified polymer polyols of the present disclosure may show a density from 4 to 120 kg / m3, preferably 15 to 80 kg / m3, most preferably 20 to 60 kg / m3. [000145].. In the context of the present disclosure, the term “modified polymer polyol” also termed as “polymer-polyol dispersions” or “polymeric polyols”, refers to a dispersion of polymeric particles, i.e a dispersion of an organic filler, in a continuous phase made up of one or more compounds having multiple hydroxyl groups (“base polyol”). [000146].. In the context of the present invention, the term functionality when referring to the compound bearing a basic-nitrogen atom is used herein to indicate the number average functionality (number of hydrogen atoms attached to nitrogen atoms per molecule) of the compound. The term “functionality”, when referring to base polyols, is used herein to indicate the number average functionality (number of hydroxyl groups per molecule) of the polyol composition, on the assumption that it is the number average functionality (number of active hydrogen atoms per molecule) of the initiator(s) used in their preparations. Although in practice the real functionality will often be somewhat less because of some terminal unsaturation, for the purpose of characterizing the base polyols, the functionality of the polyol is the functionality of the initiator(s) used for its preparation. [000147].. In the context of the present invention, the term “iOH” refers to the hydroxyl number (iOH), defined as the number of milligrams of potassium hydroxide required for the complete hydrolysis of the fully phthalylated derivative prepared from 1 gram of polyol. The hydroxyl number is determined according to ASTM D4274 – 16. [000148].. In accordance with the context of the present disclosure, the terms “stable polyol” or “stable modified polymer polyols” refers to a dispersion of polymeric particles in the at least one polyol which does not settler out, or at least which will remain in dispersion during mixing with other foam forming ingredients. [000149].. In accordance with some examples of the present disclosure, the process should permit highly stable modified polymer polyols to be produced, in which the dispersed particles are small (and therefore less prone to settling). Surprisingly, the modified polymer polyols are stable even when the base polyol is a non-reactive polyether polyol, i.e. has mainly secondary hydroxyl groups. [000150].. In the context of the present invention, the term “molecular weight” of the polyol is calculated using the following equationwherein “functionality” represents the functionality of the polyol, i.e. the average number of hydroxyl groups per molecule of polyol; and hydroxyl number (iOH) is calculated according to ASTM D4274 – 16. [000151].. In the context of the present invention, the term “equivalent molecular weight” of the polyol is calculated using the following equation: EW polyol = MW polyol / functionality = 56100 / Hydroxyl number (iOH) [000152].. In the context of the present invention, the term “weight-average molecular weight” is measured by GPC. [000153].. In the context of the present invention viscosity measurements (in mPa.s) are obtained at 25 ºC using a Haake™ Viscotester™ rheometer. [000154].. The solid content of the modified polymer polyol is calculated using the following equation[000155].. In the context of the present disclosure, the term “percentage (%) by weight” refers to the percentage of each ingredient of the combination or composition in relation to the total weight. [000156].. The modified polymer polyol “obtainable by” the process of the invention is used here to define the modified polymer polyol by the process for obtaining it and refers to the product obtainable by the preparation as defined herein. For the purposes of the invention the expressions “obtainable”, “obtained” and equivalent expressions are used interchangeably, and in any case, the expression “obtainable” encompasses the expression “obtained”. [000157].. For the purposes of the invention, any ranges given include both the lower and the upper end-points of the range. Ranges given, such as temperatures, times, sizes, and the like, should be considered approximate, unless specifically stated. [000158].. Although only a number of examples have been disclosed herein, other alternatives, modifications, uses and / or equivalents thereof are possible.Furthermore, all possible combinations of the described examples are also covered. Thus, the scope of the present disclosure should not be limited by particular examples, but should be determined only by a fair reading of the claims that follow. [000159].. The following examples are provided to illustrate the embodiments of the invention, but are not intended to limit the scope thereof. All parts and percentages are by weight unless otherwise indicated. [000160].. The modified polymer polyols of the invention can be used to prepare polyurethane foams that may meet one or more FR (Flame Resistance) standards, such as British Standard flammability test (BS 5852 - ignition source 5) using a wooden assembly (referred to as a crib) as a source of ignition; Crib 5 flammability test (BS 5852, ignition source 5), using a wooden crib prepared with 18 wooden sticks having dimensions of 40 x 6.5 x6.5 mm.1.4 mL of Propan-2-ol is added to the lint to start the test. The pass / fail criteria are: (i) no more than 60 grams of weight loss per specimen, (ii) self-extinguishing within 10 minutes from the ignition of the specimen (iii) flame cannot penetrate the full thickness of the sample, and (iv) no more than 10 cm of damage on either side of the ignition source (measured as no more than 25 cm of damage in a width-wise direction in which the crib structure having a width of 5 cm is presumed as the center. EXAMPLES [000161].. The following materials were used: − The following materials were used: − Polyol A – A sorbitol (functionality 6) initiated polyether polyol (PO / EO) with a hydroxyl number of 29.5 mgKOH / g, a content of polyethylene oxide terminal blocks of 16.2 wt%, a 81 % of primary OH groups and a viscosity at 25 ºC of 1500 mPa s − Polyol B - A glycerol (functionality 3) initiated polyether polyol (100 % PO) with a hydroxyl number of 56 mgKOH / g and a viscosity at 25 ºC of 470 mPa s. Polyol B is a non-reactive polyol. − Polyol C - A glycerol (functionality 3) initiated polyether polyol (PO / EO) with a hydroxyl number of 48 mgKOH / g, a content of polyethylene units, randomly distributed along the central backbone of the polyol, of 12 wt% and a viscosity at 25 ºC of 560 mPa s. Polyol C is a non-reactive polyol. − THPS – Tetrakis(hydroxymethyl)phosphonium sulphate salt (70-75 wt% in water) . Available from Sigma Aldrich. − KOH – Potassium hydroxide (≥85 %). Available from Sigma Aldrich.− DBTL- Dibutyltin dilaurate (95 %). Available from Sigma Aldrich. − 3-(Triethoxysilyl)propyl isocyanate (95 %). Available from Sigma Aldrich. − Kosmos T900 – Tin (II) neodecanoate available from Evonik Industries. − Tetrafluoroboric acid solution (48 %). Available from Sigma Aldrich. − Geniosil GF-80 - 3-Glycidoxypropyltrimethoxysilane (Trimethoxy({3-[(oxiran-2- yl)methoxy]propyl})silane) (≥98 %) was supplied by Wacker − Geniosil GF-91 - N-(2-Aminoethyl)-3-aminopropyltrimethoxysilane was supplied by Wacker. − Triethanolamine (TEOA) (≥99,0 %). Available from Sigma Aldrich. − Tegoamin® 33 - A solution of 33 wt% triethylene diamine in dipropyleneglycol available from Evonik Industries. − Tegoamin® BDE - Solution of 70 % Bis(2-dimethylaminoethyl)ether in dipropyleneglycol available from Evonik Industries. − Niax L-620LV - Silicone surfactant for polyurethane foam available from Momentive − TCPP - Tris (chloroisopropyl) phosphate. Available from Shekoy chemicals. − TDI-80 – Toluene diisocyanate (80 / 20). Available from Borsodchem − UR – Urea (98 %). Available from Sigma Aldrich.of NAD-stabilizer 1. [000162]..149.98 g of Polyol A, 2.98 g of 3-(Triethoxysilyl)propyl isocyanate and 44 mg of dibutyltin dilaurate were placed in a 3 necked glass flask reactor equipped with mechanical stirring. The temperature was raised at 80 ºC, under stirring and nitrogen atmosphere, and maintained for 30 min. The complete disappearance of the isocyanate band in the infrared spectra confirmed the completion of the reaction. A transparent liquid was obtained as reaction product.of NAD-stabilizer 2. [000163].. In a glass reactor equiped with mechanical stirrer 85 mg of Tetrafluoroboric acid solution (48 %) were added to 150.16 g of Polyol A. After 5 minutes of stirring, 3,46 g of 3-Glycidoxypropyl-trimethoxysilane were added into the mixture and the reaction temperature was raised to 50 ºC. The temperature was maintained at 50 ºC for 3 h. The resulting product was a transparent liquid.according to the invention). [000164].. In a 3 necked glass flask reactor equipped with mechanical stirring 179.97 g of polyol A and 626 mg of Tetrafluoroboric acid solution (48 %) were loaded. Themixture was homogenized by strirring for 5 min and then 3.60 g of 3-Glycidoxypropyl- trimethoxysilane were added. While stirring, the temperature was raised to 50 ºC. The reaction was maintained at 50 ºC under stirring for 3 h. Then 8,69 g of N-(2- Aminoethyl)-3-aminopropyltrimethoxysilane and 2,0 g of water were added and the temperature raised at 60 ºC. The reaction was maintained for 16 h. The product obtained is a translucent liquid. Example 2 Preparation of THP mixture A [000165]..1090,8 g of THPS (tetrakis(hydroxymethyl) phosphonium sulfate solution (75%)) were placed in a jacketed glass reactor equipped with a mechanical stirrer. A solution of KOH (198,9 g of KOH flakes in 200 g of water) was added slowly under stirring over the THPS. During the KOH addition step the temperature was maintained below 25 ºC. [000166].. A slurry containing sulphate salt was obtained. The solid was filtered out and the volatile compounds of the resulting solution were distilled off in the reactor at 100 mbar. Nitrogen was fluxed during the distillation through a sparger. The temperature in the distillation process was kept at 50 ºC. Once all the water was distilled, the temperature was raised at 80 ºC and the product was stripped with nitrogen for 4 hours under vacuum. [000167].. A turbid liquid product was obtained which was filtered again under nitrogen atmosphere to obtain a transparent product. [000168].. The % molar distribution of the THP derivatives was determined by 31P- NMR. Results are shown in Table 1. Other minor components may be present. Table 1. mol % THPO mTHPO dTHPO tTHPO THPS THP mTHP dTHP tTHP 8.32 2.28 0 0 0.63 63.45 22.78 2.54 0 Preparation of PIPA polyols [000169].. The PIPA polyols were prepared according to the following procedure: [000170].. In a glass reactor equipped with a mechanical stirrer polyol B was loaded together with the NAD-stabilizer then the triethanolamine was added. The mixture was stirred at 500 rpm for one minute ant then the catalyst was added into the reactor and stirred for 30 seconds. Then the stirring speed was raised to 2000 rpm and the total amount of isocyanate was added into the reactor at one time (in a single step).Results are shown in Table 2. Table 2 Polyol- NDA -Stabilizer Catalyst TEOA Example B TDI-80 Type g (g) Type (g) (g) Comparative 240.05 None 0 28.35 DBTDL 0.15 31.8 example 3 Example 3 231.1 Example 1 9,3 28.35 DBTDL 0.15 31.8 Example 4 168.0 Example 1 12.1 56.46 DBTDL 0.3 63.3 Kosmos Example 5 168.0 Example 1 12.0 56.46 0.3 63.3 T900 Comparative Comparative Kosmos 168.0 12.0 56.46 0.3 63.3 example 4 example 1 T900 Comparative Comparative Kosmos 168.0 12.0 56.46 0.3 63.3 example 5 example 2 T900 Kosmos Example 6 108.0 Example 1 12.0 56.46 0.3 63.3 T900 Kosmos Example 7 68.0 Example 1 12.0 56.46 0.3 63.3 T900 [000171].. Previous examples were prepared adding the isocyanate at one time (one step). In the following examples the isocyanate was added to the reactor progressively in a period of time. Results are shown in Table 3. Table 3 TEOA Polyol- NDA -Stabilizer Catalyst TDI-80 (g) Example B Addition (g) Type g Type g g time (sec) Kosmos Example 8 168.0 Example 1 12.0 56.46 0.3 63.3 60 T900 Kosmos Example 9 168.0 Example 1 12.0 56.46 0.3 63.3 300 T900 [000172].. The following examples were prepared in absence of catalyst leading a finely dispersed polyols (Table 4) Table 4 Example NDA -Stabilizer Catalyst TDI-80Polyol- Addition TEOA B Type g Type (g) (g) time (sec) (g) (g) Example 231.13 Example 1 9.1 28.21 None 0 31.81 60 10 Example 168 Example 1 12 56.46 None 0 63,3 60 11 [000173].. Following the procedure described for PIPA Polyol preparation, TEOA was replaced by the THP mixture prepared in the example 2 to prepare non-reactive phosphorus containing PIPA polyols (Table 6). Table 5 Polyol- THP mixture NDA -Stabilizer Catalyst TDI-80 Example B Example 2 (g) (g) Type g Type (g) (g) Comparative Kosmos 231.2 None 0 56.46 0.3 63.3 example 6 T900 Comparative Comparative Kosmos 168.0 12.0 56.46 0.3 63.3 example 7 example 1 T900 Comparative Comparative Kosmos 168.0 12.0 56.46 0.3 63.3 example 8 example 2 T900 Kosmos Example 12 108.0 Example 1 12.0 56.46 0.3 63.3 T900 [000174].. In the comparative examples 3, 4, 5, 6, 7 and 8 a white solid precipitated in less than 1 minute after the addition of the isocyanate. When the NAD-dispersant prepared in example 3 was used finely dispersed and stable PIPA polyols were obtained (Table 6). Table 6 Theoretical Particle size distribution solid Viscosity Example content (% (cps) Dx(10) Dx(50) Dx(90) D[4,3] wt) Two independent distributions with a largest fraction Example 3 20 1509 0.25 0.65 3.07 1.36 between 0.99 and 4.58 µm centered on 2.42 µm. Asmaller fraction has 0.11 and 0.99 µm particles, centered on 0.36 µm Monomodal distribution with particles in the Example 4 40 4082 2.55 3.64 5.43 3.84 range between 1.65 and 7,64 µm centered on 3.12 µm. Monomodal distribution with particles in the Example 5 40 2653 2.52 3.68 5.69 3.91 range between 1.45 and 9,86 µm centered on 3.12 µm. Two independent distributions with a largest fraction between 1.65 and 9.86 µm centered Example 6 50 6623 2.51 4.13 6.46 4.24 on 4.03 µm. A smaller fraction has 0.28 and 0.99 µm particles, centered on 0.52 µm Two independent distributions with a largest fraction between 1.45 and 16.4 µm centered Example 7 60 33123 1.11 5.1 9.46 5.43 on 5.21 µm. A smaller fraction has 0.24 and 1.28 µm particles, centered on 0.52 µm Monomodal distribution with Example 8 40 2830 0.462 0.907 1.61 0.98 particles in the range between 0.19 and 2.42 µmcentered on 0.99 µm. Monomodal distribution with particles in the Example 9 40 2667 0.378 0.798 1.53 0.88 range between 0.17 and 2.42 µm centered on 0.87 µm. Bimodal distribution with a largest fraction between 0.09 and 0.99 µm centered Example 10 20 2099 0.216 0.525 2.6 1.05 on 0.36 µm. A smaller fraction has 0.99 and 5.21 µm particles, centered on 2.13 µm Monomodal distribution with particles in the Example 11 40 2525 2.14 2.93 4.14 3.04 range between 1.28 and 2.75 µm centered on 5.92 µm. Trimodal distribution with a largest fraction between 0.594 and 6.72 µm centered on 2.13 µm. A medium fraction has 0.07 Example 12 20 9981 0.20 1.06 3.49 1.95 and 0.59 µm particles, centered on 0.24 µm. A smaller fraction has 6.72 and 35.3 µm particles, centered on 14.5 µm Preparation of modified polymer polyols[000175].. The modified polymer polyols were prepared using the THP mixture prepared in example 2 using the following recipe: [000176].. The polyol C and the NAD dispersant were placed in a jacketed glass reactor equipped with a mechanical stirrer. The temperature was raised to 80 ºC and the THP mixture obtained in the example 10 was added. The mixture was stirred for 30 min at 80 ºC and then a solution of urea in water was added under vigorous stirring. After 5 min of stirring the liquid volatile compounds were distilled off at 350 mbar. Once all the liquid compounds were distilled, the temperature was raised up to 160 ºC and the product was stripped off with nitrogen. This stripping process was performed at 150 mbar. [000177].. The following table 7 summarize different examples done following the described procedure. Table 7 Nitrogen NAD-stabilizer Polyol THP mixture containing Water compound Example Type g Type g g Type g g Comparative Comparative Polyol C 207.4 17.6 186.6 Urea 127.8 65.2 example 9 example 1 Comparative Comparative Polyol C 213.7 18.14 192.2 Urea 131.7 67.2 example 10 example 2 Example 13 Polyol C 210.5 Example 1 17.75 189.5 Urea 129.7 66.2 [000178].. The particle size obtained in comparative examples 9 and 10 was found to be bigger than in example 13 Table 8 Particle size distribution Example Dx(10) Dx(50) Dx(90) D[4,3] Three independent distributions with a largest fraction between 7,64 and 98.1 µm centered Comparative on 31.1 µm. A medium fraction has 0.24 and 12.8 29.7 52.6 31.1 example 9 1.45 µm particles, centered on 0.52 µm The smaller fraction has 1.88 and 6.72 µm particles, centered on 4.03 µmTwo independent distributions with a largest Comparative fraction between 5.21 and 40.1 µm centered 8.1 15.9 26.2 16.3 example 10 on 16.4 µm. A smaller fraction has 0.24 and 1.13 µm particles, centered on 0.52 µm Bimodal distribution with a largest fraction between 0.77 and 2.75 µm centered on 1.45 Example 13 0.371 1.02 1.93 1.08 µm. A smaller fraction has 0.17 and 0.77 µm particles, centered on 0.46 µm Polyurethane flexible foams. [000179].. Polyurethane foams were prepared according to the following procedure: [000180].. Prepare the polyols and isocyanate parts in a 1.2 liter beaker and place it in the mixer [000181].. Start the agitation [000182].. Increase the mixing speed for 30 seconds until reaching 2000 rpm. [000183].. Stir for a further 25 seconds at 2000 rpm, add the catalyst and immediately the activator, both previously weighed in syringes appropriate to the volume to be added, so that after 60 seconds of stirring all the components are added [000184].. The resulting mixture is poured into an aluminum mold at 23 ºC protected by kraft paper and the mixture is allowed to react in the mold for a period of 5 minutes, rise profile was monitored by a Foamat equipment. [000185].. The resulting foam is removed from the mold, and allowed to cure in an oven at 100ºC for 15 minutes. After that curing step the foam is storred at 23 ºC and 50 % relative humidity for at least 24h. [000186].. [000187].. The compositions prepared are showed in the following table 9. Table 9 Example 14 Polyol B 62.5 Example 10 37.5 Water 2.7 Tegoamin® BDE 0.038 TEDA_33 0.113 Kosmos T900 0.27 Niax L-620LV 0.70 TCPP 22 TDI-80 36.29 Density, Kg / m3 ISO 845 38.9CRIB5 Test Performance (BS5852) PASS

Claims

CLAIMS 1. A nitrogen-containing alkoxysilane-capped polyether polyol having from 1 to 8 hydroxyl groups per molecule and from 1 to 2 nitrogen-containing alkoxysilane groups per molecule, obtainable by a process comprising a) capping from 1 to 2 of the terminal hydroxyl groups of a polyether polyol having a functionality from 2 to 10 and a weight-average molecular weight from 2000 to 25000, determined according to the method identified in the specification, with a capping agent which is a compound having at least one alkoxysilane terminal group and at least one hydroxyl-reactive group selected from an isocyanate group, an anhydride group, and an oxirane group; wherein the reaction of the capping agent with the polyether polyol is carried out in a molar ratio from 0.05 to 2.0 mole of capping agent per mole of polyether polyol; to obtain an intermediate resulting product; b) reacting the intermediate resulting product in a) with a compound comprising an amino or -NHCONH2group and at least one alkoxysilane terminal group; to obtain the nitrogen-containing alkoxysilane-capped polyether polyol; wherein the capping agent is a compound of formula (I):wherein R1, R2and R3are each independently selected from linear or branched (C1-C6)alkyl radical, linear or branched (C1-C6)alkoxyl radical and tri(C1-C3)alkylsilyloxyl radical; with the proviso that at least one of R1, R2or R3is a (C1-C6)alkoxyl radical; and wherein A is a radical selected from the group consisting of (II), (III), (IV), (V) and (VI)the asterisk means the point of attachment to the Si atom in formula (I); m, n, p, r, t and w are independently an integer selected from 1 to 6; q, s and v are independently an integer selected from 1 to 4; R4is a radical selected from -NCO,and wherein the asterisk indicates the point of attachment to the rest of the group; X is selected from -O- and -N(R5)-; wherein R5is a radical selected from H, linear or branched (C1-C6)alkyl,wherein the asterisk indicates the point of attachment to the N atom; x and z are independently an integer selected from 1 to 6; and R8, R9and R10are each independently selected from linear or branched (C1-C6)alkyl radical, linear or branched (C1-C6)alkoxyl radical andtri(C1-C3)alkylsilyloxyl radical; with the proviso that at least one of R8, R9or R10is a (C1-C6)alkoxyl radical or a tri(C1-C3)alkylsilyloxyl radical; wherein the reaction of the at least one polyether polyol with the compound of formula (I) is carried out in a molar ratio from 0.05 to 2.0 mole of compound of formula (I) per mole of polyether polyol; the compound comprising an amino or -NHCONH2group and at least one alkoxysilane terminal group is a compound of formula (Ia)wherein R1’, R2’ and R3’ are each independently selected from linear or branched (C1-C6)alkyl radical, linear or branched (C1-C6)alkoxyl radical, and tri(C1-C3)alkylsilyloxyl radical; with the proviso that at least one of R1’, R2’ or R3’ is a (C1-C6)alkoxyl radical; and wherein A’ is selected from -(C1-C6)alkylNH2, -(C1-C6)alkylNH-(C1-C6)alkylNH2, -(C1-C6)alkylNH-(C1-C6)alkylNH-(C1-C6)alkylNH2, -(C1-C6)alkyl-NH-CO-NH2, -(C1-C6)alkylNH-(C1-C6)alkylNH-CO-NH2, and -(C1-C6)alkylNH-(C1-C6)alkylNH-(C1-C6)alkylNH-CO-NH2.

2. The nitrogen-containing alkoxysilane-capped polyether polyol according to claim 1, wherein the compound of formula (Ia) is added to the intermediate resulting product in a molar ratio with respect to the compound of formula (I) added in step (a) ranging from 0.1 to 20.

3. The nitrogen-containing alkoxysilane-capped polyether polyol according to any of claims 1-2, wherein i) the at least one polyether polyol has a functionality from 2 to 10 and a weight-average molecular weight from 2000 to 20000, and is obtainable by reacting ethylene oxide and / or propylene oxide with a polyhydric alcohol selected from glycerol, sorbitol, sucrose, trimethylolpropane, diethylene glycol, butanetriol, pentanetriol, hexanetriol erythritol and pentaerythritol; ii) the at least one capping alkoxysilane group-containing agent is acompound of formula (I), wherein the radical A is selected from ii.1) those compounds of formula (II) wherein m is an integer from 1 to 6; and R4 is selected from –NCO,wherein the asterisk indicates the point of attachment to the rest of group; ii.2) those compounds of formula (III) wherein n and p are independently an integer selected from 1 to 6, q is an integer selected from 1 to 3, X is selected from -O- and -N(R5)-, wherein R5is a radical selected from H, linear or branched (C1-C6)alkyl,wherein the asterisk indicates the point of attachment to the N atom; x and z are independently an integer selected from 1 to 6; and R8, R9and R10are each independently selected from -CH3, -CH2CH3, -OCH3, -OCH2CH3, -O-Si(CH3)3, and -O-Si(CH2CH3)3; ii.3) those compounds of formula (IV) or (V) wherein r and t are independently an integer selected from 1 to 4; and s is an integer selected from 1 to 3; or alternatively ii.4) those compounds of formula (VI), wherein w is an integer selected from 1 to 4; wherein the reaction of the at least one polyether polyol with the at least one capping alkoxysilane group-containing agent is a compound of formula (I), is carried out in a molar ratio from 0.05 to 2.0 mole of compound of formula (I) per mole of polyether polyol; and wherein the compound of formula (Ia) is added to the intermediate resulting product in a molar ratio with respect to the compound of formula (I) added in step (a) ranging from 0.1 to 20.

4. The nitrogen-containing alkoxysilane-capped polyether polyol according to any of claims 1-3, wherein the compound of formula (Ia) is selected from N-(2-aminoethyl)- 3-aminopropyltrimethoxysilane, (3-aminopropyl)triethoxysilane, 3-(2- aminoethylamino)propyldimethoxymethylsilane, 3-aminopropyl(diethoxy)methylsilane, N1-(3-trimethoxysilylpropyl)diethylenetriamine, 3-(ethoxydimethylsilyl)propylamine, (3-aminopropyl)trimethoxysilane, aminopropylmethyldiethoxysilane, 3- aminopropylsilanetriol, N-(3-triethoxysilylpropyl)ethylenediamine, 3- ureidopropyltrimethoxysilan, N-cyclohexylamino- methyltriethoxysilan, N-cyclohexyl- 3-aminopropyltrimethoxysilan, bis[3-triethoxysilyl)propyl]amine, bis[3- trimethoxysilyl)propyl]amine, aminopropylmethyldimethoxysilane, diethylaminomethyltriethoxysilane, diethylaminoethyltriethoxysilane, and N-(N-Butyl)- 3-aminopropyltrimethoxysilane.

5. A method for the preparation of modified polymer polyol dispersions, wherein the method comprises the preparation of polymeric particles in the presence of a liquid polyol mixture, wherein the liquid polyol mixture comprises at least one base polyol and at least one nitrogen-containing alkoxysilane-capped polyether polyol as defined in any of claims 1-4.

6. The method according to claim 5, wherein the method comprises the preparation of polymeric particles, in the presence of the liquid polyol mixture, by a. reacting, in the liquid polyol mixture and under polymerisation conditions a.1) at least one compound bearing at least one basic-nitrogen atom characterized by the presence in the molecule of at least one hydrogen atom attached to a nitrogen atom; with either a.2) or a.3), wherein a.2) is at least one compound or a mixture of compounds bearing a phosphorus atom selected from the group consisting of [bis(hydroxymethyl)phosphanyl]metanol (THP), tetrakis(hydroxymethyl) phosphonium salt (THPX), [bis(hydroxymethyl)phosphoryl]methanol (THPO), ({[bis(hydroxymethyl)phosphanyl]methoxy}methanol (mTHP), {bis[(hydroxymethoxy)methyl]phosphanyl}methanol (dTHP),{bis[(hydroxymethoxy)methyl]phosphanyl}methoxy)methanol (tTHP), {[bis(hydroxymethyl)phosphoryl]methoxy}methanol (mTHPO), {bis[(hydroxymethoxy)methyl]phosphoryl}methanol (dTHPO), ({bis[(hydroxymethoxy)methyl]phosphoryl}methoxy)methanol (tTHPO) and mixtures thereof; and a.3) is a mixture of condensation products resulting from the reaction of the at least one compound or mixture of compounds bearing a phosphorus atom a.2) as described above and the at least one compound bearing at least one basic nitrogen atom a.1); wherein the compound bearing at least one basic-nitrogen atom a.1) is selected from a.1i) melamine, trimethylol melamine, diethylenetriamine, tertiary octylamine, dimethylaminopropylamine, polyethyleneimines; a.1ii) those compounds of formula (VII) or formula (VIII); and a.1iii) mixtures thereof; wherein the compounds of formula (VII) are as follows R11-NH2(VII) wherein R11is selected from –H, -(C1-C3)Alkyl, (C1-C3)Alkyl-CO-, NH2-CO-, -(CH2)n-NH2, -CN, -NH2, -SO2NH2, cyclohexyl, phenyl, -SO2OH and -NHCONHNH2; wherein n is an integer from 1-18; and the compounds of formula (VIII) are as follows:wherein R12is selected from NH=C<, O=C< and S=C<; and R13is selected from H, -CN, -NH2, -CONH2, -CONHCONH2, and -CONHCONHCONH2; or alternatively b. reacting, in the liquid polyol mixture and under polymerisation conditions, optionally in the presence of a catalyst, b.1) at least one co-reactant selected from b.1.i) an amine, an alkanolamine or a diol having an equivalentweight of up to 400 and at least one active hydrogen attached to a nitrogen or oxygen atom; and b.1.ii) an olphosphine; with b.2) at least one polyisocyanate; wherein the liquid polyol mixture comprises at least one base polyol and at least one nitrogen-containing alkoxysilane-capped polyether polyol as defined in any of claims 1-5.

7. The method according to any of claims 5-6, wherein the method comprises: i. mixing the at least one base polyol with the at least one nitrogen- containing alkoxysilane-capped polyether polyol as defined in any of claims 1-4, thus obtaining a liquid polyol mixture; ii. adding to the liquid polyol mixture obtained in i) simultaneously or sequentially, in any order a.1) the at least one compound bearing at least one basic-nitrogen atom characterized by the presence in the molecule of at least one hydrogen atom attached to a nitrogen atom; and either a.2) or a.3), wherein a.2) is at least one compound or a mixture of compounds bearing a phosphorus atom selected from I. [bis(hydroxymethyl)phosphanyl]methanol (THP) in a concentration from 0-100 mol%, II. a tetrakis(hydroxymethyl) phosphonium salt (THPX) in a concentration from 0-100 mol%, III. [bis(hydroxymethyl)phosphoryl]methanol (THPO) in a concentration from 0-100 mol%, IV. {[bis(hydroxymethyl)phosphanyl]methoxy}methanol (mTHP) in a concentration from 0-80 mol%, V. {bis[(hydroxymethoxy)methyl]phosphanyl}methanol (dTHP) in a concentration from 0-30 mol%, VI. ({bis[(hydroxymethoxy)methyl]phosphanyl}methoxy)methanol (tTHP) in a concentration from 0-15 mol%, VII. {[bis(hydroxymethyl)phosphoryl]methoxy}methanol (mTHPO) in a concentration from 0-20 mol%,VIII. {bis[(hydroxymethoxy)methyl]phosphoryl}methanol (dTHPO) in a concentration from 0-10 mol%, and IX. ({bis[(hydroxymethoxy)methyl]phosphoryl}methoxy)methanol (tTHPO) in a concentration from 0-4 mol %; being the sum total of compounds bearing a phosphorus atom in the mixture 100 mol%; and a.3) is a mixture of condensation products resulting from the reaction of the at least one compound or a mixture of compounds a.2) as described above and at least one compound bearing at least one basic nitrogen atom a.1); wherein the compound bearing at least one basic-nitrogen atom a.1) is selected from - melamine, trimethylol melamine, diethylenetriamine, tertiary octylamine, dimethylaminopropylamine, polyethyleneimines; - those compounds of formula (VII) or formula (VIII); and - mixtures thereof; and wherein the liquid polyol mixture comprises at least one base polyol and at least one nitrogen-containing alkoxysilane-capped polyether polyol selected as defined in any of claims 1-4.

8. The method according to any of claims 5-7, wherein the method comprises: i. mixing the at least one base polyol with the at least one nitrogen- containing alkoxysilane-capped polyether polyol thus obtaining a liquid polyol mixture; and ii. adding to the liquid polyol mixture obtained in i) simultaneously or sequentially, in any order, optionally in the presence of a catalyst, and under polymerisation conditions, b.1) at least one co-reactant selected from b.1.i) an amine, an alkanolamine or a diol having an equivalent weight of up to 400 and at least one active hydrogen attached to a nitrogen or oxygen atom, and b.1.ii) an olphosphine; andb.2) at least one polyisocyanate; wherein the at least one co-reactant b.1) is selected from ammonia, aniline, (C1-C3)alkyl substituted aniline, fatty amines, ethylenediamine, 1,6- hexamethylenediamine, hydrazine, 2,6-diaminotoluene, 2,4-diaminotoluene, 4,4'- methylenedianiline, diethylene glycol, triethylene glycol, and polyethyelene glycol; olphosphines, such as hydroxyalkylphosphines, hydroxyalkylphosphonium salts, hydroxyalkylphosphine oxides and their derivatives; and alkanolamines, such as monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, 2-(2- aminoethoxyethanol), hydroxyethylpiperazine, monoisopropanolamine, diisopropanolamine, N-methylethanolamine, phenylethanolamine, glycol amine, and mixtures thereof; wherein the liquid polyol mixture comprises at least one base polyol and at least one nitrogen-containing alkoxysilane-capped polyether polyol as defined in any of claims 1-4.

9. The method according to any of claims 5-8, wherein the base polyol is a non- reactive polyol.

10. A modified polymer polyol dispersion of polymeric particles in a liquid polyol mixture obtainable by the method according to any of claims 5-9.

11. The modified polymer polyol dispersion according to claim 10, which is a polyisocyanate polyaddition polymer polyol dispersion, and the base polyol is a non- reactive polyol. 12 A process for preparing a polyurethane material wherein the process comprises reacting at least one polyisocyanate with an isocyanate-reactive component which comprises at least one stabilized modified polymer polyol dispersion as defined in any of claims 10-11, in the presence of at least one catalyst and optionally additives; wherein the polyisocyanate is used at an isocyanate index of from 60 to 140.

13. A polyurethane material obtainable by the process of claim 12.

14. An article of manufacture comprising the polyurethane material as defined in claim 13.

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