Stable modified polymer polyol dispersions

Abstract

The present invention relates to novel nitrogen-containing alkoxysilane-terminated polyether polyols useful as dispersants and stabilizers for modifying polymer polyol dispersions. Also disclosed are stable modified polymer polyol dispersions of polymer particles in a liquid polyol mixture and methods of making the same; also disclosed are polyurethane materials prepared using the stable modified polymer polyol dispersions of the present invention.

Description

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

[0002] This invention relates to novel compounds that can be used as dispersants and stabilizers for modified polymer polyol dispersions. Background Technology

[0003] Various modified polymeric polyols are used as raw materials for manufacturing flexible polyurethane foams and other polyurethane products. They have a continuous phase consisting of one or more compounds with multiple hydroxyl groups (“base polyols”), in which another polymer is dispersed in particulate form.

[0004] Therefore, examples of modified polymer polyols include: Polyurea dispersion (PHD) polyols are modified polymer polyols containing polyurea as a polycondensation product of an amine or polyamine and a polyfunctional isocyanate in a dispersed form. Grafted polyether polyols are synthesized by in-situ free radical polymerization of ethylene monomers in liquid polyether via batch, semi-continuous, or continuous methods. The ethylene monomers are typically selected from acrylonitrile, styrene, α-methylstyrene, methyl methacrylate, hydroxyalkyl acrylate, methacrylate, vinyl chloride, and other monomers. Polyisocyanate-plus-poly(PIPA) polymer polyols are dispersions of polyurethane and / or polyurethane-urea particles in liquid polyether polyols, obtained by polymerization of alkylene glycols, alkanolamines or olphosphine with organic polyisocyanates in the presence of polyols. And recently described polymeric polyols containing polyether carbonate polyols as base polyols, which can be obtained by copolymerizing one or more H-functional initiators, one or more epoxides and carbon dioxide in the presence of a bimetallic cyanide catalyst (DMC).

[0005] In this article, the term alkanolamine (also known as hydroxylamine) refers to an organic compound containing at least one hydroxyl group and at least one amino group (primary, secondary, or tertiary amino group).

[0006] In this document, the term hydroxyphosphine refers to an organic compound having at least one hydroxyl group and at least one phosphine group. Although hydroxyphosphine having a hydroxyl group attached to an aliphatic group and a phosphine group is most suitable in the practice of this invention, hydroxyphosphine having a hydroxyl group attached to an alicyclic, aromatic, or heterocyclic core and a phosphine group, or hydroxyphosphine having hydroxyl and phosphine groups combined with each other and / or combined with an aliphatic group, may also be used. Whether the active hydrogen in the hydroxyphosphine originates from both the hydroxyl and phosphine groups having this type of hydrogen, or only from the hydroxyl group, all of these active hydrogens are reactive with the isocyanate group. Hydroxyalkylphosphine, hydroxyalkylphosphonium salts, hydroxyalkylphosphine oxides, and their derivatives are specific examples of hydroxyphosphine that can be used to prepare PIPA polyols.

[0007] In our previous patent application WO2019008140, we disclosed a novel modified polymer polyol comprising at least one base polyol and a stable polymer particle dispersion in the at least one base polyol. The modified polymer polyol can be obtained by a method comprising preparing polymer particles through the following polycondensation reaction in the presence of at least one base polyol: i. At least one compound having at least one basic nitrogen atom and characterized in that at least one hydrogen atom is bonded to the nitrogen atom in the molecule; and ii. At least one compound containing a phosphorus atom, selected from the group consisting of: ii1. A compound containing a phosphorus atom, selected from the group consisting of at least one hydroxyalkylphosphine, at least one hydroxyalkylphosphonium salt, at least one hydroxyalkylphosphine oxide, and combinations thereof; or ii2. A condensation product obtained from a mixture of compounds b.1) and at least one compound having at least one basic nitrogen atom.

[0008] The base polyols used to prepare these modified polymer polyols can be polyether polyols, polyether carbonate polyols (POPC), or polyester polyols. Commercially, polyether polyols are produced by polymerizing propylene oxide and / or ethylene oxide in the presence of an initiator containing hydroxyl or amino groups and a basic catalyst. Polyester polyols are produced by the polycondensation reaction of polyfunctional carboxylic acids and polyhydroxy compounds.

[0009] In polyether polyols, reactive and non-reactive polyether polyols can be distinguished. Reactive polyols are ethylene oxide (EO)-terminated polyether polyols, with 5-20% by weight of ethylene oxide-terminated blocks, thus possessing a high content of primary hydroxyl groups (above 30%). Non-reactive polyols are propylene oxide (PO)-terminated polyether polyols, primarily containing secondary hydroxyl groups. Secondary hydroxyl groups are less reactive than primary hydroxyl groups.

[0010] Various methods have been proposed for stabilizing modified polymeric polyols. Therefore, introducing non-aqueous dispersant (NAD) stabilizers during polymerization has become one proposed solution. The stability of polymer dispersions in organic media is based on the principle of steric stability, which is ensured by the presence of non-aqueous dispersant (NAD) stabilizers. Thus, for example, in the case of grafted polyether polyols, the NAD comprises, with the same chemical structure, a segment with a strong affinity for carbon-chain (carbocatenary) vinyl polymers and a second segment with a strong affinity for liquid polyethers. The NAD is attached to the surface of the solid polymer particles containing the carbon-chain polymer segments, with the polyether chains outside the polymer particles located in a continuous polyether medium, forming steric hindrance and preventing polymer particle aggregation.

[0011] It is known in the art that PIPA and PHD polymeric polyols prepared using polyether polyols that primarily contain secondary hydroxyl groups will generate polymer particles that are unstable in the base polyol.

[0012] Various examples of NAD stabilizers are known in the art; however, given the recent developments in the field of modified polymer polyols, different preparation methods, and their varying chemical and physical properties, there is a current need for novel stabilizers for modified polymer polyols comprising at least one base polyol and a stable polymer particulate dispersion in the at least one base polyol. More specifically, there is a need to provide novel stabilizers for modified polymer polyol dispersions comprising at least one base polyol and a stable polymer particulate dispersion in the at least one base polyol, wherein the base polyol is a reactive polyether polyol or a non-reactive polyether polyol.

[0013] EP3838962 discloses alkoxysilane-terminated polyether polyols having 1 to 8 hydroxyl groups per molecule and 1 to 2 alkoxysilyl groups per molecule, and their use in the preparation of modified polymer polyol dispersions. Summary of the Invention

[0014] It has now been found that stable modified polymer polyol dispersions can be prepared by polymerizing one or more polymer particle precursors in the presence of a liquid polyol mixture comprising at least one base polyol and at least one nitrogen-alkoxysilane-terminated polyether polyol as described below in the nitrogen-alkoxysilane-terminated polyether polyol section and the claims.

[0015] Compared with modified polymer dispersions prepared without using at least one nitrogen-containing alkoxysilane-terminated polyether polyol, the resulting modified polymer polyol dispersion has improved stability, i.e., the modified polymer polyol dispersion does not precipitate during long-term storage, or at least remains dispersed when mixed with other foaming components.

[0016] The novel nitrogen-containing alkoxysilane-terminated polyether polyols disclosed herein can be used to stabilize modified polymer polyols prepared by using reactive or non-reactive polyether polyols as base polyols. Therefore, the use of nitrogen-containing alkoxysilane-terminated polyether polyols in liquid polyol mixtures allows for the preparation of stable modified polymer polyol dispersions, including PIPA polymer polyol dispersions and PHD polymer polyol dispersions, using non-reactive base polyols. Thus, according to one aspect of the invention, the novel nitrogen-containing alkoxysilane-terminated polyether polyols disclosed herein are provided, which can be used to stabilize modified polymer polyols prepared by using reactive or non-reactive polyether polyols as base polyols.

[0017] The novel nitrogen-containing alkoxysilane-terminated polyether polyol of the present invention can be used as a non-aqueous dispersant (NAD) for modified polymer polyol dispersions, and its advantage lies in its ease of preparation under mild reaction conditions. Therefore, this novel nitrogen-containing alkoxysilane-terminated polyether polyol is suitable for use as an NAD stabilizer in the preparation of modified polymer polyol dispersions.

[0018] This novel nitrogen-containing alkoxysilane-terminated polyether polyol can be obtained by the following methods: a) Using a capping agent, capping one or two terminal hydroxyl groups of a polyether polyol having a functionality of 2 to 10 and a weight-average molecular weight of 2,000 to 25,000 (determined according to the method specified in the instructions), said capping agent being a compound having at least one alkoxysilane terminal group and at least one hydroxyl reactive group selected from isocyanate groups, anhydride groups, and epoxy groups; wherein the reaction of said capping agent with said polyether polyol is carried out at a molar ratio of 0.05 to 2.0 moles of capping agent per mole of polyether polyol, thereby obtaining an intermediate product; b) The intermediate obtained in a) is reacted with at least one compound containing an amino or -NHCONH2 group and containing at least one alkoxysilane terminal group to obtain a nitrogen-containing alkoxysilane-terminated polyether polyol.

[0019] Therefore, a second aspect of the present invention relates to a method for preparing a nitrogen-containing alkoxysilane-terminated polyether polyol having 1 to 8 hydroxyl groups per molecule and 1 to 2 nitrogen-containing alkoxysilane groups per molecule, wherein the method comprises: a) Using a capping agent, one or two terminal hydroxyl groups of a polyether polyol having a functionality of 2 to 10 and a weight-average molecular weight of 2,000 to 25,000 (determined according to the method specified in the specification) are capped, said capping agent being a compound having at least one alkoxysilane terminal group and at least one hydroxyl reactive group selected from isocyanate groups, anhydride groups, and epoxy groups; wherein the reaction of said capping agent with said polyether polyol is carried out at a molar ratio of 0.05 to 2.0 moles, preferably 0.2 to 1.8 moles, more preferably 0.5 to 1.5 moles, and particularly preferably 0.8 to 1.2 moles of capping agent per mole of polyether polyol, thereby obtaining an intermediate product; b) The intermediate obtained in a) is reacted with at least one compound containing an amino or -NHCONH2 group and containing at least one alkoxysilane terminal group to obtain a nitrogen-containing alkoxysilane-terminated polyether polyol.

[0020] The nitrogen-containing alkoxysilane-terminated polyether polyols of the present invention can be used as dispersants and stabilizers for modified polymer polyols prepared from mixtures of PHD polyols, PIPA polyols, and hydroxyalkylphosphines and their derivatives (including salts, oxides, and hemiacetals) disclosed in WO2019008140 as polymer particle precursors. Therefore, the third aspect of the present invention relates to the use of the nitrogen-containing alkoxysilane-terminated polyether polyols of the first aspect and related embodiments of the present invention in the preparation of modified polymer polyol dispersions, and more specifically, their use as stabilizers and dispersants for modified polymer polyol dispersions.

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

[0022] The fifth aspect of the invention relates to a stable modified polymer polyol dispersion in a liquid polyol mixture, said stable modified polymer polyol dispersion being obtained by the method defined in the fourth aspect and related embodiments of the invention.

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

[0024] In a sixth aspect of the invention, a method for preparing a polyurethane material is provided, wherein at least one polyisocyanate is reacted with an isocyanate reactive component comprising at least one stable modified polymer polyol dispersion as described in the fifth aspect and related embodiments of the invention, said reaction optionally being carried out in the presence of water and additives such as at least one foaming agent, at least one catalyst and a surfactant product.

[0025] The seventh aspect of the present invention relates to polyurethane materials that can be obtained by the methods defined in the sixth aspect and related embodiments of the present invention.

[0026] The eighth aspect of the present invention relates to articles comprising polyurethane materials as defined in the seventh aspect and related embodiments of the present invention.

[0027] The stable modified polymer polyols of the present invention can be used to prepare polyurethane materials, such as polyurethane foams, adhesives, elastomers, sealants and coatings; preferably, polyurethane materials that possess flame-retardant properties due to the high P and N content of the dispersed polymer particles. Detailed Implementation

[0028] Nitrogen-containing alkoxysilane-terminated polyether polyols

[0029] According to some embodiments, optionally in combination with one or more features of the above or various embodiments described below, a nitrogen-containing alkoxysilane-terminated polyether polyol having 1 to 8 hydroxyl groups per molecule and 1 to 2 nitrogen-containing alkoxysilane groups per molecule can be obtained by methods comprising: A) Using a capping agent, one or two terminal hydroxyl groups of a polyether polyol having a functionality of 2 to 10 and a weight-average molecular weight of 2000 to 25000 (determined according to the method specified in the specification) are capped, wherein the capping agent is a compound having at least one alkoxysilane terminal group and at least one hydroxyl reactive group selected from isocyanate groups, anhydride groups and epoxy groups; wherein the reaction between the capping agent and the polyether polyol is carried out at a molar ratio of 0.05 to 2.0 moles, preferably 0.2 to 1.8 moles, more preferably 0.5 to 1.5 moles, and particularly preferably 0.8 to 1.2 moles of the capping agent per mole of polyether polyol, thereby obtaining an intermediate product; b) The intermediate obtained in a) is reacted with at least one compound containing an amino or -NHCONH2 group and containing at least one alkoxysilane terminal group to obtain a nitrogen-containing alkoxysilane-terminated polyether polyol. The capping agent is a compound of formula (I):

[0030] R1, R2, and R3 are each independently selected from straight-chain or branched (C1-C6) alkyl, straight-chain or branched (C1-C6) alkoxy, and tri(C1-C3) alkylsiloxy; provided that at least one of R1, R2, or R3 is (C1-C6) alkoxy; and

[0031] Wherein, A is a group selected from formulas (II), (III), (IV), (V), and (VI):

[0032] in, The asterisk indicates the site where the Si atom in formula (I) is connected; m, n, p, r, t, and w are independent integers selected from 1 to 6; q, s, and v are independent integers selected from 1 to 4; R4 is selected from -NCO, and group, The asterisk indicates the site where the group is attached to the rest of the group. X is selected from -O- and -N(R5)-; wherein R5 is selected from H, straight-chain or branched (C1-C6) alkyl, and group, The asterisk (*) indicates the site connected to the N atom. x and z are independent integers selected from 1 to 6; And R8, R9 and R 10 Each is independently selected from straight-chain or branched (C1-C6) alkyl, straight-chain or branched (C1-C6) alkoxy, and tri(C1-C3) alkylsiloxy; the condition is R8, R9, or R 10 At least one of them is (C1-C6)alkoxy or tri(C1-C3)alkylsiloxy; The reaction of at least one polyether polyol with the compound of formula (I) is carried out at a molar ratio of 0.05 to 2.0 moles of the compound of formula (I) per mole of polyether polyol. A compound of formula (Ia) that contains at least one amino or -NHCONH2 group and at least one alkoxysilane terminal group:

[0033] R1', R2' and R3' are each independently selected from straight-chain or branched (C1-C6) alkyl, straight-chain or branched (C1-C6) alkoxy and tri(C1-C3) alkylsiloxy; The condition is that at least one of R1', R2' or R3' is a (C1-C6) alkoxy group; 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.

[0034] According to some embodiments, optionally in combination with one or more features of the above or various embodiments described below, the compounds of formula (I) and formula (Ia) are compounds in which R1, R2, R3, R1', R2' and R3' are each independently 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-; provided that at least one of R1, R2 or R3 is selected from CH3-O-, CH3CH2-O-, CH3CH2CH2-O-, (CH3)2CH-O-; and at least one of R1', R2' and R3' is selected from CH3-O-, CH3CH2-O-, CH3CH2CH2-O-, (CH3)2CH-O-.

[0035] According to certain embodiments, optionally in combination with one or more features of the above or various embodiments described below, the compounds of formula (I) and formula (Ia) are compounds in which R1, R2, R3, R1', R2' and R3' are each independently 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-; provided that at least one of R1, R2 or R3 is selected from CH3-O- and CH3CH2-O-; and at least one of R1', R2' and R3' is selected from CH3-O- and CH3CH2-O-.

[0036] In the capping agent of formula (I), A is a group containing a terminal functional group that can react with the hydroxyl group on the polyether polyol. The terminal functional group that can react with the hydroxyl group is selected from -NCO, acid anhydride group and epoxy group.

[0037] According to certain embodiments, optionally in combination with one or more features of the above or the various embodiments described below, the compound of formula (I) is selected from the following compounds: wherein group A is a compound selected from formulas (II), (III), (IV), (V) and (VI):

[0038] in, The asterisk indicates the site where the Si atom in formula (I) is connected; m, n, p, r, t, and w are independently integers selected from 1 to 6; preferably 1, 2, 3, 4, 5, or 6; q, s, and v are independently integers selected from 1 to 4; preferably 1, 2, 3, or 4; R4 is selected from -NCO, and group, The asterisk indicates the site where the group is attached to the rest of the group. X is selected from -O- and -N(R5)-; wherein R5 is selected from H, straight-chain or branched (C1-C6) alkyl, and group, The asterisk (*) indicates the site connected to the N atom. x and z are independently integers selected from 1 to 6; preferably 1, 2, 3, 4, 5 or 6; And R8, R9 and R 10 Each is independently selected from straight-chain or branched (C1-C6) alkyl, straight-chain or branched (C1-C6) alkoxy, and tri(C1-C3) alkylsiloxy; the condition is R8, R9, or R 10 At least one of them is (C1-C6)alkoxy or tri(C1-C3)alkylsiloxy; preferably, R8, R9 and R 10 Each is independently selected from -CH3, -CH2CH3, -OCH3, -OCH2CH3, -O-Si(CH3)3 and -O-Si(CH2CH3)3.

[0039] In some embodiments, optionally in combination with one or more features of the above or various embodiments described below, group A is selected from 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, and group, The asterisk indicates the site where the group is attached to the rest of the group.

[0040] According to a particular embodiment, optionally in combination with one or more features of the above or various embodiments described below, the compound of formula (I) is selected from (3-isocyanopropyl)trimethoxysilane (also known as 3-(trimethoxysilyl)propyl isocyanate), (3-isocyanopropyl)dimethoxy(methyl)silane, (3-isocyanopropyl)(methoxy)dimethylsilane, (3-isocyanopropyl)dimethoxyethylsilane, diethyl(3-isocyanopropyl)methoxysilane, and (3-isocyanopropyl)triethoxysilane (also known as 3-(triethoxysilyl)). Propyl isocyanate), diethoxy(3-isocyanopropyl)methylsilane, ethoxy(3-isocyanopropyl)dimethylsilane, (3-isocyanopropyl)diethoxy(ethyl)silane, ethoxydiethyl(3-isocyanopropyl)silane, trimethoxy(2-isocyanoethyl)silane, (2-isocyanoethyl)dimethoxy(methyl)silane, (2-isocyanoethyl)(methoxy)dimethylsilane, ethyl(2-isocyanoethyl)dimethoxysilane, diethyl(2-isocyanoethyl)methoxysilane, triethoxy(2-isocyanoethyl) Silane, diethoxy(2-isocyanate-ethyl)methylsilane, ethoxy(2-isocyanate-ethyl)dimethylsilane, diethoxy(ethyl)(2-isocyanate-ethyl)silane, ethoxydiethyl(2-isocyanate-ethyl)silane, triethoxy(isocyanate-methyl)silane, (isocyanate-methyl)trimethoxysilane, trimethoxy({7-oxabicyclo[4.1.0]hept-3-yl}methyl)silane, triethoxy({7-oxabicyclo[4.1.0]hept-3-yl}methyl)silane, trimethoxy(2-{7-oxabicyclo[4.1.0]hept-3-yl}ethyl Triethoxy(methyl)(2-{7-oxabicyclo[4.1.0]hept-3-yl}ethyl)silane, triethoxy(2-{7-oxabicyclo[4.1.0]hept-3-yl}ethyl)silane, triethoxy(3-{7-oxabicyclo[4.1.0]hept-3-yl}propyl)silane, trimethoxy(3-{7-oxabicyclo[4.1.0]hept-3-yl}propyl)silane, triethoxy(4-{7-oxabicyclo[4.1.0]hept-3-yl}butyl)silane, and trimethoxy(4-{7-oxabicyclo[4.1.0]hept-3-yl}butyl)silane.

[0041] In some embodiments, optionally in combination with one or more features of the above or various embodiments described below, group A is selected from compounds of formula (III) above. In one embodiment, optionally in combination with one or more features of the above or various embodiments described below, group A is selected from compounds of formula (III), wherein, n and p are independently integers selected from 1 to 6; in particular 1, 2, 3, 4, 5, or 6; even more particularly 1, 2, 3, or 4; and q is an integer selected from 1 to 4; in particular 1, 2, 3 or 4, and even more particularly 1 or 3; X is selected from -O- and -N(R5)-; Wherein, R5 is selected from H, straight-chain or branched (C1-C6) alkyl, and group, The asterisk (*) indicates the site connected to the N atom. x and z are independent integers selected from 1 to 6; in particular 1, 2, 3, 4, 5 or 6; And R8, R9 and R 10 Each is independently selected from -CH3, -CH2CH3, -OCH3, -OCH2CH3, -O-Si(CH3)3 and -O-Si(CH2CH3)3.

[0042] According to a particular embodiment, optionally in combination with one or more features of the above or various embodiments described below, the compound of formula (I) is selected from trimethoxy({3-[(ethylene oxide-2-yl)methoxy]propyl})silane (also known as propylene oxide propyl-trimethoxysilane), dimethoxy(methyl){3-[(ethylene oxide-2-yl)methoxy]propyl}silane, methoxydimethyl{3-[(ethylene oxide-2-yl)methoxy]propyl}silane, dimethoxy(ethyl){3-[(ethylene oxide-2-yl)methoxy]propyl}silane, diethyl(methoxy){3-[(ethylene oxide-2-yl)methoxy]propyl}silane, triethoxy({3-[(ethylene oxide-2-yl)methoxy]propyl}silane, and triethoxy({3-[(ethylene oxide-2-yl)methoxy]propyl}) propyl silane (also known as propylene oxide propyl-triethoxysilane), diethoxy(methyl){3-[(ethylene oxide-2-yl)methoxy]propyl}silane, ethoxydimethyl{3-[(ethylene oxide-2-yl)methoxy]propyl}silane, diethoxyethyl[3-(ethylene oxide-2-ylmethoxy)propyl]silane, ethoxydiethyl{3-[(ethylene oxide-2-yl)methoxy]propyl}silane, trimethoxy({2-[(ethylene oxide-2-yl)methoxy]ethyl})silane, dimethoxy(methyl){2-[(ethylene oxide-2-yl)methoxy]ethyl}silane, methoxydimethyl{2-[(ethylene oxide-2-yl)methoxy]ethyl}silane, ethyldimethoxy{2-[ [(ethylene oxide-2-yl)methoxy]ethyl}silane, diethyl(methoxy){2-[(ethylene oxide-2-yl)methoxy]ethyl}silane, triethoxy({2-[(ethylene oxide-2-yl)methoxy]ethyl})silane, diethoxy(methyl){2-[(ethylene oxide-2-yl)methoxy]ethyl}silane, ethoxydimethyl{2-[(ethylene oxide-2-yl)methoxy]ethyl}silane, diethoxy(ethyl){2-[(ethylene oxide-2-yl)methoxy]ethyl}silane, diethoxy(ethyl){2-[(ethylene oxide-2-yl)methoxy]ethyl}silane, trimethoxy({[(ethylene oxide-2-yl)methoxy]methyl})silane, dimethoxy(methyl){[(ethylene oxide-2-yl)methoxy]methyl})silane, dimethoxy(methyl){[(ethylene oxide-2-yl)methoxy]ethyl})silane, dieth ... Silane, methoxydimethyl{[(ethylene oxide-2-yl)methoxy]methyl}silane, ethyldimethoxy{[(ethylene oxide-2-yl)methoxy]methyl}silane, diethyl(methoxy){[(ethylene oxide-2-yl)methoxy]methyl}silane, triethoxy({[(ethylene oxide-2-yl)methoxy]methyl})silane, diethoxy(methyl){[(ethylene oxide-2-yl)methoxy]methyl}silane, ethoxydimethyl{[(ethylene oxide-2-yl)methoxy]methyl}silane, diethoxy(ethyl){[(ethylene oxide-2-yl)methoxy]methyl}silane, ethoxydiethyl{[(ethylene oxide-2-yl)methoxy]methyl}silaneButyl[(ethylene oxide-2-yl)methyl][3-(trimethoxysilyl)propyl]amine, butyl[(ethylene oxide-2-yl)methyl][3-(triethoxysilyl)propyl]amine, ethyl[(ethylene oxide-2-yl)methyl][3-(trimethoxysilyl)propyl]amine, ethyl[(ethylene oxide-2-yl)methyl][3-(triethoxysilyl)propyl]amine, methyl ... [3-(trimethoxysilyl)propyl]amine, N-[(ethylene oxide-2-yl)methyl][3-(triethoxysilyl)propyl]amine, N-[(ethylene oxide-2-yl)methyl]-N-[3-(trimethoxysilyl)propyl]aniline, N-[(ethylene oxide-2-yl)methyl]-N-[3-(triethoxysilyl)propyl]aniline, N-[(ethylene oxide-2-yl)methyl]-N-[3-(triethoxysilyl)propyl]aniline, N-[(ethylene oxide-2-yl)methyl] [3-(trimethoxysilyl)methyl]aniline, N-[(ethylene oxide-2-yl)methyl]-N-[(triethoxysilyl)methyl]aniline, methyl[(ethylene oxide-2-yl)methyl][(trimethoxysilyl)methyl]amine, methyl[(ethylene oxide-2-yl)methyl][(triethoxysilyl)methyl]amine, 3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)methyl]amine Alkyl)propyl)-N-((ethylene oxide-2-yl)methyl)propyl-1-amine, 3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)-N-((ethylene oxide-2-yl)methyl)propyl-1-amine, N,N-bis((trimethoxysilyl)methyl)(ethylene oxide-2-yl)methylamine, and N,N-bis((triethoxysilyl)methyl)(ethylene oxide-2-yl)methylamine.

[0043] In some embodiments, optionally in combination with one or more features of the above or various embodiments described below, group A is selected from compounds of formula (IV) or (V). In one embodiment, optionally in combination with one or more features of the above or various embodiments described below, group A is selected from compounds of formula (IV) or (V), wherein, r and t are independent integers selected from 1, 2, 3, or 4; and s is an integer selected from 1, 2 or 3.

[0044] According to a particular embodiment, optionally in combination with one or more features of the above or various embodiments described below, the compound of formula (I) is selected from (ethylene oxide-2-yl)methyl N-[3-(trimethoxysilyl)propyl]carbamate, (ethylene oxide-2-yl)methyl N-[3-(triethoxysilyl)propyl]carbamate, (ethylene oxide-2-yl)methyl N-[4-(trimethoxysilyl)butyl]carbamate, (ethylene oxide-2-yl)methyl N-[4-(triethoxysilyl)butyl]carbamate, (ethylene oxide-2-yl)methyl N-[2-(trimethoxysilyl)ethyl]carbamate, (ethylene oxide-2-yl)methyl N-[2-(triethoxysilyl)ethyl]carbamate Carbamates, (ethylene oxide-2-yl)methyl N-[(trimethoxysilyl)methyl]carbamate, (ethylene oxide-2-yl)methyl N-[(triethoxysilyl)methyl]carbamate, 3-trimethoxysilylpropylcarbamoyl ethylene oxide-2-carboxylic acid ester, 3-triethoxysilylpropylcarbamoyl ethylene oxide-2-carboxylic acid ester, ethylene oxide-2-carbonyl-N-[(trimethoxysilyl)methyl]carbamate, ethylene oxide-2-carbonyl-N-[(triethoxysilyl)methyl]carbamate, ethylene oxide-2-carbonyl-N-[4-(trimethoxysilyl)butyl]carbamate, and ethylene oxide-2-carbonyl-N-[4-(triethoxysilyl)butyl]carbamate.

[0045] In some embodiments, group A is optionally combined with one or more features of the above or the various embodiments described below, wherein group A is selected from compounds of formula (VI) above.

[0046] In one embodiment, optionally in combination with one or more features of the above or the various embodiments described below, group A is selected from compounds of formula (VI), wherein, w is an integer selected from 1, 2, 3, or 4; in particular, 2, 3, or 4.

[0047] According to a particular embodiment, optionally in combination with one or more features of the above or the various embodiments described below, the compound of formula (I) is selected from 3-[3-(triethoxysilyl)propyl]tetrahydrofuran-2,5-dione and 3-[3-(trimethoxysilyl)propyl]tetrahydrofuran-2,5-dione.

[0048] According to certain specific embodiments, optionally in combination with one or more features of the above or below various embodiments, the reaction of the capping agent with the polyether polyol is carried out at a molar ratio of 0.05 to 2.0 moles of capping agent per mole of polyether polyol, preferably 0.2 to 1.8 moles, more preferably 0.50 to 1.5 moles, and particularly preferably 0.8 to 1.2 moles.

[0049] Therefore, according to certain embodiments, optionally in combination with one or more features of the above or below various embodiments, each molecule of the nitrogen-containing alkoxysilane-terminated polyether polyol contains 1 to 8 hydroxyl groups, preferably 2 to 7, more preferably 3 to 6, and even more preferably 4 to 5 hydroxyl groups; and each molecule contains 1 to 2, preferably 1, nitrogen-containing alkoxysilane group.

[0050] As described above, nitrogen-containing alkoxysilane-terminated polyether polyols are obtained by: using a capping agent, capping one or two terminal hydroxyl groups of a polyether polyol (polyether polyol raw material) with a functionality of 2 to 10 and a weight-average molecular weight of 2,000 to 25,000 to obtain an intermediate product (first capping step); then reacting the intermediate product with a compound containing an amino or -NHCONH2 group and containing at least one alkoxysilane terminal group to obtain a nitrogen-containing alkoxysilane-terminated polyether polyol.

[0051] According to specific embodiments, optionally in combination with one or more features of the various embodiments described above or below, the OH functionality of the polyether polyol used as a raw material in the first end-capping step is 2-10, preferably 2-8, more preferably 3-7; and even more preferably 3-6. In some specific embodiments, the OH functionality is 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0052] According to a specific embodiment, optionally in combination with one or more features of the above or below embodiments, the weight-average molecular weight of the polyether polyol is 2,000 to 25,000, preferably 2,000 to 20,000, more preferably 3,000 to 20,000, particularly preferably 8,000 to 15,000, and even more preferably 11,000 to 14,000.

[0053] According to a specific embodiment, optionally in combination with one or more features of the above or below embodiments, the hydroxyl value of the polyether polyol is 20-600 mg KOH / g, preferably 24-380 mg KOH / g, more preferably 26-80 mg KOH / g.

[0054] According to a specific embodiment, optionally in combination with one or more features of the above or below embodiments, the viscosity of the polyether polyol at 25°C is 50 to 12,500 mPa s, preferably 200 to 8,000 mPa s, more preferably 450 to 5,000 mPa s, and even more preferably 500 to 2,000 mPa s.

[0055] According to certain specific embodiments, optionally in combination with one or more features of the above or below various embodiments, the polyether polyol is a polyether polyol with a functionality of 3-6, a weight-average molecular weight of 2000 to 20000, and a viscosity of 200 to 8000 mPa s at 25°C.

[0056] According to certain embodiments of the invention, optionally in combination with one or more features of the various embodiments described above or below, the polyether polyol does not contain any organic filler dispersed therein. Thus, according to one embodiment, the first polyol is not or does not contain a modified polymer polyol because it is substantially free of any organic filler dispersed therein.

[0057] According to certain embodiments of the present invention, optionally in combination with one or more features of the various embodiments described above or below, the polyether polyol contains a certain amount of organic filler dispersed therein; thus, in some embodiments, the polyether polyol may contain 0% to 50% by weight, preferably 0.01% to 30% by weight, more preferably 0.02% to 15% by weight, and even more preferably 0.5% to 5% by weight of organic filler dispersed therein. Examples of organic fillers are polyethylene, polypropylene, and vinyl polymer particles, such as acrylonitrile, polystyrene, methacrylonitrile, methyl methacrylate, polyisocyanate-polymer (PIPA), polyurea (PHD), and styrene-acrylonitrile particles.

[0058] In some embodiments, optionally in combination with one or more features of the above or the various embodiments described below, at least one polyether polyol has a functionality of 2 to 10 and a weight-average molecular weight of 2,000 to 20,000, and can be obtained by reacting ethylene oxide and / or propylene oxide with a polyol selected from glycerol, sorbitol, sucrose, trimethylolpropane, diethylene glycol, glycerol, pentanediol, hexanediol, erythritol, and pentaerythritol.

[0059] According to certain embodiments of the present invention, optionally in combination with one or more features of the above or below various embodiments, the polyether polyol is a poly(ethylene oxide and / or propylene oxide) adduct of a polyol selected from glycerol, sorbitol, sucrose, trimethylolpropane, diethylene glycol, glycerol, pentanediol, hexanediol, erythritol and pentaerythritol; wherein the polyether polyol has a functionality of 2-10 and a weight-average molecular weight of 2000 to 20000.

[0060] According to specific embodiments, optionally in combination with one or more features of the above or below embodiments, the polyether polyol is an ethylene oxide (EO) or propylene oxide (PO)-terminated polyether polyol. In one specific embodiment, optionally in combination with one or more features of the above or below embodiments, the polyether polyol is a reactive polyether polyol, i.e., an ethylene oxide (EO)-terminated polyether polyol with a terminal primary hydroxyl content of 35 to 99.9%, 35 to 98%, 40 to 95%, 45 to 90%, 50 to 85%, 75 to 99%, 77 to 98%, or 78 to 95% as determined by 13C nuclear magnetic resonance (RMN-13C). According to some specific embodiments, optionally in combination with one or more features of the above or below embodiments, the polyether polyol is a reactive polyether polyol with a polyethylene oxide terminal block content of 5-20% by weight, preferably 10-19.5% by weight, more preferably 12-19% by weight, and even more preferably 13-18% by weight.

[0061] According to another specific embodiment, optionally in combination with one or more features of the above or below various embodiments, the polyether polyol is a non-reactive polyether polyol, namely a propylene oxide (PO)-terminated polyether polyol.

[0062] In certain embodiments of the invention, optionally in combination with one or more features of the above or various embodiments described below, at least one compound comprising an amino or -NHCONH2 group and comprising at least one alkoxysilane terminal group is a compound of formula (Ia):

[0063] Wherein, R1', R2' and R3' are each independently selected from straight-chain or branched (C1-C6)alkyl, straight-chain or branched (C1-C6)alkoxy and tri(C1-C3)alkylsilyloxy groups; preferably 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- groups; The condition is that at least one of R1', R2' or R3' is a (C1-C6)alkoxy group; preferably, at least one of R1', R2' and 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, -CH2CH2C H2NHCH2CH2CH2NH2, -CH2CH(CH3)NHCH(CH3)CH2NH2, -CH2NHCH2NHCH2NH2, -CH2CH2NHCH2NHCH2NH2, -CH2CH2NHCH2NHCH2CH2NH2, -CH2C H2NHCH2CH2NHCH2CH2NH2, -CH2CH2CH2NHCH2NHCH2CH2CH2NH2, -CH2CH2CH2NHCH2CH2NHCH2CH2CH2NH2, -CH2CH2CH2NHCH2CH2CH2NHCH2 CH2CH2NH2, -CH2CH2CH2NHCH2CH2NHCH2NH2, -CH2CH2CH2NHCH2CH2NHCH2CH2NH2, -CH2CH(CH3)NHCH(CH3)CH2NHCH(CH3)NH2, -CH2NHCON H2, -CH2CH2NHCONH2, -CH2CH2CH2NHCONH2, -CH2CH(CH3)NHCONH2, -CH2NHCH2NHCONH2, -CH2CH2NHCH2NHCONH2, -CH2CH2NHCH2CH2NHCON H2, -CH2CH2CH2NHCH2NHCONH2, -CH2CH2CH2NHCH2CH2NHCONH2, -CH2CH2CH2NHCH2CH2CH2NHCONH2, -CH2CH(CH3)NHCH(CH3)CH2NHCONH2.

[0064] According to some embodiments, optionally in combination with one or more features of the above or various embodiments described 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-aminopropyldiethoxymethylsilane (CAS 3179-76-8), N1-(3-trimethoxysilylpropyl)diethylenetriamine (CAS 35141-30-1), 3-(ethoxydimethylsilyl)propylamine (CAS 18306-79-1), (3-aminopropyl)trimethoxysilane (CAS 18306-79-1), and N1-(3-trimethoxysilylpropyl)diethylenetriamine (CAS 18306-79-1). 13822-56-5), aminopropylmethyldiethoxysilane (CAS 3179-76-8), 3-aminopropylsilanetriol (CAS 58160-99-9), N-(3-triethoxysilylpropyl)ethylenediamine (CAS 5089-72-5), 3-ureopropyltrimethoxysilane (CAS 23843-64-3), N-cyclohexylamino-methyltriethoxysilane (CAS 26495-91-0), N-cyclohexyl-3-aminopropyltrimethoxysilane (CAS 3068-78-8), bis[3-triethoxysilyl)propyl]amine (CAS 13497-18-2), bis[3-trimethoxysilyl)propyl]amine (CAS 82985-35-1), aminopropylmethyldiethoxysilane (CAS 13822-56-5 ...diethoxysilane (CAS 13822-56-5), aminopropylmethyldiethoxysilane (CAS 13822-56-5), aminopropylmethyldiethoxysilane (CAS 13822-56-5), aminopropylmethyldiethoxysilane (CAS 13822-56-5), aminopropylmethyldiethoxysilane (CAS 13822-56-5), aminopropylmethyl 3663-44-3), diethylaminomethyltriethoxysilane (CAS 15180-47-9), diethylaminoethyltriethoxysilane (CAS 41051-80-3), N-(n-butyl)-3-aminopropyltrimethoxysilane (CAS 31024-56-3).

[0065] In some embodiments, optionally in combination with one or more features of the above or below various embodiments, at least one compound of formula (Ia) is added to the intermediate in a molar ratio of 0.1 to 20, 0.5 to 10, 0.7 to 5, 0.9 to 5, 0.99 to 3.5, or 1.5 to 2.75 relative to the compound of formula (I) added in step (a).

[0066] In certain embodiments of the present invention, optionally in combination with one or more features of the above or various embodiments described below, nitrogen-containing alkoxysilane-terminated polyether polyols are obtained in the following manner: a) Cap the 1 to 2 terminal hydroxyl groups of i) using ii). i) A polyether polyol having a functionality of 2 to 10 and a weight-average molecular weight of 2,000 to 20,000, which can be obtained by reacting ethylene oxide and / or propylene oxide with a polyol selected from glycerol, sorbitol, sucrose, trimethylolpropane, diethylene glycol, glycerol, pentanetriol, hexanetriol, erythritol and pentaerythritol. ii) The compound of formula (I) is used as a capping agent; wherein the reaction between the capping agent and the polyether polyol is carried out at a molar ratio of 0.05 to 2.0 moles of capping agent per mole of polyether polyol, preferably 0.2 to 1.8 moles, more preferably 0.5 to 1.5 moles, and particularly preferably 0.8 to 1.2 moles, to obtain an intermediate product; and b) Reaction of the intermediate obtained in a) with at least one compound of formula (Ia) containing an amino or -NHCONH2 group and containing at least one alkoxysilane terminal group to obtain a nitrogen-containing alkoxysilane-terminated polyether polyol. in, At least one end-capping agent containing an alkoxysilyl end-capping group is a compound of formula (I), wherein group A is selected from: ii.1) Compounds of formula (II), wherein m is an integer from 1 to 6; and R4 is selected from -NCO, and , The asterisk indicates the site where the group is attached to the rest of the group. ii.2) Compounds of formula (III), wherein n and p are independently integers selected from 1 to 6, q is an integer selected from 1 to 3, and X is selected from -O- and -N(R5)-, wherein R5 is selected from H, straight-chain or branched (C1-C6) alkyl, and group, Wherein, the asterisk indicates the site connected to the N atom; x and z are independent integers selected from 1 to 6; and R8, R9, and R 10 Each is independently selected from -CH3, -CH2CH3, -OCH3, -OCH2CH3, -O-Si(CH3)3 and -O-Si(CH2CH3)3; ii.3) Compounds of formula (IV) or formula (V), wherein r and t are independently integers selected from 1 to 4; and s is an integer selected from 1 to 3; Or as an option ii.4) Compounds of formula (VI), wherein w is an integer selected from 1 to 4; and In this process, at least one compound of formula (Ia) is added to the intermediate product at a molar ratio of 0.1 to 20, preferably 0.5 to 10, more preferably 0.7 to 5, even more preferably 0.9 to 5, even more preferably 0.99 to 3.5, and even more preferably 1.5 to 2.75, relative to the compound of formula (I) added in step (a).

[0067] In certain embodiments of the present invention, optionally in combination with one or more features of the above or various embodiments described below, nitrogen-containing alkoxysilane-terminated polyether polyols are obtained in the following manner: a) One or two terminal hydroxyl groups of a polyether polyol having a functionality of 2 to 10 and a weight average molecular weight of 2,000 to 20,000, which can be obtained by reacting ethylene oxide and / or propylene oxide with a polyol selected from glycerol, sorbitol, sucrose, trimethylolpropane, diethylene glycol, glycerol, pentanediol, hexanediol, erythritol and pentaerythritol; End-capping is performed using a compound of formula (I) as an end-capping agent; wherein the reaction between the end-capping agent and the polyether polyol is carried out at a molar ratio of 0.05 to 2.0 moles of end-capping agent per mole of polyether polyol, preferably 0.2 to 1.8 moles, more preferably 0.5 to 1.5 moles, and particularly preferably 0.8 to 1.2 moles of end-capping agent, thereby obtaining an intermediate product; and b) Reaction of the intermediate obtained in a) with at least one compound of formula (Ia) containing an amino or -NHCONH2 group and containing at least one alkoxysilane terminal group to obtain a nitrogen-containing alkoxysilane-terminated polyether polyol. In the compound of formula (I), group A is selected from: i) A compound of formula (II), wherein m is an integer selected from 1, 2, 3, 4, 5 and 6; and R4 is selected from -NCO, and , The asterisk indicates the site where the group is attached to the rest of the group. ii) Compounds of formula (III), wherein n and p are independently integers selected from 1, 2, 3, 4, 5 and 6, q is an integer selected from 1, 2 and 3, and X is selected from -O- and -N(R5)-, wherein R5 is selected from H, straight-chain or branched (C1-C6) alkyl, and group, Where, the asterisk indicates the site connected to the N atom; x and z are independently integers selected from 1, 2, 3, 4, 5, and 6; and R8, R9, and R 10Each is independently selected from -CH3, -CH2CH3, -OCH3, -OCH2CH3, -O-Si(CH3)3 and -O-Si(CH2CH3)3; iii) Compounds of formula (IV) or (V), wherein r and t are independently integers selected from 1, 2, 3 and 4; and s is an integer selected from 1, 2 and 3; Or as an option iv) Compounds of formula (VI), wherein w is an integer selected from 1, 2, 3 and 4, such as 3-[3-(triethoxysilyl)propyl]tetrahydrofuran-2,5-dione and 3-[3-(trimethoxysilyl)propyl]tetrahydrofuran-2,5-dione; In the compound of formula (Ia), R1', R2' and R3' are each independently selected from straight-chain or branched (C1-C6)alkyl, straight-chain or branched (C1-C6)alkoxy and tri(C1-C3)alkylsilyloxy groups; preferably 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- groups; The condition is that at least one of R1', R2' or R3' is a (C1-C6)alkoxy group; preferably, at least one of R1', R2' and R3' is CH3-O-, CH3CH2-O-, CH3CH2CH2-O-, or (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, -CH2CH2C H2NHCH2CH2CH2NH2, -CH2CH(CH3)NHCH(CH3)CH2NH2, -CH2NHCH2NHCH2NH2, -CH2CH2NHCH2NHCH2NH2, -CH2CH2NHCH2NHCH2CH2NH2, -CH2C H2NHCH2CH2NHCH2CH2NH2, -CH2CH2CH2NHCH2NHCH2CH2CH2NH2, -CH2CH2CH2NHCH2CH2NHCH2CH2CH2NH2, -CH2CH2CH2NHCH2CH2CH2NHCH2 CH2CH2NH2, -CH2CH2CH2NHCH2CH2NHCH2NH2, -CH2CH2CH2NHCH2CH2NHCH2CH2NH2, -CH2CH(CH3)NHCH(CH3)CH2NHCH(CH3)NH2, -CH2NHCON H2, -CH2CH2NHCONH2, -CH2CH2CH2NHCONH2, -CH2CH(CH3)NHCONH2, -CH2NHCH2NHCONH2, -CH2CH2NHCH2NHCONH2, -CH2CH2NHCH2CH2NHCON H2, -CH2CH2CH2NHCH2NHCONH2, -CH2CH2CH2NHCH2CH2NHCONH2, -CH2CH2CH2NHCH2CH2CH2NHCONH2, -CH2CH(CH3)NHCH(CH3)CH2NHCONH2; and The compound of formula (Ia) is added to the intermediate product at a molar ratio of 0.1 to 20, preferably 0.5 to 10, more preferably 0.7 to 5, even more preferably 0.9 to 5, even more preferably 0.99 to 3.5, and even more preferably 1.5 to 2.75, relative to the compound of formula (I) added in step (a).

[0068] In certain embodiments of the invention, optionally in combination with one or more features of the above or various embodiments described below, nitrogen-containing alkoxysilane-terminated polyether polyols can be obtained in the following manner: a) One or two terminal hydroxyl groups of at least one polyether polyol having a functionality of 2 to 10 and a weight average molecular weight of 2,000 to 20,000, which can be obtained by reacting ethylene oxide and / or propylene oxide with a polyol selected from glycerol, sorbitol, sucrose, trimethylolpropane, diethylene glycol, glycerol, pentanediol, hexanediol, erythritol and pentaerythritol; End-capping is performed using at least one end-capping agent of formula (I) containing an alkoxysilyl end-capping group, selected from (3-isocyanopropyl)trimethoxysilane, (3-isocyanopropyl)dimethoxy(methyl)silane, (3-isocyanopropyl)(methoxy)dimethylsilane, (3-isocyanopropyl)dimethoxyethylsilane, 3-isocyanopropyltriethoxysilane, (3-isocyanopropyl)diethoxy(ethyl)silane, tri... Ethoxy(2-isocyanate-ethyl)silane, Triethoxy(isocyanate-methyl)silane, Trimethoxy({3-[(ethylene oxide-2-yl)methoxy]propyl})silane, Dimethoxy(methyl){3-[(ethylene oxide-2-yl)methoxy]propyl}silane, Methoxydimethyl{3-[(ethylene oxide-2-yl)methoxy]propyl}silane, Dimethoxy(ethyl){3-[(ethylene oxide-2-yl)methoxy]propyl} Silane, Triethoxy({3-[(ethylene oxide-2-yl)methoxy]propyl})silane, Diethoxyethyl[3-(ethylene oxide-2-ylmethoxy)propyl]silane, 3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)-N-((ethylene oxide-2-yl)methyl)propyl-1-amine, 3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)-N-((ethylene oxide) Alkyl)methyl)prop-1-amine, N,N-bis((trimethoxysilyl)methyl)(ethylene oxide-2-yl)methylamine, 3-trimethoxysilylpropylcarbamoyl ethylene oxide-2-carboxylic acid ester, 3-triethoxysilylpropylcarbamoyl ethylene oxide-2-carboxylic acid ester, 3-trimethoxysilylethylcarbamoyl ethylene oxide-2-carboxylic acid ester and 3-triethoxysilylethylcarbamoyl ethylene oxide-2-carboxylic acid ester; The reaction between the end-capping agent and the polyether polyol is carried out at a molar ratio of 0.05 to 2.0 moles of end-capping agent per mole of polyether polyol, preferably 0.2 to 1.8 moles, more preferably 0.50 to 1.5 moles, and particularly preferably 0.8 to 1.2 moles. b) Reaction of the intermediate obtained in a) with at least one compound of formula (Ia), wherein 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-aminopropyldiethoxymethylsilane (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 18306-79-1), N1-(3-trimethoxysilylpropyl)diethylenetriamine (CAS 18306-79-1), N1-(3-aminopropyl)trimethoxysilane (CAS 18306-79-1), N1-(3-aminopropyl)trimethoxysilane (CAS 18306-79-1), N1-(3-aminopropyl)trimethoxysilane (CAS 18306-79-1), N1-(3-aminopropyl)di ...30-2), N1-(3-aminopropyl)dimethoxysilane (CAS 18306-30-2), N1-(3-aminopropyl)dimethoxysilane (CAS 18306-30-2), N1-(3-aminopropyl) 3179-76-8), 3-aminopropylsilanetriol (CAS 58160-99-9), N-(3-triethoxysilylpropyl)ethylenediamine (CAS 5089-72-5), 3-ureopropyltrimethoxysilane (CAS 23843-64-3), N-cyclohexylamino-methyltriethoxysilane (CAS 26495-91-0), N-cyclohexyl-3-aminopropyltrimethoxysilane (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 5179-76-8), 3-aminopropylsilanetriol (CAS 58160-99-9), N-(3-triethoxysilylpropyl)ethylenediamine (CAS 5089-72-5), 3-ureopropyltrimethoxysilane (CAS 23843-64-3), N-cyclohexylamino-methyltriethoxysilane (CAS 26495-91-0), N-cyclohexyl-3-aminopropyltrimethoxysilane (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), diethylaminomethyltrieth ... 15180-47-9), diethylaminoethyltriethoxysilane (CAS 41051-80-3), N-(n-butyl)-3-aminopropyltrimethoxysilane (CAS 31024-56-3).

[0069] Therefore, since the intermediate product in step a) can be obtained by reacting at least one polyether polyol as defined above with at least one compound of formula (I), the intermediate product can be described as an alkoxysilane-terminated polyether polyol, wherein one or two, preferably one, hydroxyl groups of the polyether polyol react with hydroxyl reactive groups present in the end-capping agent containing alkoxysilane-terminated groups. Thus, for example, when a polyether polyol with a functionality of 6 (i.e., the number of OH groups in the molecule is 6) reacts with a compound of formula (I) at a molar ratio of 0.8 to 1.2 moles of the compound of formula (I) per mole of polyether polyol, the resulting alkoxysilane-modified compound is a polyether polyol in which one hydroxyl group reacts with a hydroxyl reactive group present in the end-capping agent containing alkoxysilane-terminated groups of formula (I), while the remaining hydroxyl groups remain free.

[0070] According to one embodiment, optionally in combination with one or more features of the above or below various embodiments, the reaction between the polyether polyol and the compound of formula (I) is carried out in a temperature range of 0°C to 160°C, preferably 10°C to 120°C, and particularly preferably 20°C to 80°C.

[0071] This reaction can be carried out in the presence of a catalyst. Anyone skilled in the art can determine any suitable catalyst based on the reactants.

[0072] In some embodiments, optionally in combination with one or more features of the above or below embodiments, the reaction can be carried out in the presence of a urethanization catalyst known to those skilled in the art, such as a potassium catalyst, organotin compound, or amine catalyst. Other catalysts, such as zinc catalysts, may also be used. In some specific embodiments, optionally in combination with one or more features of the above or below embodiments, the potassium catalyst is selected from potassium acetate and potassium octanoate; the organotin catalyst is selected from dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetylacetone, tin carboxylates such as tin octanoate, tin ricinoleate, and tin neodecanoate; and the amine catalyst is selected from tertiary amines. In some embodiments, the reaction is carried out in the presence of at least one tin catalyst or at least one amino catalyst.

[0073] In another embodiment, optionally in combination with one or more features of the above or various embodiments described below, particularly when the compound of formula (I) has an epoxy group as a hydroxyl reactive group, the reaction can be carried out in the presence of a catalyst selected from: Lewis acids and Brønsted superacids, such as BF3, PF5, SbF5, HPF6, HBF4, HSbF6, CF3SO3H, Al(CF3SO3)3, Y(CF3SO3)3, Nd(CF3SO3)3; anionic catalysts, such as NaOH, KOH, CsOH, Sr(OH)2, Ba(OH)2, calcium naphthenate, calcium octanoate, phosphazeneonium compounds; coordination catalysts, such as alkylaluminum, alkylzinc and alcohols [Al(OR)3, Zn(OR)2], tetraphenylporphyrin aluminum and tetraphenylporphyrin zinc, alkoxytitanium [Ti(OR)4], and bimetallic cyanide catalysts (DMC) based on Zn3[Co(CN)6]3.

[0074] The reaction can be carried out continuously, for example in a static mixer or extruder, or intermittently, for example in a stirred reactor.

[0075] Step b) in the preparation of the nitrogen-containing alkoxysilane-terminated polyether polyol comprises reacting the intermediate product from step a) (i.e., the alkoxysilane-terminated polyether polyol (intermediate product)) with a compound of formula Ia to obtain the nitrogen-containing alkoxysilane-terminated polyether polyol. In the first step, the alkoxysilane-terminated polyether polyol (intermediate product) undergoes a hydrolysis reaction to generate silanol groups, yielding the corresponding hydrolyzed alkoxysilane-terminated polyether polyol derivative; then, the alkoxysilane moiety present in the compound of formula Ia or its corresponding hydrolyzed derivative reacts with the silanol moiety present in the hydrolyzed alkoxysilane-terminated polyether polyol derivative to generate the nitrogen-containing alkoxysilane-terminated polyether polyol.

[0076] The hydrolysis reaction is carried out in the presence of water, which may be intentionally added to the reaction medium or introduced along with the reactants provided as an aqueous solution. The amount of water present in the reaction medium should be sufficient to hydrolyze the intermediate product to generate the corresponding silanol-containing derivative (i.e., hydrolyzed alkoxysilane-terminated polyether polyol derivative).

[0077] Modified polymer polyol dispersion

[0078] The present invention also relates to novel stable modified polymeric polyol dispersions that can be obtained by polymerizing one or more polymeric particle precursors in a liquid polyol mixture under polymerization conditions, characterized in that the liquid polyol mixture comprises at least one base polyol and at least one nitrogen-containing alkoxysilane-terminated polyether polyol as defined herein.

[0079] The base polyol used to prepare the modified polymer polyol dispersions and / or polyurethane foams of the present invention may be any suitable type known in the art.

[0080] According to the present invention, representative base polyols that can be used to prepare modified polymer polyols may include polyether polyols, polyester polyols, polymer polyols, polyhydroxy-terminated acetal resins, hydroxyl-terminated amines, polyalkylene carbonate polyols, acrylic polyols, polyphosphate polyols, and polyols containing polyether carbonate polyols (POPC). Suitable polymer polyols include PDH polyols, PIPA polyols, SAN polyols, copolymer polyols, and polymer polyols containing polyether carbonate polyols (POPC) as base polyols. All other types of polyols, such as polyols derived from renewable resources (so-called natural oil polyols or NOP), may also be used in pure form or as mixtures, provided they have suitable physicochemical properties.

[0081] According to one embodiment, optionally in combination with one or more features of the embodiments described above or below, the preferred base polyol is selected from polyether polyols, polyester polyols, PDH polyols, PIPA polyols, SAN polyols, and polyols comprising polyether carbonate polyols (POPC). Some particularly preferred base polyols are selected from polyether carbonate polyols (POPC) and polyether polyols.

[0082] In a preferred embodiment, optionally in combination with one or more features of the embodiments described above or below, the base polyol comprises at least one ethylene oxide (EO) or propylene oxide (PO)-terminated polyether polyol.

[0083] According to one particular embodiment, optionally in combination with one or more features of the embodiments described above or below, the OH functionality of a suitable base polyol can be 2 to 10; in other particular embodiments, the OH functionality is 2 to 8, more particularly 2 to 6, and even more particularly 3 to 6. In some particular embodiments, the OH functionality is 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0084] According to a particular embodiment, optionally in combination with one or more features of the embodiments described above or below, a suitable base polyol is a reactive polyether polyol, i.e., an ethylene oxide (EO)-terminated polyether polyol having a terminal primary hydroxyl content of 35 to 99.9%, 35 to 99.9%, 35 to 98%, 40 to 95%, 45 to 90%, 50 to 85%, 75 to 99%, 77 to 98%, or 78 to 95% as determined by 13C nuclear magnetic resonance (RMN-13C). According to some particular embodiments, optionally in combination with one or more features of the embodiments described above or below, the base polyol is a reactive polyether polyol having a polyethylene oxide terminal block content of 5-20% by weight, preferably 10-19.5% by weight, more preferably 12-19% by weight, and even more preferably 13-18% by weight.

[0085] However, as described above, novel nitrogen-containing alkoxysilane-terminated polyether polyols allow for the preparation of stable modified polymer polyol dispersions, including PIPA polymer polyol dispersions and PHD polymer polyol dispersions, using non-reactive base polyols. Therefore, according to another specific embodiment, optionally in combination with one or more features of the 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)-terminated polyether polyol with a terminal primary hydroxyl content of 0 to 40%, 0.1 to 35%, 0.2 to 30%, 0.3 to 25%, 0.4 to 20%, or 0.5 to 15% as determined by 13C nuclear magnetic resonance (RMN-13C); more preferably, the base polyol is a non-reactive propylene oxide (PO)-terminated polyether polyol with a terminal primary hydroxyl content of 0 to 10%.

[0086] In some embodiments, optionally in combination with one or more features of the embodiments described above or below, the molecular weight (MW) of the base polyol is 150 to 16,000; preferably 200 to 12,500, more preferably 250 to 12,000. Some base polyols of the present invention have a molecular weight (MW) of 300 to 6,500, particularly 350 to 4,800, even more particularly 400 to 3,500. In other specific embodiments, optionally in combination with one or more features of the embodiments described above or below, the molecular weight of the base polyol can be 3,000 to 12,000, particularly 4,500 to 12,000, even more particularly 4,600 to 10,000, and even more particularly 5,000 to 9,000. In some specific embodiments, optionally in combination with one or more features of the embodiments described above or below, a base polyol with a molecular weight (MW) of 400 to 3,000 is used; alternatively, in some specific embodiments, the molecular weight of the base polyol is 4,500 to 12,000.

[0087] In some embodiments, optionally in combination with one or more features of the embodiments described above or below, the viscosity of the base polyol at 25°C is 50 to 25,000 mPa s, preferably 65 to 9,500 mPa s, more preferably 150 to 8,000 mPa s. In some embodiments, optionally in combination with one or more features of the embodiments described above or below, the viscosity of the base polyol at 25°C is 250 to 6,500 mPa s, particularly 400 to 2,000 mPa s, 420 to 1,800 mPa s, 450 to 1,600 mPa s, and 470 to 1,500 mPa s.

[0088] In some embodiments, optionally in combination with one or more features of the embodiments described above or below, the hydroxyl value (iOH) of the base polyol is 5 to 1800 mg KOH / g, 5 to 1500 mg KOH / g, 7 to 1400 mg KOH / g, 8 to 1300 mg KOH / g, 9 to 1200 mg KOH / g, or 10 to 1100 mg KOH / g. In other embodiments, the iOH of the base polyol is 5 to 800 mg KOH / g, 10 to 600 mg KOH / g, 15 to 500 mg KOH / g, or 25 to 460 mg KOH / g. In certain specific embodiments, the iOH of the base polyol is 20 to 80 mg KOH / g, 25 to 70 mg KOH / g, 26 to 65 mg KOH / g, or 26 to 58 mg KOH / g. In some embodiments, the iOH of the base polyol is 80 to 700 mg KOH / g, 81 to 650 mg KOH / g, 90 to 550 mg KOH / g, or 120 to 520 mg KOH / g. In some examples, the iOH of the base polyol is 28-280 mg KOH / g; according to additional examples, the iOH is 28-56 mg KOH / g, and in further examples, the iOH is 160-490 mg KOH / g.

[0089] It is well known in the art to use mixed polyols to modify the reactivity of a system or to impart desired properties to the resulting polyurethane. Therefore, according to one embodiment of the invention, mixtures of base polyols, mixtures of polymer polyols, or mixtures of base polyols and polymer polyols may also be used, optionally in combination with one or more features of the embodiments described above or below.

[0090] According to one embodiment of the invention, optionally in combination with one or more features of the embodiments described above or below, the stable modified polymer polyol dispersion is a polyisocyanate plus polypolymer polyol dispersion (PIPA polyol), and the base polyol is a non-reactive polyol.

[0091] According to one embodiment of the present invention, optionally in combination with one or more features of the embodiments described above or below, a method for preparing a modified polymer polyol dispersion includes preparing polymer particles in the presence of a liquid polyol mixture by: a. In a liquid polyol mixture and under polymerization conditions a.1) At least one compound having at least one basic nitrogen atom and characterized in that at least one hydrogen atom bonded to the nitrogen atom is present in the molecule; Reacts with a.2) or a.3), wherein, a.2) is at least one compound or mixture of compounds containing a phosphorus atom, selected from the group consisting of [bis(hydroxymethyl)phosphino]methanol (THP), tetra(hydroxymethyl)phosphonium salt (THPX), [bis(hydroxymethyl)phosphonyl]methanol (THPO), ({[bis(hydroxymethyl)phosphino]methoxy}methanol (mTHP), {bis[(hydroxymethoxy)methyl]phosphino}methanol (dTHP), ({bis[(hydroxymethoxy)methyl]phosphino}methoxy)methanol (tTHP), {[bis(hydroxymethyl)phosphonyl]methoxy}methanol (mTHPO), {bis[(hydroxymethoxy)methyl]phosphonyl}methanol (dTHPO), ({bis[(hydroxymethoxy)methyl]phosphonyl}methoxy)methanol (tTHPO), and mixtures thereof; as well as a.3) is a mixture of at least one of the above-mentioned compounds containing phosphorus atoms or compounds; a.2) is a mixture of condensation products obtained by reacting at least one compound containing at least one basic nitrogen atom; Among them, compound a.1) containing at least one basic nitrogen atom is selected from: a.1i) Melamine, trimethylol melamine, diethylenetriamine, tert-octylamine, dimethylaminopropylamine, polyethyleneimine; a.1ii) Compounds of formula (VII) or (VIII); and a.1iii) Its mixture; Among them, the compounds of formula (VII) are as follows: R 11 -NH2 (VII) Among them, R 11Selected from -H, -(C1-C3)alkyl, (C1-C3)alkyl-CO-, NH2-CO-, -(CH2) n -NH2, -CN, -NH2, -SO2NH2, cyclohexyl, phenyl, -SO2OH and -NHCONHNH2; where n is an integer from 1 to 18; And the compounds of formula (VIII) are as follows:

[0092] (VIII)

[0093] Among them, R 12 Selected from NH=C<, O=C< and S=C<; and R 13 Selected from H, -CN, -NH2, -CONH2, -CONHCONH2, and -CONHCONHCONH2; Or as an option b. Reacting b.1) with b.2) in a liquid polyol mixture and under polymerization conditions, optionally in the presence of a catalyst. b.1) At least one co-reactant selected from: b.1.i) An amine, alkanolamine, or diol having an equivalent weight of at most 400 and having at least one active hydrogen atom bonded to a nitrogen or oxygen atom; b.1.ii) Hydroxyphosphine; b.2) At least one polyisocyanate; The liquid polyol mixture comprises at least one base polyol and at least one nitrogen-containing alkoxysilane-terminated polyether polyol as defined in the first aspect and related embodiments of the present invention.

[0094] In the context of this invention, when referring to co-reactants, the term "equivalent weight" refers to the molecular weight of each isocyanate reactive hydrogen atom in the molecule.

[0095] According to some embodiments, optionally in combination with one or more features of the embodiments described above or below, the modified polymer polyol dispersion is prepared by using at least one co-reactant selected from the following as a polymer particle precursor: b.1.i) An amine, alkanolamine, or diol having an equivalent weight of at most 400 and having at least one active hydrogen atom bonded to a nitrogen or oxygen atom; and b.1.ii) Hydroxyphosphine.

[0096] In embodiments where the polymer particle precursor is defined as in b.1), the resulting modified polymer polyol dispersion is a PIPA polyol or a PHD polyol.

[0097] If a polyol forming a PHD is desired, the co-reactants forming the PHD may include amines, such as ammonia, aniline and substituted anilines, aliphatic amines, and mixtures thereof. Co-reactants forming the PHD may also include diamines, such as ethylenediamine and 1,6-hexanediamine; alkanolamines; hydrazine, 2,6-diaminotoluene, 2,4-diaminotoluene, 4,4'-methylenediphenylamine, and mixtures thereof.

[0098] Particularly preferred co-reactants are aromatic diamines, such as 2,6-diaminotoluene, 2,4-diaminotoluene, and 4,4'-methylenediphenylamine, which can optionally be obtained as recycled polyurethane materials.

[0099] If a PIPA polymer polyol is required, the co-reactants forming the PIPA may include alkylene glycols, alkanolamines, and hydroxyphosphines. In some embodiments, the co-reactants forming the PIPA may include glycols such as diethylene glycol, triethylene glycol, and polyethylene glycol; hydroxyphosphines 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 that may be considered include N-methylethanolamine, phenylethanolamine, ethylene glycolamine, and mixtures thereof.

[0100] It is also possible to provide a mixture of co-reactants that form PHD and PIPA to form hybrid PHD-PIPA particles.

[0101] At least one co-reactant forming the PHD and / or PIPA polymer is added to the mixture at a concentration of about 2% to about 80% by weight, preferably about 5% to about 60% by weight, of the total weight of the polyol mixture. All individual values ​​and sub-ranges between about 2% and about 80% by weight are included and disclosed herein.

[0102] According to some implementation methods, catalytic amounts of organometallic compounds can be used. Organometallic compounds that can be used as catalysts include compounds 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-ethylhexanoate, lead benzoate, lead oleate, dibutyltin dilaurate, tributyltin, butyltin trichloride, dimethyltin, dimethyltin dinedecanoate, tin tetrachloride, stannous octoate, stannous oleate, stannous ricinoleate, di(2-ethylhexanoate)dibutyltin, zinc octoate, zinc ricinoleate, ferric chloride, antimony trichloride, antimony glycolate, tin glycolate, iron acetylacetone, etc. Catalysts can accelerate the reaction of diisocyanates with the primary hydroxyl groups of alkanolamines.

[0103] Therefore, according to some embodiments, a method for preparing modified polymer polyols, optionally in combination with one or more features of the embodiments described above or below, includes: i. Mixing at least one base polyol with at least one nitrogen-containing alkoxysilane-terminated polyether polyol as defined in the first aspect and related embodiments of the present invention to obtain a liquid polyol mixture; and ii. Optionally, in the presence of a catalyst and under polymerization conditions, add to the liquid polyol mixture obtained in i) simultaneously or in any order the following: b.1) At least one co-reactant selected from: b.1.i) An amine, alkanolamine, or diol having an equivalent weight of at most 400 and having at least one active hydrogen atom bonded to a nitrogen or oxygen atom; and b.1.ii) Hydroxyphosphine; b.2) At least one polyisocyanate; In this embodiment, at least one co-reactant b.1) is selected from ammonia, aniline, (C1-C3)alkyl-substituted aniline, aliphatic amines, ethylenediamine, 1,6-hexanediamine, hydrazine, 2,6-diaminotoluene, 2,4-diaminotoluene, 4,4'-methylenediphenylamine, diethylene glycol, triethylene glycol, and polyethylene glycol; hydroxyphosphine, such as hydroxyalkylphosphine, hydroxyalkylphosphonium salts, hydroxyalkylphosphine oxides, and derivatives thereof; and alkanolamines, such as monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, 2-(2-aminoethoxyethanol), hydroxyethylpiperazine, monoisopropanolamine, diisopropanolamine, N-methylethanolamine, phenylethanolamine, ethylene glycolamine, and mixtures thereof.

[0104] According to certain embodiments, a method for preparing modified polymer polyols, optionally in combination with one or more features described above or below, includes: i. Mixing at least one base polyol with at least one nitrogen-containing alkoxysilane-terminated polyether polyol as defined in the first aspect and related embodiments of the present invention to obtain a liquid polyol mixture; ii. Add, simultaneously or in any order, the following to the liquid polyol mixture obtained in i). a.1) At least one compound having at least one basic nitrogen atom and characterized in that at least one hydrogen atom bonded to the nitrogen atom is present in the molecule; And a.2) or a.3), where, a.2) is at least one compound or mixture of compounds containing phosphorus atoms, selected from: I. [bis(hydroxymethyl)phosphino]methanol (THP), at concentrations of 0-100 mol%, 0-99.9 mol%, 20-95 mol%, 30-90 mol%, 35-85 mol%, 50-75 mol%, or 60-72 mol%; II. Tetra(hydroxymethyl)phosphonium salt (THPX), in concentrations of 0-100 mol%, 0-99.9 mol%, 0-90.0 mol%, 0.05-75 mol%, 0.05-50 mol%, 0.1-40 mol%, 0.1-25 mol%, 0.2-15 mol% or 0.5-10 mol% THPX; III. [bis(hydroxymethyl)phosphoryl]methanol (THPO), in concentrations of 0-100 mol%, 0-99.9 mol%, 0-40 mol%, 1-15 mol%, 2-12 mol%, or 2-7 mol% THPO; IV. {[bis(hydroxymethyl)phosphine]methoxy}methanol (mTHP), in concentrations of 0-80 mol%, 0.1-60 mol%, 0.2-45 mol%, 0.4-40 mol%, 0.5-30 mol%, or 1-25 mol% mTHP; V. {bis[(hydroxymethoxy)methyl]phosphonyl}methanol (dTHP), at concentrations of 0-30 mol%, 0.1-20 mol%, 0.2-15 mol%, or 0.25-10 mol% dTHP; VI. ({bis[(hydroxymethoxy)methyl]phosphino}methoxy)methanol (tTHP), at concentrations of 0-15 mol%, 0.05-5 mol%, 0.075-2 mol%, or 0.1-1 mol% tTHP; VII. {[bis(hydroxymethyl)phosphoryl]methoxy}methanol (mTHPO), with a concentration of 0-20 mol%, 0.05-10 mol%, 0.1-6.5 mol%, and 0-6.1 mol% mTHPO; VIII. {bis[(hydroxymethoxy)methyl]phosphoryl}methanol (dTHPO), at concentrations of 0-10 mol%, 0.05-5 mol%, and 0.1-1 mol% dTHPO; and IX. ({bis[(hydroxymethoxy)methyl]phosphoryl}methoxy)methanol (tTHPO), at concentrations of 0-4 mol%, 0.01-1 mol%, 0.05-0.2 mol%, and 0-0.5 mol% tTHPO; The total amount of phosphorus-containing compounds in the mixture is 100 moles.

[0105] as well as

[0106] a.3) is a mixture of at least one of the above compounds or compounds; a.2) is a mixture of condensation products obtained by reacting at least one compound a.1) having at least one basic nitrogen atom; Among them, compound a.1) containing at least one basic nitrogen atom is selected from: Melamine, trimethylol melamine, diethylenetriamine, tert-octylamine, dimethylaminopropylamine, polyethyleneimine; Compounds of formula (VII) or (VIII); and Its mixture.

[0107] Specific examples of compounds having at least one basic nitrogen atom and characterized by the presence of at least one hydrogen atom bonded to the nitrogen atom in the molecule include NH3, primary aliphatic and primary alicyclic amines, aliphatic and alicyclic primary and secondary polyamines, and aromatic primary, secondary, and tertiary amines and primary, secondary, and tertiary polyamines, such as cyanamide, guanidine, 2-cyanoguanidine, methylamine, ethylenediamine, diethylenetriamine, hexamethylenediamine, hydrazine, tert-octylamine, dimethylaminopropylamine, cyclohexylamine, trimethylolmelamine, urea, thiourea, aniline, and polyethyleneimine. NH3, cyanamide, melamine, urea, thiourea, diethylenetriamine, hydrazine, and ethylenediamine are particularly preferred examples.

[0108] Those skilled in the art will know, when necessary, methods and suitable media for dissolving compounds containing at least one basic nitrogen atom.

[0109] According to a particularly preferred embodiment, the modified polymer polyol dispersion is obtained using a mixture of hydroxyalkylphosphine (e.g., [bis(hydroxymethyl)phosphino]methanol (THP)) and its derivatives (including salts, oxides and hemiacetals) as polymer particle precursors.

[0110] It is known that when tetra(hydroxymethyl)phosphonium salt (THPX) reacts with a base (e.g., KOH), a mixture of THP, formaldehyde, the salt KX, and water can be obtained. Furthermore, depending on the alkaline conditions used, [bis(hydroxymethyl)phosphonyl]methanol (THPO, also known as tri(hydroxymethyl)phosphine oxide) can also be obtained as a byproduct along with THP. Additionally, THP and THPO may react with formaldehyde to form the corresponding hemiacetals (yielding mono-, di-, and tri-substituted hemiacetals of THP and THPO as reaction products). In some cases, the reaction can be carried out under insufficient alkalinity, in which case unreacted THPX may be present in the reaction medium along with the resulting products. The amount of THPO generated depends on the reaction conditions. Alkaline pH favors the formation of THPO. Therefore, depending on the conditions used, the reaction products between THPX and a base can be a complex mixture of phosphorus compounds (THP, THPO, their corresponding hemiacetals, and unreacted THPX), water, the corresponding salt, and formaldehyde.

[0111] According to some embodiments, optionally in combination with one or more features of the embodiments described above or below, the mixture of compounds containing phosphorus atoms comprises a tetra(hydroxymethyl)phosphonium salt (THPX) at a concentration of 0-100 mol%; wherein the antication (X) of the salt is a monovalent, divalent, or trivalent ligand selected from chloride, bromine, iodine, sulfate, phosphate, hydrogen phosphate, dihydrogen phosphate, hydroxide, acetate, oxalate, and citrate.

[0112] In some embodiments, optionally in combination with one or more features of the embodiments described above or below, the hydroxyalkyl phosphonium salt is selected from: tetra(hydroxymethyl)phosphonium chloride (THPC), bis[tetra(hydroxymethyl)phosphonium]sulfate (THPS), tetra(hydroxymethyl)phosphonium phosphate (THPP (3:1)), tetra(hydroxymethyl)phosphonium monohydrogen phosphate (THPP (2:1)), tetra(hydroxymethyl)phosphonium dihydrogen phosphate (THPP (1:1)), tetra(hydroxymethyl)phosphonium hydroxide (THPOH), tetra(hydroxymethyl)phosphonium oxalate (THPOx), and tetra(hydroxymethyl)phosphonium acetate (THPA).

[0113] Specific examples of hydroxyalkyl phosphonium salts are tetra(hydroxymethyl)phosphonium chloride (THPC) and bis[tetra(hydroxymethyl)phosphonium]sulfate (THPS).

[0114] If a hydroxyalkylphosphonium salt is used, it can be treated with an alkali to obtain the corresponding hydroxyalkylphosphine. This alkali can be an organic or inorganic base; preferably selected from KOH, NaOH, Ca(OH)₂, Mg(OH)₂, Ba(OH)₂, triethylamine (NEt₃), and tributylamine (NBu₃). Alternatively, the hydroxyalkylphosphonium salt can be treated with a basic ion exchange resin. Both strong and weak ion exchange resins are suitable for this method. An example of a strong base is Amberlite. ® IRN78 or Amberlist ® A26. An example of a weak base is Amberlite. ® IRA 67, Lewatit ® MP-62 and Lewatit ® VP OC1065.

[0115] As described above, when hydroxyalkylphosphonium salts react with a base, the corresponding hydroxyalkylphosphine, the corresponding salt, the corresponding aldehyde, and water can be obtained, while other phosphorus compounds may appear as reaction products. THPO is usually obtained as a byproduct along with THP. Furthermore, THP and THPO can react with formaldehyde to produce the corresponding hemiacetals. Monosubstituted, disubstituted, and trisubstituted hemiacetals of THP and THPO can be obtained as reaction products.

[0116] According to some embodiments, a method for preparing modified polymer polyols, optionally in combination with one or more features of the embodiments described above or below, includes: i. Preferably, at least one tetra(hydroxymethyl)phosphonium salt (THPX) is mixed with an aqueous or alcoholic solution of an alkali at a temperature of 0°C to 60°C; ii. Optionally, filter out the resulting solution; iii. The solvent and volatiles (especially formaldehyde) are removed by distillation to obtain at least one compound or mixture of compounds containing a phosphorus atom, a.2), selected from the group consisting of [bis(hydroxymethyl)phosphino]methanol (THP), tetra(hydroxymethyl)phosphonium salt (THPX), [bis(hydroxymethyl)phosphonyl]methanol (THPO), ({[bis(hydroxymethyl)phosphino]methoxy}methanol (mTHP), {bis[(hydroxymethoxy)methyl]phosphino}methanol (dTHP), ({bis[(hydroxymethoxy)methyl]phosphino]methoxy)methanol (tTHP), {[bis(hydroxymethyl)phosphonyl]methoxy}methanol (mTHPO), {bis[(hydroxymethoxy)methyl]phosphonyl]methanol (dTHPO), ({bis[(hydroxymethoxy)methyl]phosphonyl]methoxy)methanol (tTHPO), and mixtures thereof; iv. Optionally, filter out the resulting solution; v. Optionally, the product obtained in iii or the solution obtained in iv is oxidized, wherein the oxidation can be accomplished by simply heat treatment in an air atmosphere or by using an oxidizing agent such as hydrogen peroxide, thereby obtaining a mixture with a high content of oxidized components (a.2). vi. Mix at least one basic polyol with at least one alkoxysilyl group modified compound as defined above to obtain a liquid polyol mixture; vii. In the presence of the liquid polyol mixture obtained in vi, polymer particles are prepared by reacting the following substances simultaneously or sequentially with the liquid polyol mixture obtained in vi, either in any order or in any other manner. At least one compound a.1) having at least one basic nitrogen atom, characterized in that at least one hydrogen atom is present in the molecule bonded to the nitrogen atom, and is selected from melamine, trimethylolmelamine, diethylenetriamine, tert-octylamine, dimethylaminopropylamine, polyethyleneimine, compounds of formula (VII) or (VIII) as defined above, and mixtures thereof; and At least one compound or mixture of compounds containing phosphorus atoms obtained in iii, and the filtrate or mixture thereof obtained in iv.

[0117] According to certain embodiments, optionally in combination with one or more features of the embodiments described above or below, the aqueous or alcoholic solution of the base used in i may be selected from KOH, NaOH, Ca(OH)2, Mg(OH)2, Ba(OH)2, triethylamine (NEt3), and tributylamine (NBu3). Alternatively, the hydroxyalkyl phosphonium salt can be treated with a basic ion exchange resin. Both strong and weak ion exchange resins are suitable for this method. An example of a strong base is Amberlite. ® IRN78 or Amberlist ® A26. An example of a weak base is Amberlite. ® IRA 67, Lewatit ® MP-62 and Lewatit ® VP OC1065.

[0118] According to certain embodiments, optionally in combination with one or more features of the embodiments described above or below, the distillation removal step is carried out under vacuum and at a temperature of 25-99°C, preferably 40-90°C, more preferably 60-80°C.

[0119] The molar ratio used between the compound containing a phosphorus atom and the compound containing at least one basic nitrogen atom depends on the functionality of the compound containing at least one basic nitrogen atom. Those skilled in the art will know how to adjust the molar ratio according to the description and examples of the present invention to obtain a solid product.

[0120] Compounds containing at least one basic nitrogen atom can be added to the reactor as a solid or dissolved in a suitable solvent. An aqueous solution of an amine is preferred.

[0121] The reaction can be carried out under atmospheric pressure, vacuum, or pressure. Furthermore, the reaction can be carried out under an inert atmosphere (nitrogen, argon) or an oxidizing atmosphere (air).

[0122] Vigorous stirring is necessary to ensure particle formation and prevent product agglomeration.

[0123] Regarding the specific conditions for implementing the method of the present invention, those skilled in the art will adjust the parameters of the above steps according to the description and examples of the present invention.

[0124] In some embodiments, optionally in combination with one or more features of the embodiments described above or below, the method for preparing modified polymer polyol dispersions includes: i) Mixing at least one basic polyol with at least one alkoxysilyl group modified compound as defined above to obtain a liquid polyol mixture; ii) Add, simultaneously or in any order, the liquid polyol mixture obtained in i. At least one compound a.1) as defined above, having at least one basic nitrogen atom, characterized in that at least one hydrogen atom bonded to a nitrogen atom is present in the molecule; and a.3) is a mixture of condensation products as defined above.

[0125] The condensation product a.3) is obtained by reacting at least one compound or a mixture of compounds a.2) with at least one compound a.1) having at least one basic nitrogen atom; wherein the condensation reaction is carried out at a temperature of 2-140°C, preferably 25-120°C, more preferably 40-100°C, and particularly preferably 60-90°C. Those skilled in the art can adjust the temperature conditions according to the compound a.1) used in this method.

[0126] According to certain specific embodiments, optionally in combination with one or more features of the embodiments described above or below, a method for preparing modified polymer polyols includes: i) Mixing at least one basic polyol with at least one alkoxysilyl group modified compound as defined above to obtain a liquid polyol mixture; ii) Add, simultaneously or in any order, the liquid polyol mixture obtained in i. At least one compound containing at least one basic nitrogen atom (a.1), selected from: Melamine, trimethylol melamine, diethylenetriamine, tert-octylamine, dimethylaminopropylamine, polyethyleneimine; Compounds of formula (VII), wherein R 11 Selected from H, methyl, -CN, CH3-CO-, NH2-CO-; Compounds of formula (VIII), wherein R 12 Selected from O=C<, S=C<, and R 13 For H; and Its mixture; as well as The mixture of condensation products (a.3) can be obtained at a temperature of 2-140°C, preferably 25-120°C, more preferably 40-100°C, and particularly preferably 60-90°C.

[0127] According to some embodiments, a method for preparing modified polymer polyols, optionally in combination with one or more features of the embodiments described above or below, includes: i) Preferably, at a temperature of 0°C to 60°C, at least one tetra(hydroxymethyl)phosphonium salt (THPX) is mixed with an aqueous or alcoholic solution of an alkali. ii) Optionally, filter out the resulting solution; iii) The solvent and volatiles are removed by distillation to obtain at least one compound or mixture of compounds containing phosphorus atoms as defined above, a.2); iv) Optionally, filter out the resulting solution; v) Optionally, the product obtained in iii or the solution obtained in iv is oxidized, wherein the oxidation can be carried out by simply heat treatment in an air atmosphere or by using an oxidizing agent such as hydrogen peroxide, thereby obtaining at least one compound or a mixture of compounds with a high content of oxidized components a.2); vi) Preferably at a temperature of 2 to 140°C, more preferably 25 to 120°C, more preferably 40 to 100°C, and most preferably 60 to 90°C; reacting at least one compound or mixture of compounds obtained in iii, the filtrate obtained in iv, the oxidized mixture obtained in v, or a mixture thereof with at least one compound having at least one basic nitrogen atom, thereby obtaining a mixture of condensation products a.3), wherein the at least one compound having at least one basic nitrogen atom is characterized in that at least one hydrogen atom is present in the molecule and is selected from melamine, trimethylolmelamine, diethylenetriamine, tert-octylamine, dimethylaminopropylamine, polyethyleneimine, compounds of formula (VII) or (VIII) as defined above, and mixtures thereof; vii) Mix at least one basic polyol with at least one alkoxysilyl group modified compound as defined above to obtain a liquid polyol mixture; viii) In the presence of the liquid polyol mixture obtained in vii, polymer particles are prepared by reacting the following substances simultaneously or sequentially with the liquid polyol mixture obtained in vii, either in the same order or in any other order. At least one compound a.1) having at least one basic nitrogen atom, characterized in that the molecule contains at least one hydrogen atom bonded to the nitrogen atom, selected from melamine, trimethylolmelamine, diethylenetriamine, tert-octylamine, dimethylaminopropylamine, polyethyleneimine, compounds of formula (VII) or (VIII) as defined above, and mixtures thereof; and The mixture of condensation products obtained in vi (a.3).

[0128] According to certain specific embodiments, optionally in combination with one or more features of the embodiments described above or below, the aqueous or alcoholic solution of the base used in step i) above is selected from KOH, NaOH, Ca(OH)2, Mg(OH)2, Ba(OH)2, triethylamine (NEt3), and tributylamine (NBu3). Alternatively, hydroxyalkyl phosphonium salts can be treated with basic ion exchange resins. Both strong and weak ion exchange resins are suitable for this method. An example of a strong base is Amberlite. ® IRN78 or Amberlist ® A26. An example of a weak base is Amberlite. ® IRA 67, Lewatit ® MP-62 and Lewatit ® VPOC1065.

[0129] According to certain specific embodiments, optionally in combination with one or more features of the embodiments described above or below, the condensation product obtained by reacting at least one compound or mixture of compounds a.2 obtained in step iii), the filtrate obtained in step iv), the oxidized mixture obtained in step v), or a mixture thereof with at least one compound a.1 bearing at least one basic nitrogen atom (selected from melamine, trimethylolmelamine, diethylenetriamine, tert-octylamine, dimethylaminopropylamine, polyethyleneimine, compounds of formula (VII) or (VIII) as described above, and mixtures thereof) can be obtained at a temperature of 2 to 140°C, preferably 25 to 120°C, more preferably 40 to 100°C, and most preferably 60 to 90°C. Those skilled in the art will recognize how to adjust the temperature and reaction time to complete the condensation reaction according to the description and examples herein.

[0130] In some embodiments, optionally in combination with one or more features of the embodiments described above or below, the modified polymer polyol dispersion obtained by the methods described herein can be purified by vacuum stripping; removing solids including unreacted compounds with at least one basic nitrogen atom and complex mixtures of reaction byproducts; and recovering the purified modified polymer polyol dispersion. The resulting purified modified polymer polyol dispersion can be used to prepare polyurethane foams exhibiting improved porosity and wet compression set; and polyisocyanurate foams exhibiting improved pyrolysis according to DIN 4102-1.

[0131] Therefore, according to some embodiments, optionally in combination with one or more features of the embodiments described above or below, the method for preparing the above-described modified polymer polyol dispersion further includes: i) Purify the crude modified polymer polyol obtained in (1) by vacuum stripping, removing solids including unreacted compounds with at least one basic nitrogen atom and a complex mixture of reaction byproducts; and ii) Recover the purified modified polymer polyol dispersion.

[0132] Unrestricted by theory, the removed solids include unreacted compounds with at least one basic nitrogen atom and complex mixtures of reaction byproducts, such as formaldehyde and various oligomers generated as reaction byproducts.

[0133] According to one particular implementation, the stripping step can be carried out by blowing inert gas, steam, or air into a reaction chamber or stripping tower containing crude modified polymer polyols to remove solids trapped in the cold trap and recover the purified modified polymer polyols.

[0134] Alternatively, known methods for removing solids, including complex mixtures of unreacted compounds containing at least one basic nitrogen atom and reaction byproducts, can be applied instead of stripping methods, such as thin-film evaporation or falling-film evaporation. Further examples of alternative methods are known to those skilled in the art.

[0135] The stable modified polymer polyol dispersion obtained by the above method is a polyol with high nitrogen and phosphorus content and finely dispersed polymer particles.

[0136] In some embodiments, optionally in combination with one or more features of the embodiments described above or below, the stable modified polymer polyol dispersion comprises 5% to 95% by weight, 10% to 90% by weight, 15% to 80% by weight, and 20% to 70% by weight of dispersed polymer particles.

[0137] Therefore, the phosphorus content of the polymer particles dispersed in at least one polyol is 0.1 to 50% by weight; preferably 5 to 40% by weight, most preferably 13 to 35% by weight. The nitrogen content of the polymer particles dispersed in at least one polyol is 0.1 to 40% by weight; preferably 5 to 40% by weight, most preferably 7 to 30% by weight. The total content of nitrogen and phosphorus is 0.1 to 90% by weight; preferably 10 to 70% by weight, most preferably 20 to 60% by weight.

[0138] According to a particular embodiment of the invention, polymer particles dispersed in at least one base polyol may be further oxidized using a suitable oxidant, such as manganate, permanganate, peroxide, and molecular oxygen; preferably, the oxidant is molecular oxygen and / or hydrogen peroxide.

[0139] The oxidation step is carried out by introducing at least one oxidant into the medium after the polycondensation reaction has occurred. If hydrogen peroxide is used as the oxidant, it can be added in aqueous solution to the modified polymer polyol, which contains a stable dispersion of polymer particles in the base polyol. If molecular oxygen is used as the oxidant, oxidation can be accomplished by blowing air or oxygen into the system after the formation of polymer particles.

[0140] The polyol composition of the present invention comprises polymer particles, wherein at least 90% by volume of the particles have a particle size of less than 30 µm, preferably from 0.5 µm to 20 µm, more preferably from 0.6 µm to 15 µm, and even more preferably from 0.8 µm to 10 µm (the particle size was determined using a Malvern Instruments Mastersizer 3000 equipped with a hydro SM dispersion device and ethanol was used as the eluent).

[0141] Particle size distribution can be trimodal, bimodal, unimodal, or even have different independent distributions.

[0142] The modified polymer polyols of the present invention can be used to prepare polyurethane materials, such as polyurethane foams, adhesives, elastomers, sealants and coatings; preferably, polyurethane materials with flame-retardant properties.

[0143] Regarding the specific conditions for implementing the method of the present invention, those skilled in the art will adjust the parameters of the above steps according to the description and examples of the present invention.

[0144] polyurethane materials

[0145] Another object of the present invention is to provide a method for preparing a polyurethane material, wherein the method comprises reacting at least one polyisocyanate with an isocyanate reactive component comprising at least one stable modified polymer polyol dispersion as defined in the corresponding aspects and related embodiments of the present invention, in the presence of at least one catalyst and optional additives.

[0146] Another object of the present invention is to provide polyurethane materials that can be obtained by the methods defined herein.

[0147] At least one polyisocyanate that can be used in this invention includes aliphatic, alicyclic, aryliphatic, and aromatic isocyanates. Examples of suitable aromatic polyisocyanates include 4,4'-, 2,4'-, and 2,2'- isomers of diphenylmethane diisocyanate (MDI), mixtures thereof, and mixtures of MDI polymers and MDI monomers, toluene-2,4-diisocyanate and toluene-2,6-diisocyanate (TDI), isophenyl diisocyanate and terephenyl diisocyanate, chlorophenyl-2,4-diisocyanate, diphenyl-4,4'-diisocyanate, 4,4'-diisocyanate-3,3'-dimethyldiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate, diphenyl ether diisocyanate, 2,4,6-triisocyanate-toluene, and 2,4,4'-triisocyanate-diphenyl ether. Mixtures of polyisocyanates can be used, such as mixtures of the 2,4- and 2,6-isomers of commercially available toluene diisocyanate. In embodiments of the invention, crude polyisocyanates can also be used, such as crude toluene diisocyanate obtained by phosgenation of a mixture of p-toluene diamine or crude diphenylmethane diisocyanate obtained by phosgenation of crude methylene diphenylamine. TDI / MDI mixtures can 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 analogs of the above aromatic polyisocyanates, and mixtures thereof.

[0148] Polyisocyanates can be used at isocyanate indices of 60 to 140, preferably 80 to 120, and most preferably 90 to 110. The isocyanate index is defined as the ratio of isocyanate groups to reactive hydrogen atoms in a polyurethane formulation. Therefore, the isocyanate index represents the percentage of the amount of isocyanate actually used in the formulation relative to the theoretically required amount of isocyanate based on the amount of reactive hydrogen atoms in the isocyanate used in the formulation.

[0149] In the preparation of polyurethane foam, polyisocyanate, water, and additives commonly used in polyurethane foam manufacturing can be used in combination with the modified polymer polyol of this invention. The amounts and reaction conditions will vary depending on the type of polyurethane foam to be prepared and the desired properties. Those skilled in the art know the different types of reactants, catalysts, and conditions required for the preparation of polyurethane foam.

[0150] In the preparation of polyurethane foam, polyisocyanate, water, and additives commonly used in polyurethane foam manufacturing can be used in combination with the modified polymer polyol of this invention. The amounts and reaction conditions will vary depending on the type of polyurethane foam to be prepared and the desired properties. Those skilled in the art know the different types of reactants, catalysts, and conditions required for the preparation of polyurethane foam.

[0151] The blowing agent can be selected from any blowing agent well known in the art. The primary blowing agent is carbon dioxide produced by the decarboxylation of carbamic acid generated from the reaction of water and isocyanate. Depending on regulations and the target foam properties, alternative blowing agents (ABA), such as liquid carbon dioxide, dichloromethane, HCFC, pentane, etc., may be used.

[0152] In the expandable polymer composition, the concentration of the foaming agent is preferably 0% to 120% by weight relative to the total weight of the expandable polymer mixture; more preferably 0% to 40% by weight; and even more preferably 0% to 10% by weight.

[0153] Any known catalyst can be used, including amine 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'-dimethylisopropylpropylenediamine, N,N-diethyl-3-diethylaminopropylamine, and dimethylbenzylamine. Metal catalysts based on tin, zinc, bismuth, and other metals can be used in foam formulations, such as tin octoate, dibutyltin dilaurate, zinc octoate, and other similar compounds.

[0154] The amount of catalyst in the formulation can be 0 to 4%; preferably 0 to 2%, and most preferably 0 to 1%. Another option is to use autocatalytic polyols based on tertiary amine initiators instead of amine catalysts, thereby reducing volatile organic compounds in the foam.

[0155] Other additives that can be used in the preparation of polyurethane polymers include fillers (such as talc, silica, titanium dioxide, magnesium oxide, calcium carbonate, carbon black, graphite, magnesium silicate, or clays such as kaolinite and montmorillonite); flame retardants (such as halogenated flame retardants like hexabromocyclododecane and brominated polymers, or phosphorus flame retardants like triphenyl phosphate, dimethyl methylphosphonate, red phosphorus, or aluminum diethylphosphonate); acid removers (such as calcium stearate, magnesium oxide, zinc oxide, tetrasodium pyrophosphate, or hydrotalcite); antioxidants (such as hindered phenols, phosphites, and mixtures thereof); and pigment and foaming agent stabilizers. Silicone surfactants may be needed to stabilize the foam formulation; these are available from major suppliers such as EVONIK, MOMENTIVE, AIRPRODUCTS, and STRUKSILON.

[0156] Polyurethane foam can be prepared by any known method. Thus, for example, polyurethane foam can be formed by the so-called prepolymer method, in which a stoichiometric excess of polyisocyanate is first reacted with a high stoichiometric amount of polyol to form a prepolymer, and in a second step, the prepolymer is reacted with a chain extender and / or water to form the desired foam. The foaming method is also suitable. A so-called one-step method can also be used. In this type of one-step method, the polyisocyanate and all isocyanate reactive components are simultaneously mixed together and allowed to react. Three widely used one-step methods applicable to this paper include the slabstock foam method, the high-resilience slabstock foam method, the molded foaming method, and the box-type foaming method.

[0157] The polyurethane foam prepared from the stable modified polymer polyol of the present invention can have a density of 4 to 120 kg / m³. 3 Preferably 15 to 80 kg / m 3 The optimal value is 20 to 60 kg / m³. 3 .

[0158] In the context of this invention, the term "modified polymeric polyol" is also referred to as "polymeric polyol dispersion" or "polymeric polyol," which means a dispersion of polymeric particles, i.e., a dispersion of organic fillers in a continuous phase composed of one or more compounds having multiple hydroxyl groups ("base polyols").

[0159] In the context of this invention, when referring to compounds containing a basic nitrogen atom, the term "functionality" is used herein to denote the number-average functionality (the number of hydrogen atoms bonded to a nitrogen atom per molecule) of the compound. When referring to a base polyol, the term "functionality" is used to denote the number-average functionality (the number of hydroxyl groups per molecule) of the polyol composition, assumed to be equal to the number-average functionality (the number of active hydrogen atoms per molecule) of the initiator used in the preparation. Although the actual functionality is usually slightly lower in practice due to some terminal unsaturation, for the purpose of characterizing a base polyol, the functionality of the polyol is the same as the functionality of the initiator used in the preparation.

[0160] In the context of this invention, the term "iOH" refers to the hydroxyl value (iOH), defined as the number of milligrams of potassium hydroxide required to prepare a fully phthaliclated derivative completely from 1 gram of polyol via hydrolysis. The hydroxyl value is determined according to ASTM D4274-16.

[0161] According to some examples of the invention, the term "stable polyol" or "stable modified polymer polyol" refers to a dispersion of polymer particles in at least one polyol that does not precipitate or at least remains dispersed when mixed with other foaming components.

[0162] According to some examples of the invention, the method should be able to produce highly stable modified polymeric polyols in which the dispersed particles are small (and therefore less prone to precipitation). Surprisingly, the modified polymeric polyols remain stable even when the base polyol is a non-reactive polyether polyol (i.e., predominantly containing secondary hydroxyl groups).

[0163] In the context of this invention, the "molecular weight" of the term polyol is calculated using the following equation:

[0164] "Functionality" refers to the functionality of the polyol, that is, the average number of hydroxyl groups in each polyol molecule; the hydroxyl value (iOH) is calculated according to ASTM D4274-16.

[0165] In the context of this invention, the "equivalent molecular weight" of polyols is calculated using the following equation: Polyol equivalent molecular weight = polyol molecular weight / functionality = 56100 / hydroxyl value (iOH) In the context of this invention, the "weight-average molecular weight" was determined by gel permeation chromatography (GPC).

[0166] In the context of this invention, viscosity measurements (in mPa·s) were obtained at 25°C using a Haake™ Viscotester™ rheometer.

[0167] The solids content of the modified polymer polyol is calculated using the following equation:

[0168] In the context of this invention, the term "weight percentage (%)" refers to the percentage of each component in a combination or composition relative to the total weight.

[0169] The term "obtainable" in this invention refers to a modified polymer polyol as defined herein by its preparation method, and to a product obtainable by the preparation method defined herein. For the purposes of this invention, the expressions "obtainable," "obtained," and equivalents are used interchangeably, and in any case, the expression "obtainable" includes the expression "obtained."

[0170] For the purposes of this invention, any range given includes both the lower and upper limits of the range. Ranges given (e.g., temperature, time, size, etc.) should be considered approximate unless otherwise explicitly stated.

[0171] Although only a few examples have been disclosed herein, other alternatives, modifications, uses, and / or equivalents may exist. Furthermore, all possible combinations of the described examples are covered. Therefore, the scope of the invention should not be limited to the specific examples, but should be determined only through a reasonable interpretation of the following claims.

[0172] The following examples are used to illustrate implementation of the invention, but are not intended to limit its scope. Unless otherwise stated, all parts and percentages are by weight.

[0173] The modified polymeric polyols of this invention can be used to prepare polyurethane foams that meet one or more FR (flame retardant) standards, such as the British Standard Flammability Test (BS5852 - Flame Source 5) using a wooden component (referred to as a crib) as an ignition source; the Crib 5 Flammability Test (BS5852, Flame Source 5) uses a crib made of 18 wooden sticks with dimensions of 40 × 6.5 × 6.5 mm. 1.4 mL of propan-2-ol is added to the lint to initiate the test. The pass / fail criteria are: (i) weight loss of each specimen not exceeding 60 grams; (ii) self-extinguishing of the specimen within 10 minutes after ignition; (iii) flame not penetrating the entire thickness of the specimen; and (iv) damage on both sides of the ignition source not exceeding 10 cm (measured in the width direction, assuming damage not exceeding 25 cm centered on a 5 cm wide crib structure).

[0174] Example

[0175] The following materials were used: - Polyol A - a polyether polyol (PO / EO) initiated by sorbitol (functionality 6), with a hydroxyl value of 29.5 mgKOH / g, an ethylene oxide-terminated block content of 16.2% by weight, a primary OH group content of 81%, and a viscosity of 1500 mPa s at 25°C.

[0176] - Polyol B – a glycerol (functionality 3)-initiated polyether polyol (100% PO) with a hydroxyl value of 56 mg KOH / g and a viscosity of 470 mPa s at 25°C. Polyol B is a non-reactive polyol.

[0177] - Polyol C – a glycerol (functionality 3)-initiated polyether polyol (PO / EO) with a hydroxyl value of 48 mg KOH / g, containing 12% by weight of randomly distributed polyethylene units along the central backbone of the polyol, and a viscosity of 560 mPa s at 25°C. Polyol C is a non-reactive polyol.

[0178] - THPS—Titra(hydroxymethyl)phosphonium sulfate (70-75% by weight aqueous solution). Available from Sigma Aldrich.

[0179] - KOH — Potassium hydroxide (≥85%). Available from Sigma Aldrich.

[0180] - DBTL — Dibutyltin dilaurate (95%). Available from Sigma Aldrich.

[0181] - 3-(triethoxysilyl)propyl isocyanate (95%). Available from Sigma Aldrich.

[0182] - Kosmos T900 - Stannous neodecanoate, available from Evonik Industries.

[0183] - Tetrafluoroboric acid solution (48%). Available from Sigma Aldrich.

[0184] - Geniosil GF-80 — 3-Epoxypropoxypropyltrimethoxysilane (trimethoxy({3-[(epoxyethylene-2-yl)methoxy]propyl})silane) (≥98%), supplied by Wacker.

[0185] - Geniosil GF-91 — N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, supplied by Wacker.

[0186] - Triethanolamine (TEOA) (≥99.0%). Available from Sigma Aldrich.

[0187] - Tegoamin® 33 — a 33% by weight dipropylene glycol solution of triethylenediamine, available from Evonik Industries.

[0188] - Tegoamin® BDE - a 70% dipropylene glycol solution of bis(2-dimethylaminoethyl) ether, available from Evonik Industries.

[0189] - Niax L-620LV - A polysiloxane surfactant for polyurethane foams, available from Momentive.

[0190] - TCPP—Tris(chloroisopropyl) phosphate. Available from Shekoy chemicals.

[0191] - TDI-80 — Toluene diisocyanate (80 / 20). Available from Borsodchem.

[0192] - UR - Urea (98%). Available from Sigma Aldrich.

[0193] Comparative Example 1. Preparation of NAD Stabilizer 1

[0194] 149.98 g of polyol A, 2.98 g of 3-(triethoxysilyl)propyl isocyanate, and 44 mg of dibutyltin dilaurate were placed in a three-necked glass flask reactor equipped with a mechanical stirrer. Under stirring and a nitrogen atmosphere, the temperature was raised to 80 °C and maintained for 30 minutes. The complete disappearance of the characteristic peak of isocyanate in the infrared spectrum confirmed the completion of the reaction. The resulting reaction product was a transparent liquid.

[0195] Comparative Example 2. Preparation of NAD Stabilizer 2

[0196] In a glass reactor equipped with a mechanical stirrer, 85 mg of tetrafluoroboric acid solution (48%) was added to 150.16 g of polyol A. After stirring for 5 minutes, 3.46 g of 3-epoxypropoxypropyltrimethoxysilane was added to the mixture, and the reaction temperature was raised to 50 °C. The temperature was maintained at 50 °C for 3 hours. The resulting product was a clear liquid.

[0197] Example 1. Preparation of NAD stabilizer 3 (Example of the present invention)

[0198] In a three-necked glass flask reactor equipped with a mechanical stirrer, 179.97 g of polyol A and 626 mg of tetrafluoroborate solution (48%) were added. The mixture was homogenized by stirring for 5 minutes, and then 3.60 g of 3-epoxypropoxypropyltrimethoxysilane was added. The temperature was raised to 50 °C while stirring. The reaction was maintained at 50 °C for 3 hours with stirring. Subsequently, 8.69 g of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and 2.0 g of water were added, and the temperature was raised to 60 °C. The reaction continued for 16 hours. The resulting product was a translucent liquid.

[0199] Example 2 Preparation of THP mixture A

[0200] 1090.8 g of THPS (phosphonium tetra(hydroxymethyl)sulfate solution (75%)) was placed in a jacketed glass reactor equipped with a mechanical stirrer. While stirring, a KOH solution (198.9 g of flake KOH dissolved in 200 g of water) was slowly added dropwise to the THPS. During the KOH addition step, the temperature was maintained below 25°C.

[0201] A slurry containing sulfates was obtained. The solids were filtered off, and the volatile compounds in the resulting solution were removed by distillation at 100 mbar in a reactor. Nitrogen gas was introduced through a sparger during distillation. The temperature was maintained at 50°C during the distillation process. After the water was completely distilled, the temperature was raised to 80°C, and the product was stripped with nitrogen under vacuum for 4 hours.

[0202] The resulting turbid liquid product was filtered again under a nitrogen atmosphere to obtain a transparent product.

[0203] The molar percentage distribution of the THP derivatives was determined by 31P-NMR. The results are shown in Table 1. Other minor components may be present.

[0204] Table 1

[0205] Preparation of PIPA polyols

[0206] PIPA polyols are prepared according to the following process: In a glass reactor equipped with a mechanical stirrer, polyol B and NAD stabilizer were added, followed by triethanolamine. The mixture was stirred at 500 rpm for 1 minute, after which the catalyst was added to the reactor and stirred for 30 seconds. The stirring speed was then increased to 2000 rpm, and the entire amount of isocyanate was added to the reactor in one step.

[0207] The results are shown in Table 2.

[0208] Table 2

[0209] The above embodiments were prepared by adding isocyanate in a single step. In the following embodiments, isocyanate was added gradually to the reactor over a period of time. The results are shown in Table 3.

[0210] Table 3

[0211] The following examples were prepared under catalyst-free conditions to obtain finely dispersed polyols (Table 4).

[0212] Table 4

[0213] Following the procedure described in the preparation of PIPA polyols, The THP mixture prepared in Example 2 was used to replace TEOA to prepare non-reactive phosphorus-containing PIPA polyols (Table 6).

[0214] Table 5

[0215] In Comparative Examples 3, 4, 5, 6, 7, and 8, a white solid precipitated within 1 minute after the addition of isocyanate. When the NAD dispersant prepared in Example 3 was used, finely dispersed and stable PIPA polyols were obtained (Table 6).

[0216] Table 6

[0217] Preparation of modified polymer polyols

[0218] Modified polymer polyols were prepared using the THP mixture prepared in Example 2, according to the following formulation: Polyol C and NAD dispersant were placed in a jacketed glass reactor equipped with a mechanical stirrer. The temperature was raised to 80°C, and the THP mixture obtained in Example 10 was added. The mixture was stirred at 80°C for 30 minutes, and then an aqueous solution of urea was added with vigorous stirring. After stirring for 5 minutes, the liquid volatile compounds were distilled off at 350 mbar. After the liquid compounds were completely distilled, the temperature was raised to 160°C, and the product was stripped with nitrogen. This stripping process was carried out at 150 mbar.

[0219] Table 7 below summarizes the different embodiments completed according to the described process.

[0220] Table 7

[0221] The particle size obtained in Comparative Examples 9 and 10 was found to be larger than that in Example 13.

[0222] Table 8

[0223] Polyurethane flexible foam

[0224] Polyurethane foam is prepared according to the following process: Prepare the polyol and isocyanate portions in a 1.2-liter beaker and place them in a mixer.

[0225] Start the mixer.

[0226] Increase the mixing speed within 30 seconds until it reaches 2000 rpm.

[0227] Continue stirring at 2000 rpm for 25 seconds, add the catalyst and immediately add the activator, both pre-weighed in a syringe appropriate for the volume to be added, so that all components are added after stirring for 60 seconds.

[0228] The resulting mixture was poured into an aluminum mold protected by kraft paper at 23°C, and the mixture was allowed to react in the mold for 5 minutes. The rise curve was monitored using a Foamat device.

[0229] Remove the resulting foam from the mold and allow it to cure in an oven at 100°C for 15 minutes. After this curing step, store the foam at 23°C and 50% relative humidity for at least 24 hours.

[0230] The prepared compositions are shown in Table 9 below.

[0231] Table 9

Claims

1. A nitrogen-containing alkoxysilane-terminated polyether polyol, each molecule having 1 to 8 hydroxyl groups and each molecule having 1 to 2 nitrogen-containing alkoxysilane groups, which can be obtained by a method comprising the following steps: a) Using a capping agent, one or two terminal hydroxyl groups of a polyether polyol having a functionality of 2 to 10 and a weight-average molecular weight of 2000 to 25000, as determined by the method specified in the instructions, are capped, wherein the capping agent is a compound having at least one alkoxysilane terminal group and at least one hydroxyl reactive group selected from isocyanate groups, anhydride groups, and epoxy groups; wherein, The reaction between the capping agent and the polyether polyol is carried out at a molar ratio of 0.05 to 2.0 moles of capping agent per mole of polyether polyol, thereby obtaining an intermediate product; b) Reaction of the intermediate obtained in a) with a compound containing an amino or -NHCONH2 group and containing at least one alkoxysilane terminal group to obtain the nitrogen-containing alkoxysilane-terminated polyether polyol. The capping agent is a compound of formula (I): R1, R2, and R3 are each independently selected from straight-chain or branched (C1-C6) alkyl, straight-chain or branched (C1-C6) alkoxy, and tri(C1-C3) alkylsiloxy; provided that at least one of R1, R2, or R3 is (C1-C6) alkoxy; and Wherein, A is a group selected from formulas (II), (III), (IV), (V), and (VI): in, The asterisk indicates the site where the Si atom in formula (I) is connected; m, n, p, r, t, and w are independent integers selected from 1 to 6; q, s, and v are independent integers selected from 1 to 4; R4 is selected from -NCO, and group, The asterisk indicates the site where the group is attached to the rest of the group. X is selected from -O- and -N(R5)-; wherein R5 is selected from H, straight-chain or branched (C1-C6) alkyl, and group, The asterisk (*) indicates the site connected to the N atom. x and z are independent integers selected from 1 to 6; And R8, R9 and R 10 Each is independently selected from straight-chain or branched (C1-C6) alkyl, straight-chain or branched (C1-C6) alkoxy, and tri(C1-C3) alkylsiloxy; the condition is R8, R9, or R 10 At least one of them is (C1-C6)alkoxy or tri(C1-C3)alkylsiloxy; The reaction of the at least one polyether polyol with the compound of formula (I) is carried out at a molar ratio of 0.05 to 2.0 moles of the compound of formula (I) per mole of polyether polyol. The compound containing an amino or -NHCONH2 group and at least one alkoxysilane terminal group is a compound of formula (Ia): R1', R2' and R3' are each independently selected from straight-chain or branched (C1-C6) alkyl, straight-chain or branched (C1-C6) alkoxy and tri(C1-C3) alkylsiloxy; The condition is that at least one of R1', R2' or R3' is a (C1-C6) alkoxy group; 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-terminated polyether polyol as described in claim 1, wherein, The compound of formula (Ia) is added to the intermediate product at a molar ratio of 0.1 to 20 relative to the compound of formula (I) added in step (a).

3. The nitrogen-containing alkoxysilane-terminated polyether polyol according to any one of claims 1 to 2, wherein: i) The at least one polyether polyol has a functionality of 2 to 10 and a weight-average molecular weight of 2,000 to 20,000, and can be obtained by reacting ethylene oxide and / or propylene oxide with a polyol selected from glycerol, sorbitol, sucrose, trimethylolpropane, diethylene glycol, glycerol, pentanetriol, hexanetriol, erythritol and pentaerythritol; ii) The at least one alkoxysilyl end-capping agent is a compound of formula (I), wherein group A is selected from: ii.1) Compounds of formula (II), wherein m is an integer from 1 to 6; and R4 is selected from -NCO, and , The asterisk indicates the site where the group is attached to the rest of the group. ii.2) Compounds of formula (III), wherein n and p are independently integers selected from 1 to 6, q is an integer selected from 1 to 3, and X is selected from -O- and -N(R5)-, wherein R5 is selected from H, straight-chain or branched (C1-C6) alkyl, and group, Wherein, the asterisk indicates the site connected to the N atom; x and z are independent integers selected from 1 to 6; and R8, R9, and R 10 Each is independently selected from -CH3, -CH2CH3, -OCH3, -OCH2CH3, -O-Si(CH3)3 and -O-Si(CH2CH3)3; ii.3) Compounds of formula (IV) or formula (V), wherein r and t are independently integers selected from 1 to 4; and s is an integer selected from 1 to 3; Or as an option ii.4) Compounds of formula (VI), wherein w is an integer selected from 1 to 4; The reaction of the at least one polyether polyol with the at least one end-capping agent containing an alkoxysilyl end-capping group of the compound of formula (I) is carried out at a molar ratio of 0.05 to 2.0 moles of the compound of formula (I) per mole of polyether polyol. and In this process, the compound of formula (Ia) is added to the intermediate product at a molar ratio of 0.1 to 20 relative to the compound of formula (I) added in step (a).

4. The nitrogen-containing alkoxysilane-terminated polyether polyol according to any one of claims 1 to 3, wherein, The compound of formula (Ia) is selected from N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, (3-aminopropyl)triethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, N1-(3-trimethoxysilylpropyl)diethylenetriamine, 3-(ethoxydimethylsilyl)propylamine, (3-aminopropyl)trimethoxysilane, aminopropylmethyldiethoxysilane, and 3-aminopropylsilanetriol. N-(3-triethoxysilylpropyl)ethylenediamine, 3-ureopropyltrimethoxysilane, N-cyclohexylamino-methyltriethoxysilane, N-cyclohexyl-3-aminopropyltrimethoxysilane, bis[3-triethoxysilyl)propyl]amine, bis[3-trimethoxysilyl)propyl]amine, aminopropylmethyldimethoxysilane, diethylaminomethyltriethoxysilane, diethylaminoethyltriethoxysilane, and N-(n-butyl)-3-aminopropyltrimethoxysilane.

5. A method for preparing modified polymer polyol dispersions, wherein, The method includes preparing polymer 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-terminated polyether polyol as defined in any one of claims 1 to 4.

6. The method of claim 5, wherein, The method includes preparing polymer particles in the presence of the liquid polyol mixture by the following manner: a. In the liquid polyol mixture and under polymerization conditions a.1) At least one compound having at least one basic nitrogen atom and characterized in that at least one hydrogen atom bonded to the nitrogen atom is present in the molecule; Reacts with a.2) or a.3), wherein, a.2) is at least one compound or mixture of compounds containing a phosphorus atom, selected from the group consisting of [bis(hydroxymethyl)phosphino]methanol (THP), tetra(hydroxymethyl)phosphonium salt (THPX), [bis(hydroxymethyl)phosphonyl]methanol (THPO), ({[bis(hydroxymethyl)phosphino]methoxy}methanol (mTHP), {bis[(hydroxymethoxy)methyl]phosphino}methanol (dTHP), ({bis[(hydroxymethoxy)methyl]phosphino}methoxy)methanol (tTHP), {[bis(hydroxymethyl)phosphonyl]methoxy}methanol (mTHPO), {bis[(hydroxymethoxy)methyl]phosphonyl}methanol (dTHPO), ({bis[(hydroxymethoxy)methyl]phosphonyl}methoxy)methanol (tTHPO), and mixtures thereof; as well as a.3) is a mixture of at least one of the above-mentioned compounds containing phosphorus atoms or compounds; a.2) is a mixture of condensation products obtained by reacting at least one compound containing at least one basic nitrogen atom; Wherein, the compound a.1) having at least one basic nitrogen atom is selected from: a.1i) Melamine, trimethylol melamine, diethylenetriamine, tert-octylamine, dimethylaminopropylamine, polyethyleneimine; a.1ii) Compounds of formula (VII) or (VIII); and a.1iii) Its mixture; Among them, the compounds of formula (VII) are as follows: R 11 -NH2 (VII) Among them, R 11 Selected from -H, -(C1-C3)alkyl, (C1-C3)alkyl-CO-, NH2-CO-, -(CH2) n -NH2, -CN, -NH2, -SO2NH2, cyclohexyl, phenyl, -SO2OH and -NHCONHNH2; where n is an integer from 1 to 18; And the compounds of formula (VIII) are as follows: (VIII) Among them, R 12 Selected from NH=C<, O=C< and S=C<; and R 13 Selected from H, -CN, -NH2, -CONH2, -CONHCONH2, and -CONHCONHCONH2; Or as an option b. Reacting b.1) and b.2) in the liquid polyol mixture and under polymerization conditions, optionally in the presence of a catalyst, b.1) At least one co-reactant selected from: b.1.i) An amine, alkanolamine, or diol having an equivalent weight of at most 400 and having at least one active hydrogen atom bonded to a nitrogen or oxygen atom; and b.1.ii) Hydroxyphosphine; b.2) At least one polyisocyanate; The liquid polyol mixture comprises at least one base polyol and at least one nitrogen-containing alkoxysilane-terminated polyether polyol as defined in any one of claims 1 to 5.

7. The method according to any one of claims 5 to 6, wherein, The method includes: i. Mix the at least one basic polyol with at least one nitrogen-containing alkoxysilane-terminated polyether polyol as defined in any one of claims 1 to 4 to obtain a liquid polyol mixture; ii. Add simultaneously or sequentially in any order to the liquid polyol mixture obtained in i). a.1) The at least one compound having at least one basic nitrogen atom and characterized in that at least one hydrogen atom bonded to the nitrogen atom is present in the molecule; And a.2) or a.3), where, a.2) is at least one compound or mixture of compounds containing phosphorus atoms, selected from: I. [bis(hydroxymethyl)phosphine]methanol (THP) at a concentration of 0-100 mol%; II. Tetra(hydroxymethyl)phosphonium salts (THPX) at concentrations of 0-100 mol%; III. [bis(hydroxymethyl)phosphoryl]methanol (THPO) at a concentration of 0-100 mol%; IV. {[bis(hydroxymethyl)phosphine]methoxy}methanol (mTHP) at a concentration of 0-80 mol%; V. Di[(hydroxymethoxy)methyl]phosphine]methanol (dTHP) at a concentration of 0-30 mol%; VI. 0-15 mol% of ({bis[(hydroxymethoxy)methyl]phosphine}methoxy)methanol (tTHP); VII. A concentration of 0-20 mol% of {[bis(hydroxymethyl)phosphoryl]methoxy}methanol (mTHPO); VIII. 0-10 mol% of {bis[(hydroxymethoxy)methyl]phosphoryl}methanol (dTHPO); IX. 0-4 mol% of ({bis[(hydroxymethoxy)methyl]phosphoryl}methoxy)methanol (tTHPO); The total amount of phosphorus-containing compounds in the mixture is 100 mol%; as well as a.3) is a mixture of at least one of the above compounds or compounds; a.2) is a mixture of condensation products obtained by reacting at least one compound a.1) having at least one basic nitrogen atom; Wherein, the compound a.1) having at least one basic nitrogen atom is selected from: - Melamine, trimethylol melamine, diethylenetriamine, tert-octylamine, dimethylaminopropylamine, polyethyleneimine; - Compounds of formula (VII) or (VIII); and - Its mixture; and The liquid polyol mixture comprises at least one base polyol and at least one nitrogen-containing alkoxysilane-terminated polyether polyol as defined in any one of claims 1 to 4.

8. The method according to any one of claims 5 to 7, wherein, The method includes: i. Mixing the at least one basic polyol with the at least one nitrogen-containing alkoxysilane-terminated polyether polyol to obtain a liquid polyol mixture; and ii. Optionally, in the presence of a catalyst and under polymerization conditions, add to the liquid polyol mixture obtained in i) simultaneously or in any order the following substances: b.1) At least one co-reactant selected from: b.1.i) An amine, alkanolamine, or diol having an equivalent weight of at most 400 and having at least one active hydrogen atom bonded to a nitrogen or oxygen atom; and b.1.ii) Hydroxyphosphine; as well as 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, aliphatic amines, ethylenediamine, 1,6-hexanediamine, hydrazine, 2,6-diaminotoluene, 2,4-diaminotoluene, 4,4'-methylenediphenylamine, diethylene glycol, triethylene glycol, and polyethylene glycol; hydroxyphosphine, such as hydroxyalkylphosphine, hydroxyalkylphosphonium salts, hydroxyalkylphosphine oxides, and derivatives thereof; and alkanolamines, such as monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, 2-(2-aminoethoxyethanol), hydroxyethylpiperazine, monoisopropanolamine, diisopropanolamine, N-methylethanolamine, phenylethanolamine, ethylene glycolamine, and mixtures thereof; The liquid polyol mixture comprises at least one base polyol and at least one nitrogen-containing alkoxysilane-terminated polyether polyol as defined in any one of claims 1 to 4.

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

10. A modified polymer polyol dispersion of polymer particles in a liquid polyol mixture, which can be obtained by the method of any one of claims 5 to 9.

11. The modified polymer polyol dispersion of claim 10, wherein it is a polyisocyanate plus a polypolymer polyol dispersion, and wherein the base polyol is a non-reactive polyol.

12. A method for preparing polyurethane materials, wherein, The method comprises reacting at least one polyisocyanate with an isocyanate reactive component comprising at least one stable modified polymer polyol dispersion as defined in any one of claims 10 to 11 in the presence of at least one catalyst and optional additives; wherein the polyisocyanate is used at an isocyanate index of 60 to 140.

13. A polyurethane material, which can be obtained by the method of claim 12.

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

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