Polyether-siloxane block copolymers for the production of polyurethane foam

Abstract

The present invention relates to polyether-siloxane block copolymers for producing polyurethane foams. A process for preparing polyether-siloxane block copolymers is described, wherein an α,ω-modified hydrogensiloxane is hydrosilylated with an α,ω-modified di(meth)allyl polyether in the presence of a hydrosilylation catalyst, wherein the reaction is carried out in a solvent mixture comprising an aromatic solvent, a polyether and an alkoxylated alcohol.

Description

Technical Field

[0001] The invention belongs to the field of polyether siloxane, foam and polyurethane foam. Background Art

[0002] More particularly, the present invention relates to the preparation of specific polyether-siloxane block copolymers and their use for producing polyurethane foams, preferably mechanically foamed polyurethane foams.

[0003] Mechanically foamed polyurethane foams are produced without the use of physical or chemical blowing agents and are used in a wide variety of different coating processes. For example, they are used for backing foams for carpets and synthetic turf, for producing two-dimensional seals and so-called gap fillers, such as electronic components, so-called battery pads in lithium-ion battery packs, as footstep sound insulation materials for floor coverings, and in the field of adhesive coatings. The relevant foam is typically produced by mechanical foaming of a polyol-isocyanate mixture, wherein air or nitrogen is forced to enter the polyol-isocyanate mixture with high shear input. The resulting foam material can then be applied to any desired substrate, such as the reverse side of a carpet or release paper, and cured at elevated temperatures. Due to its production, mechanically foamed polyurethane foams are also referred to as beaten foams in the professional field. The term "beaten foam" is also used in this way in the present invention.

[0004] For all of the above applications, it is important to obtain as fine-pored a foam as possible during mechanical foaming. Furthermore, the foam must have a high stability so that defects in the foam can be avoided during the subsequent coating and drying processes. For this reason, foam stabilizers are usually added to the polyol-isocyanate mixture before or during mechanical foaming. Polyether-siloxane block copolymers have been found to be particularly effective for this application. These stabilizers are generally characterized by a linear [AB] structure of alternating polyether and siloxane chains. n Block structure. The higher the molecular weight of the compound used as a foam stabilizer, the more effective it is.

[0005] Non-hydrolyzable [AB] n Polyether siloxanes are known to those skilled in the art. For example, US Pat. No. 3,957,842 describes such polymers. This patent describes the preparation of these structures by hydrosilylation of diallyl polyethers with α,ω-SiH-functional siloxanes in toluene. The resulting polymers have molecular weights of approximately 36,000-56,000 g / mol.

[0006] US 4150048 describes non-hydrolyzable [AB] nPolyether siloxanes are prepared by the hydrosilylation of polyethers having two CH2=C(R)CH2 terminal groups per molecule, where R is a monovalent hydrocarbon group. They are prepared using α,ω-SiH-functional siloxanes in the presence of a platinum catalyst under hydrosilylation reaction conditions. The linear block copolymers produced are particularly useful as surfactants and foam stabilizers for the production of polyurethane foams. The low tendency of the CH2=C(R)CH2- groups to isomerize to non-reactive species during the hydrosilylation reaction results in the copolymers' unexpectedly high molecular weight.

[0007] US Pat. No. 5,869,727 describes a vacuum process for preparing siloxane-alkylene oxide copolymers.

[0008] US 20190233646 describes a method comprising [AB] n A polyether siloxane composition comprising a polyether-polysiloxane block copolymer and a liquid organic monool compound, wherein the organic monool compound is a glycol ether compound having a low degree of polymerization and terminal hydrogen or an alcohol compound having a branched alkyl group with 12 or more carbon atoms.

[0009] As already mentioned, a high molar mass is important and therefore it is particularly desirable to provide a particularly effective foam stabilizer for mechanically foamed polyurethane foams. Foam stabilizers with too low a molar mass can lead to a reduced foam stabilization effect, which will produce coarse and irregular foams. In addition, the use of low molecular weight foam stabilizers limits the density range of mechanically foamed polyurethane foams that can be produced, and the production of low-density (<400 g / l) foams is a particular problem. However, in addition to the maximum molecular weight of the foam stabilizer, it is also important that the molar mass distribution is as narrow as possible. In particular, a tailing of the molar mass distribution towards very high molar masses can have a negative impact. This tailing can lead to a very high viscosity of the foam stabilizer, which greatly impairs its processability during foam production. Summary of the Invention

[0010] The problem addressed by the present invention was therefore to provide polyether-siloxane block copolymers which are distinguished by a particularly high molecular weight combined with a very narrow molar mass distribution, and which are associated with a particularly effective efficacy as foam stabilizers.

[0011] Surprisingly, it has been found that the use of specific solvent mixtures makes it possible to prepare corresponding polyether-siloxane block copolymers and thus solve the problems described.

[0012] Therefore, the present invention provides a method for preparing a polyether-siloxane block copolymer of Formula 1

[0013]

[0014] in

[0015] a=0 to 100, preferably 5 to 75, more preferably 10 to 50,

[0016] b=0 to 100, preferably 5 to 75, more preferably 5 to 25,

[0017] c=0 to 100, preferably 5 to 75, more preferably 5 to 25,

[0018] a+b+c>3,

[0019] d = 1 to 100, preferably 5 to 50, more preferably 7 to 30, most preferably 8-20,

[0020] n=5-200, preferably 10-100, more preferably 15-50, and

[0021] where R 1 The groups are independently identical or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, most preferably methyl groups,

[0022] And where R 2 The radicals are independently identical or different monovalent aliphatic, saturated or unsaturated hydrocarbon radicals having 1 to 20 carbon atoms or H, particularly preferably a methyl radical,

[0023] And where R 3 The groups are independently identical or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, preferably methyl groups,

[0024] And where R 4 The groups are independently selected from R 5 、R 6 、R 7 group or H, where R 5 The group conforms to formula 2

[0025]

[0026] And where R 6 The group conforms to formula 3

[0027]

[0028] And where R 7 The group conforms to formula 4

[0029]

[0030] The coefficients a, b, and c and R 2 and R 3The group is as defined above, by hydrosilylation of an α,ω-modified hydrogensiloxane with an α,ω-modified di(meth)allyl polyether in the presence of a hydrosilylation catalyst capable of catalyzing the formation of SiC bonds by the addition of Si—H groups to (meth)allylic double bonds,

[0031] The reaction is carried out in a solvent mixture comprising an aromatic solvent, preferably toluene and / or alkylbenzene, a polyether of formula 5 and an alkoxylated alcohol of formula 6.

[0032]

[0033] in

[0034] g=0 to 75, preferably 0 to 50, more preferably 0 to 25,

[0035] h=1 to 100, preferably 2 to 50, more preferably 3 to 25,

[0036] i=1 to 100, preferably 2 to 50, more preferably 3 to 25, and

[0037] where R 8 The groups are independently identical or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, preferably methyl groups,

[0038]

[0039] in

[0040] j=0 to 30, preferably 0 to 10, more preferably 0,

[0041] k=0 to 20, preferably 0 to 10, more preferably 0 to 5,

[0042] l=1 to 20, preferably 2 to 10, more preferably 3 to 5, and

[0043] where R 9 The radical is a monovalent aliphatic saturated or unsaturated, linear or branched hydrocarbon radical having 6 to 40, preferably 8 to 30, even more preferably 10 to 22 carbon atoms,

[0044] And where R 8 The groups are as defined above.

[0045] The sequence of the different oxyalkylene units between square brackets and specified by lowercase coefficients in the polyoxyalkylene group, polyol or alkoxylated alcohol can be random (statistically distributed), in blocks, gradually varying, or any mixture of these options within the chain segment. The structural formula specified here is only a simplified diagrammatic illustration with respect to the sequence.

[0046] The solvent mixture according to the present invention therefore comprises at least three components: an aromatic solvent, a polyether of formula 5 and an alkoxylated alcohol of formula 6.

[0047] The advantage of the process according to the invention is not only that it can provide corresponding polyether-siloxane block copolymers having a high molecular weight and at the same time a very narrow molar mass distribution, but also that the resulting preparations having a relatively high active ingredient content have a relatively low viscosity and thus considerable processing advantages.

[0048] Another advantage is that the resulting polyether-siloxane block copolymers with high molecular weight have a narrow molar mass distribution. In particular, it is possible to ensure that the weight-average molar mass M w (g / mol) ≥ 60,000, advantageously > 80,000, preferably > 90,000, especially > 100,000 polyether-siloxane block copolymer of formula 1, wherein M w / M n <3.1, preferably <3.0, especially <2.9. n is the number average molar mass.

[0049] In this context, a high molar mass is particularly advantageous for the inventive use of polyether-siloxane block copolymers as foam stabilizers for producing polyurethane foams, especially scalable polyurethane foams, because it allows the production of particularly fine-pored and stable foams. This also enables particularly efficient mechanical foaming of polyol-isocyanate mixtures, which in turn leads to numerous processing advantages in the production of scalable polyurethane foams. From this perspective, low viscosity and a narrow molar mass distribution are also valuable.

[0050] In summary, it can be said that the polyether-siloxane block copolymers resulting from the present invention exhibit excellent properties, especially in the production of mechanically blown PU foams. They ensure optimal processability while being able to provide the highest quality PU foams.

[0051] Polyether-siloxane block copolymers are known per se. Throughout the present invention, the term "polyether" encompasses polyoxyalkylenes, particularly preferably polyoxyethylene and polyoxypropylene, as well as polyoxyethylene-polyoxypropylene copolyethers. The distribution of the various oxyalkylene units along the polymer backbone may vary. Mixed polyethers can, for example, be constructed statistically in blocks or with a gradient of monomer units that differ from one another. In this case, a statistical construction means that the polyoxyethylene and polyoxypropylene units are distributed in a random order throughout the polyether chain, while a block-structured polyether consists of defined polyoxyethylene and polyoxypropylene blocks.

[0052] Throughout the present invention, the term "silicone" includes compounds from the class of polyorganosiloxanes, particularly preferably polydimethylsiloxanes. Throughout the present invention, the term "polyether-siloxane block copolymer" includes polymers built up from alternating polyether and siloxane blocks.

[0053] The polyether-siloxane block copolymer of the present invention conforms to Formula 1.

[0054] The term "polyurethane foam" is known per se to those skilled in the art (see, for example, Adam et al., "Polyurethanes," Ullmann's Encyclopedia of Industrial Chemistry—Paragraph 7, 2012, Wiley VCH-Verlag, Weinheim). Throughout the present invention, the term "sprayable polyurethane foam" includes polyurethane foams produced by mechanically blowing air, nitrogen, CO2, or other inert gases into a polyol-isocyanate mixture using only small amounts of additional physical or chemical blowing agents (preferably none). "Sprayable polyurethane foam" is synonymous with the term "mechanically foamed polyurethane foam."

[0055] The preparation of the polyether-siloxane block copolymers according to the present invention is based on a hydrosilylation reaction known to those skilled in the art and can be achieved by reacting such α,ω-modified hydrosiloxanes with α,ω-modified di(meth)allyl polyethers. The chemical reactions underlying this preparation are known and described in detail in the technical literature (e.g., Silicones—Chemistry and Technology, Vulkan-Verlag Essen, 1989).

[0056] The present invention is further described below by examples, but it is not intended to limit the present invention to these illustrative embodiments. Where the range, structural formula or class of compounds is stated below, these are not only intended to cover the corresponding compound ranges or classes explicitly mentioned, but also all sub-ranges and compound subsets that can be obtained by extracting a single value (range) or compound. When a document is cited in the context of this specification, the entire content of the document, in particular the content of the subject matter forming the context of the citation of the document, is intended to form a part of the disclosure of the present invention. Unless otherwise stated, percentages are all weight percentages. Mole percentages are expressed in the abbreviation form of m%. Unless otherwise stated, where parameters determined by measurement are given below, these measurements were carried out at a temperature of 25°C and a pressure of 101325Pa. In the case of using chemical (empirical) formulas in the present invention, the specified coefficients can be not only absolute values, but also average values. For polymeric compounds, the coefficients preferably represent average values. The structures and empirical formulas given in the present invention represent all isomers that may be produced by different arrangements of repeating units. In the context of the present invention, where compounds such as polyethers, siloxanes or polyethersiloxanes are described which may have different units multiple times, these units may be present in a statistical distribution (statistical oligomers or polymers), in an ordered form (block oligomers or block polymers) or in a gradient distribution in these compounds.

[0057] In addition to the aromatic solvent, the solvent mixture according to the present invention also contains the polyether of formula 5 and the alkoxylated alcohol of formula 6. When the polyether of formula 5 and the alkoxylated alcohol of formula 6 are used in a weight ratio of 1:4 to 4:1, preferably in a mass ratio of 1:3 to 3:1, it corresponds to a preferred embodiment of the present invention.

[0058] It is further preferred that the aromatic solvent, preferably comprising toluene and / or alkylbenzenes, is used in an amount of >15% by weight, preferably >20% by weight, in particular >30% by weight, based on the total solvent mixture used. This also corresponds to a preferred embodiment of the present invention.

[0059] The reactants used are α,ω-modified hydrogen siloxane and α,ω-modified di(methyl)allyl polyether, and are used in the presence of a hydrosilylation catalyst.

[0060] It is a further preferred embodiment of the present invention when the ratio of the sum of the masses of the polyether of formula 5 and the alkoxylated alcohol of formula 6 to the sum of the masses of the reactants is from 7:3 to 1:4.

[0061] The α,ω-modified di(meth)allyl polyether is preferably used in a concentration such that the molar ratio of polyether-bound double bonds to Si—H groups is in the range of 0.95:1.05 to 1.05:0.95, preferably in the range of 0.97:1.03 to 1.03:0.97, and more preferably in the range of 0.99:1.01 to 1.01:0.99. This also corresponds to a preferred embodiment of the present invention.

[0062] The hydrosilylation according to the invention is carried out in the presence of a hydrosilylation catalyst. It is a further preferred embodiment of the invention when the hydrosilylation catalyst used in the reaction is selected from platinum catalysts, especially platinum (0) catalysts, very particularly preferably platinum (0) catalysts in the form of Karstedt catalysts.

[0063] Such catalysts are known; see, for example, Lewis et al., “Platinum Catalysts used in Silicones Industry”, Platinum Metal Review, 1997, 44(23), 66-74.

[0064] Optionally, the aromatic solvent can be removed from the mixture after the hydrosilylation, for example by distillation, in particular when the aromatic solvent is toluene. This corresponds to a further preferred embodiment of the process according to the invention.

[0065] The polyether siloxanes prepared by the process according to the invention preferably have a weight-average molar mass M of at least 60,000 g / mol, preferably at least 70,000 g / mol, more preferably at least 80,000 g / mol. w , and having a number average molar mass M of at least 25000 g / mol, preferably at least 27500 g / mol, more preferably at least 30000 g / mol n When M w / M n It is further preferred that the ratio of is less than 3.1, preferably less than 3.0, more preferably less than 2.9. w ” and “number average molar mass M n " are known to the person skilled in the art. These two parameters can preferably be determined by gel permeation chromatography (GPC), preferably calibrated with polystyrene. For this purpose, for example, a SECcurity2 GPC system from PCC can be used and calibrated with polystyrene. In particular, a SECcurity 1260 GPC system from PCC can be used, preferably with the following experimental framework parameters: SDV Column combination, PSS SECurity 1260RI detector, THF mobile phase, flow rate 1 ml / min), calibration with polystyrene (162-2 520 000 g / mol).

[0066] The mixture obtained by the process according to the invention can be used according to the invention for producing polyurethane foams, in particular blown polyurethane foams.

[0067] Therefore, the present invention also provides a preparation suitable as an additive for producing polyurethane foam, preferably blown PU foam, comprising the following components:

[0068] (a) Polyether-siloxane block copolymer of formula 1

[0069]

[0070] in

[0071] a=0 to 100, preferably 5 to 75, more preferably 10 to 50,

[0072] b=0 to 100, preferably 5 to 75, more preferably 5 to 25,

[0073] c=0 to 100, preferably 5 to 75, more preferably 5 to 25,

[0074] d = 1 to 100, preferably 5 to 50, more preferably 7 to 30, most preferably 8-20,

[0075] n=5-200, preferably 10-100, more preferably 15-50, and

[0076] where R 1 The radicals are each independently identical or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably having 1 to 10 carbon atoms, particularly preferably a methyl radical,

[0077] And where R 2 The radicals are independently identical or different monovalent aliphatic, saturated or unsaturated hydrocarbon radicals having 1 to 20 carbon atoms or H, particularly preferably a methyl radical,

[0078] And where R 3 The groups are independently identical or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, preferably methyl groups,

[0079] And where R 4 The groups are independently selected from R 5 、R 6 、R 7 group or H, where R 5 The group conforms to formula 2

[0080]

[0081] And where R 6 The group conforms to formula 3

[0082]

[0083] And where R 7 The group conforms to formula 4

[0084]

[0085] The coefficients a, b, and c and R 2 and R 3 The group is as defined above,

[0086] (b) Polyether of Formula 5

[0087]

[0088] in

[0089] g=0 to 75, preferably 0 to 50, more preferably 0 to 25,

[0090] h=1 to 100, preferably 2 to 50, more preferably 3 to 25,

[0091] i=1 to 100, preferably 2 to 50, more preferably 3 to 25, and

[0092] where R 8 The groups are independently identical or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, preferably methyl groups,

[0093] (c) Alkoxylated alcohol of formula 6

[0094]

[0095] in

[0096] j=0 to 30, preferably 0 to 10, more preferably 0 to 5,

[0097] k=1 to 20, preferably 2 to 10, more preferably 3 to 5,

[0098] l=1 to 20, preferably 2 to 10, more preferably 3 to 5, and

[0099] where R 9 The radical is a monovalent aliphatic saturated or unsaturated, linear or branched hydrocarbon radical having 6 to 40, preferably 8 to 30, even more preferably 10 to 22 carbon atoms, and wherein R 8The groups are independently identical or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, preferably a methyl group,

[0100] (d) Optional aromatic solvents. In a preferred embodiment, the formulation contains substantially no aromatic solvents, ie, less than 5% by weight aromatic solvents or less than 1% by weight aromatic solvents, or contains no aromatic solvents at all.

[0101] In a preferred embodiment of the present invention, components b) and c) are present in the formulation in a mass ratio of 1:4 to 4:1, preferably in a mass ratio of 1:3 to 3:1.

[0102] Furthermore, preference is given to formulations in which the mass ratio of the sum of b) and c) to a) is from 8:2 to 1:4. This corresponds to a preferred embodiment of the present invention.

[0103] Furthermore, preference is given to formulations in which the polyether-siloxane block copolymer of formula 1 is present in a concentration of at least 20% by weight, preferably at least 25% by weight, more preferably at least 30% by weight, based on the entire formulation.

[0104] As described above, the present invention can provide a polyether-siloxane block copolymer having both a high molecular weight and a narrow molar mass distribution.

[0105] The preparation according to the invention comprising a polyether-siloxane block copolymer of formula 1, M w (g / mol)≥60000, preferably>70000, especially>80000, wherein M w / M n <3.1, preferably <3.0, especially <2.9, corresponds to a particularly preferred embodiment of the present invention. As already described further, within the scope of the present invention, M w and M n It can preferably be determined by gel permeation chromatography (GPC), preferably calibrated with polystyrene.

[0106] Furthermore, it may be preferred if the formulation according to the invention also contains a pendent stabilizer as an additional component. The pendent stabilizer here is likewise a polyether siloxane, but it has a siloxane chain with pendent and / or terminal polyether chains. The polyether chain here can be bonded to the siloxane chain via a silicon-carbon bond (Si-C) or a silicon-oxygen-carbon bond (Si-OC), particularly preferably a silicon-carbon bond. Particularly preferred are those pendent Si-C-based polyether siloxanes that conform to formula 7.

[0107]

[0108] in

[0109] x=0 to 50, preferably 1 to 25, more preferably 2 to 15,

[0110] y=0 to 250, preferably 5 to 150, more preferably 5 to 100,

[0111] where R 9 The groups are independently the same or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and most preferably a methyl group, and wherein R 10 The groups are independently identical or different OH-functional or OH-terminated, preferably methyl- or acetyl-terminated, polyoxyalkylene groups, preferably polyoxyethylene polyoxypropylene groups, and wherein R 11 The group corresponds to R 9 or R 10 .

[0112] The preparation according to the invention can be obtained by the process according to the invention as described above, and optionally with subsequent removal of the aromatic solvent, especially when the latter is toluene. Additional components such as stabilizers, in particular of the side chains of formula 7, may also be added.

[0113] As described above, since the polyether-siloxane block copolymers according to the invention are effective stabilizers for the production of polyurethane foams, in particular slap-type polyurethane foams, the present invention also provides the use of the preparations according to the invention as additives, in particular in combination with stabilizers of the side chains of formula 7, in particular as foam stabilizing additives for the production of polyurethane foams, preferably slap-type PU foams.

[0114] It is a particularly preferred embodiment of the present invention when the polyurethane foam to be produced is a mechanically foamed polyurethane foam containing less than 2% by weight, preferably less than 1% by weight, more preferably less than 0.5% by weight, most preferably less than 0.1% by weight of chemical or physical blowing agents.

[0115] Therefore, the present invention also provides a polyurethane foam, preferably a blown PU foam, produced using the above-described formulation according to the invention.

[0116] In the context of the present invention, the term "polyurethane foam" refers to foams formed by reacting polyisocyanates with compounds reactive therewith, preferably having OH groups ("polyols") and / or NH groups (Adam et al., "Polyurethanes", Ullmann's Encyclopedia of Industrial Chemistry, 2012, Wiley VCH-Verlag, Weinheim). Polyols for producing the corresponding foams are known per se. Particularly suitable polyols in the context of the present invention are any organic substances having a plurality of isocyanate-reactive groups, as well as formulations of such substances. Preferred polyols are any polyether polyols and polyester polyols commonly used for producing polyurethane foams. Polyether polyols can be obtained by reacting polyols or amines with alkylene oxides. Polyester polyols are based on esters of polycarboxylic acids (typically phthalic acid, adipic acid, or terephthalic acid) with polyols (typically diols). Preferred polyols are also short-chain diols, such as ethylene glycol, propylene glycol, diethylene glycol, or dipropylene glycol, which can be used, for example, as chain extenders.

[0117] Isocyanates for producing polyurethane foams are also known per se. The isocyanate component preferably comprises one or more organic isocyanates having two or more isocyanate functional groups. Examples of suitable isocyanates in the context of the present invention are any polyfunctional organic isocyanates, such as diphenylmethane 4,4'-diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI) and isophorone diisocyanate (IPDI). Also particularly suitable are prepolymers based on isocyanates, in particular prepolymers based on MDI.

[0118] Within the scope of the present invention, the ratio of isocyanate to polyol (expressed as the NCO coefficient) is preferably in the range of 40 to 500, more preferably 60 to 350, particularly preferably 80 to 120. The NCO coefficient here describes the ratio of the isocyanate actually used to the isocyanate calculated (for a stoichiometric reaction with the polyol). An NCO coefficient of 100 represents a molar ratio of reactive groups of 1:1.

[0119] In addition to the polyether-siloxane block copolymers according to the invention, the polyurethanes may also contain further additives and auxiliaries, such as fillers, blowing agents, catalysts, organic and inorganic pigments, stabilizers, such as hydrolysis or UV stabilizers, antioxidants, absorbers, crosslinkers, dyes, emulsifiers or dispersing additives, leveling agents or thickeners / rheology additives.

[0120] In the context of the present invention, particularly suitable catalysts for producing polyurethane foams, in particular for producing blown polyurethane foams, are gel catalysts which catalyze the polyurethane reaction between isocyanates and polyols. These can be selected from amine catalysts, for example triethylamine, dimethylcyclohexylamine, tetramethylethylenediamine, tetramethylhexanediamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, triethylenediamine, dimethylpiperazine, 1,2-dimethylimidazole, N-ethylmorpholine, tris(dimethylaminopropyl)hexahydro-1,3,3-triazine, dimethylaminoethanol, dimethylaminoethoxyethanol, tetramethylguanidine and 1,8-diazabicyclo[5.4.0]undec-7-ene. In addition, the amine catalyst can be selected from the class of so-called emission-free amine catalysts, which are characterized by a catalytically active nitrogen atom and a group reactive toward NCO groups, such as an OH group. Suitable emission-free amine catalysts are commercially available, for example as The NE product line is available from Evonik. Furthermore, the catalyst can be selected from metal catalysts, such as tin, zinc, bismuth, iron, copper, nickel, or zirconium-based catalysts. The metal catalysts can be present in the form of salts or organic derivatives. The aforementioned catalysts can be used in pure form or as catalyst mixtures. In the case of blown polyurethane foams, particularly suitable are thermolatent catalysts, i.e., catalysts that only become effective above a certain activation temperature and thus delay the curing of the foam.

[0121] In the context of the present invention, polyurethane foam is preferably a slapped polyurethane foam produced by mechanically whipping a polyol-isocyanate mixture. Such slapped foams preferably contain less than 2% by weight, more preferably less than 1% by weight, particularly preferably less than 0.5% by weight, and most preferably less than 0.1% by weight of chemical or physical blowing agents. The polyurethane foam particularly preferably contains no physical or chemical blowing agents at all.

[0122] As already described, the use of a formulation comprising a polyether-siloxane block copolymer according to the invention for producing a sparge polyurethane foam is a particularly preferred subject of the present invention. Preferably, such a sparge polyurethane foam can be produced by a process comprising the following steps:

[0123] a) providing a polyol component, an isocyanate component, a formulation comprising the polyether-siloxane block copolymer according to the invention and optionally further additives,

[0124] b) mixing all components to obtain a homogeneous mixture,

[0125] c) mechanically frothing the mixture while introducing a gas such as air or nitrogen to produce a uniform, fine-cell foam,

[0126] d) applying the foamed reaction mixture to a substrate,

[0127] e) solidifying the foamed reaction mixture.

[0128] It is clear that the process steps of the method described above are not subject to any fixed temporal order. For example, process steps b) and c) can be performed simultaneously, meaning that the individual components are added to and mixed with the reaction mixture during the foaming process. For mechanically foamed reaction mixtures, it is also possible to add individual additives, such as catalysts, only after process step c).

[0129] A preferred embodiment of the present invention occurs when the reaction mixture of polyol, isocyanate and optionally further additives is foamed in process step c) by applying high shear forces. The foaming can be carried out with the aid of shearing devices familiar to those skilled in the art, such as dispermats, dissolvers, Hansa mixers or Oakes mixers.

[0130] Furthermore, it is preferred if the mechanically foamed reaction mixture after process step c) has a density in the range from 50 to 1000 g / l, preferably in the range from 75 to 600 g / l, more preferably in the range from 100 to 450 g / l.

[0131] In process step d), the reaction mixture can be applied to virtually any desired substrate, for example carpet backings, synthetic turf backings, adhesive coatings, textile carrier webs, release liners or release films, and also to metals, either leaving them permanently on the metal or removing the cured reaction mixture later.

[0132] It is further preferred that, in process step e), the foamed reaction mixture is cured at elevated temperature. According to the invention, a curing temperature of at least 50° C., preferably 60° C., more preferably at least 70° C. is preferred here.

[0133] The present invention also provides the use of the polyurethane foam according to the invention, preferably the expandable PU foam as described above, for producing floor coverings such as carpets, footfall sound insulation or synthetic turf, and for producing textile coatings or sealing materials, gap fillers, shock-absorbing pads or compression pads.

[0134] As already mentioned above, the polyether siloxanes obtainable by the process according to the invention are distinguished by particularly favorable molar masses and particularly favorable molar mass distributions, which means that they are particularly suitable as additives for the production of polyurethane foams, preferably PU foams of the scalding type.

[0135] Polyether-siloxane block copolymer of Formula 1

[0136]

[0137] in

[0138] a=0 to 100, preferably 5 to 75, more preferably 10 to 50,

[0139] b=0 to 100, preferably 5 to 75, more preferably 5 to 25,

[0140] c=0 to 100, preferably 5 to 75, more preferably 5 to 25,

[0141] a+b+c>3,

[0142] d = 1 to 100, preferably 5 to 50, more preferably 7 to 30, most preferably 8-20,

[0143] n=5-200, preferably 10-100, more preferably 15-50, and

[0144] And where R 1 The groups are independently identical or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, most preferably methyl groups,

[0145] And where R 2 The radicals are independently identical or different monovalent aliphatic, saturated or unsaturated hydrocarbon radicals having 1 to 20 carbon atoms or H, particularly preferably a methyl radical,

[0146] And where R 3 The groups are independently identical or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, preferably methyl groups,

[0147] And where R 4 The groups are independently selected from R 5 、R 6 、R 7 group or H, where R 5 The group conforms to formula 2

[0148]

[0149] And where R 6 The group conforms to formula 3

[0150]

[0151] And where R 7 The group conforms to formula 4

[0152]

[0153] The coefficients a, b, and c and R 2 and R3 The group is as defined above,

[0154] The polyether-siloxane block copolymer has a weight average molar mass M of at least 60,000 g / mol, preferably at least 70,000 g / mol, more preferably at least 80,000 g / mol. w and a number-average molar mass M of at least 25,000 g / mol, preferably at least 27,500 g / mol, more preferably at least 30,000 g / mol n , when M w / M n It is particularly preferred if the ratio is less than 3.1, preferably less than 3.0, more preferably less than 2.9. These polyether-siloxane block copolymers can preferably be prepared by the process according to the invention as described in detail above.

[0155] The present invention also provides the use of these polyether-siloxane block copolymers according to the invention as additives for the production of polyurethane foams, preferably PU foams of the scalding type, in particular in combination with at least one additional polyether siloxane-based stabilizer having a siloxane chain with pendent and / or terminal polyether chains, wherein the polyether chain can be bonded to the siloxane chain via a silicon-carbon bond (Si—C) or a silicon-oxygen-carbon bond (Si—O—C), particularly preferably a silicon-carbon bond, particularly preferably those pendent Si—C-based polyether siloxanes corresponding to the formula 7 already defined above, reference being made in this context to the preceding description in its entirety. DETAILED DESCRIPTION

[0156] Example:

[0157] Determination of OH value:

[0158] All OH values ​​were determined using the following method. For this purpose, the substance to be analyzed was first acetylated with a specified amount of acetic anhydride. The excess acetic anhydride was then hydrolyzed with water, and the amount of acetic acid liberated was determined by titration with 0.5 N potassium hydroxide in ethanol against phenolphthalein. Furthermore, a blank run was performed using the same method but without the substance to be analyzed. The OH value of the sample was then calculated using the following formula:

[0159]

[0160] a = ml of 0.5N potassium hydroxide aqueous solution consumed in the main test

[0161] b = ml of 0.5N potassium hydroxide aqueous solution consumed in the blank test

[0162] E = starting weight (g)

[0163] Material:

[0164] a) SiH Siloxane A

[0165] In the subsequent synthesis, siloxanes of the general formula a are used.

[0166]

[0167] Typically, in siloxane polymers, the linear siloxane chains also contain a certain proportion of cyclic siloxanes, such as octamethylcyclotetrasiloxane. The SiH siloxane used in the experiment, for example, contained 4.2% by mass of octamethylcyclotetrasiloxane and 2.8% by mass of decamethylcyclopentasiloxane.

[0168] b) Bismethallyl polyether A

[0169] In the subsequent synthesis, the polyethers of the general formula b are used.

[0170]

[0171] Bismethallyl polyether A is prepared by reacting the corresponding polyether diol with methallyl chloride by a conventional method. The residual OH value is <1 mgKOH / 100 g.

[0172] c) Polyether of Formula 5

[0173] In the synthesis, the polyether of formula 5 used is polyether diol 1200 (CAS No. 25322-69-4). BASF® 1200 is a difunctional polyether alcohol from BASF Polyurethanes GmbH with a hydroxyl number of about 250 mgKOH / g, determined according to DIN 53240.

[0174] d) Alkoxylated alcohol of formula 6

[0175] In the synthesis, the alkoxylated alcohol of formula 6 used is APM T. APM T is PPG-3 myristyl ether from Evonik. The general formula of APM T is shown in formula c.

[0176]

[0177] e) Karstedt catalyst solution

[0178] The catalyst used was a solution of Karstedt's catalyst (1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0)) in decamethylcyclopentasiloxane, with a platinum content w (Pt) of 0.6%.

[0179] Synthesis Example:

[0180] Example 1: Synthesis in toluene

[0181] Initially, 73 g of bismethallyl polyether A was charged to a 500 ml three-necked flask equipped with a precision glass stirrer and a reflux condenser. Subsequently, 103 g of toluene and 30 g of SiH Siloxane A were added. The reaction mixture was heated to 80°C. 10 ppm of Pt was then added in the form of a Karstedt catalyst solution. The reaction mixture was heated to 95°C and stirred at this temperature for 3 hours. The result was a gel-like product, which was diluted with an additional 103 g of toluene to maintain stirrability.

[0182] A clear product was obtained in the form of a gel. Due to the very high viscosity, it was not possible to remove the solvent by distillation.

[0183] Example 2: Synthesis in toluene / polypropylene glycol

[0184] Initially, 73 g of bis(meth)allyl polyether A was placed in a 1000 ml three-necked flask equipped with a precision glass stirrer and a reflux condenser. Subsequently, 103 g of toluene, 103 g of 1200 and 30 g of SiH Siloxane A. The reaction mixture was heated to 80°C. 10 ppm of Pt was then added in the form of a Karstedt catalyst solution. The reaction mixture was heated to 95°C and stirred at this temperature for 3 hours. Subsequently, the volatile components were removed under reduced pressure at 130°C and 1 mbar.

[0185] An extremely turbid product was obtained.

[0186] Example 3: Synthesis in toluene / alkoxylated alcohol

[0187] Initially, 73 g of bis(meth)allyl polyether A was placed in a 1000 ml three-necked flask equipped with a precision glass stirrer and a reflux condenser. Subsequently, 103 g of toluene, 103 g of APM T and 30 g of SiH Siloxane A. The reaction mixture was heated to 80°C. 10 ppm of Pt was then added in the form of a Karstedt catalyst solution. The reaction mixture was heated to 95°C and stirred at this temperature for 3 hours. Subsequently, the volatile components were removed under reduced pressure at 130°C and 1 mbar.

[0188] An extremely turbid product was obtained.

[0189] Example 4: Synthesis in toluene / polypropylene glycol / alkoxylated alcohol

[0190] First, 73g of bis(meth)allyl polyether A was placed in a 1000mL three-necked flask equipped with a precision glass stirrer and a reflux condenser. Subsequently, 103g of toluene, 77g of 1200, 26g APM T and 30 g of SiH Siloxane A. The reaction mixture was heated to 80°C. 10 ppm of Pt was then added in the form of a Karstedt catalyst solution. The reaction mixture was heated to 95°C and stirred at this temperature for 3 hours. Subsequently, the volatile components were removed under reduced pressure at 130°C and 1 mbar.

[0191] A clear product was obtained.

[0192] Example 5: Synthesis in Toluene / Polypropylene Glycol / Alkoxylated Alcohol

[0193] First, 73g of bis(meth)allyl polyether A was placed in a 1000mL three-necked flask equipped with a precision glass stirrer and a reflux condenser. Subsequently, 103g of toluene, 26g of 1200, 77g APM T and 30 g of SiH Siloxane A. The reaction mixture was heated to 80°C. 10 ppm of Pt was then added in the form of a Karstedt catalyst solution. The reaction mixture was heated to 95°C and stirred at this temperature for 3 hours. Subsequently, the volatile components were removed under reduced pressure at 130°C and 1 mbar.

[0194] A clear product was obtained.

[0195] Example 6: Synthesis in Toluene / Polypropylene Glycol / Alkoxylated Alcohol

[0196] First, 146g of bis(meth)allyl polyether A was placed in a 1000mL three-necked flask equipped with a precision glass stirrer and a reflux condenser. Subsequently, 206g of toluene, 103g of 1200, 103g APM T and 60 g of SiH Siloxane A. The reaction mixture was heated to 80°C. 10 ppm of Pt was then added in the form of a Karstedt catalyst solution. The reaction mixture was heated to 95°C and stirred at this temperature for 3 hours. Subsequently, the volatile components were removed under reduced pressure at 130°C and 1 mbar.

[0197] A clear product was obtained.

[0198] For all experiments, the molar masses of the polyether siloxanes obtained were determined by gel permeation chromatography (GPC). For this purpose, a SECurity2 GPC system from PCC was used, calibrated with polystyrene. The average molar mass M obtained from these measurements was w and M nListed in Table 1. The viscosity of all samples was also measured. For this purpose, a Brookfield LV Brookfield viscometer equipped with a #64 rotor was used. All measurements of viscosities exceeding 100,000 mPas were performed at 2.5 rpm. All measurements of viscosities below 100,000 mPas were performed at 10 rpm. The values ​​thus obtained are also listed in Table 1.

[0199] Table 1: Experimental Overview

[0200]

[0201] When made of toluene, polyether 1200 and alkoxylated alcohols When the reaction is carried out in the presence of a solvent with the composition of APM T, it is found that the width of the molar mass distribution is significantly reduced. The obtained product is also clear. The width of the molar mass distribution can be determined from the M w / M n The larger the ratio, the broader the molar mass distribution; in the case of the non-inventive samples described here (Examples 1-3), at high M w / M n At values ​​of , a tailing of the molar mass distribution towards very high molar masses can be observed.

[0202] If the polyether diol or alkoxylated alcohol is omitted, the result is a turbid product, and the resulting polyether siloxane has a broader molar mass distribution. If toluene is used as the sole solvent, clear products can be obtained, but the molar mass distribution of these products is even broader. Consequently, the resulting product is gel-like and no longer free-flowing.

[0203] A turbid product is also undesirable because, depending on the length of storage, separation may occur. An inhomogeneous product complicates the production process.

[0204] Polyurethane preparations:

[0205] In order to evaluate the efficacy of the polyether-siloxane block copolymers prepared in Examples 1-6 as stabilizers for producing foamable polyurethane foams, a series of foaming tests were conducted. These tests were completed using the polyurethane formulations described in Table 2:

[0206] Table 2: Overview of formulations used in foaming experiments.

[0207]

[0208] Example 7: Machine foaming operation:

[0209] The machine foaming operation was performed using a Pico-Mix XL fully automatic laboratory foam generator from Hansa-Mixer equipped with two independent eccentric screw hopper pumps. To this end, a premix of polyol, stabilizer, catalyst and calcium carbonate (batch size of approximately 5 kg) was first prepared and then loaded into one of the two hopper pumps of the foam generator. The other hopper pump was filled with the isocyanate component. The formulations described in Table 1 were used here. For the foaming experiments, the polyol premix and isocyanate were simultaneously injected into the mixing head of the foam generator and foamed therein by simultaneously introducing air. In all experiments, the mixing head was operated at 850 rpm. The delivery rate of the two hopper pumps was continuously adjusted so that the polyol and isocyanate were injected into the mixing head in an appropriate ratio (corresponding to the NCO coefficient of the formulation) with a total mass flow rate of 9 kg / hour. The air flow entering the mixing head was selected so that foam densities of 250 and 300 g / l were obtained after foaming. The uniformity and stability of the foam obtained when discharged from the mixing head were evaluation criteria for the effectiveness of the foam stabilizer. The foamed reaction mixture was then applied to the coated release paper (layer thickness 6 mm) using a laboratory coating table / dryer (Labcoater LTE-S from Mathis AG) and cured for 15 minutes at 120°C. The cell structure and cell homogeneity of the cured foam were further evaluation criteria for the effectiveness of the foam stabilizer.

[0210] Table 3: Machine foaming operation results

[0211] (Ratings range from - = very poor, to o = average, to ++ = very good)

[0212]

[0213] As is apparent from the compositions in Table 2, the foams produced by the method according to the invention and containing the polyether-siloxane block copolymer according to the invention exhibit improved foam stability and a finer, more uniform cell structure. In contrast, the stabilizers not according to the invention from Examples 1-3 produced rather coarse, irregular foams with reduced stability, as evidenced, for example, by the coarser cells upon curing of the foams. Thus, the foaming results clearly demonstrate the improved efficacy of the foam stabilizers produced by the method according to the invention.

Claims

1. Method for preparing polyether-siloxane block copolymer of formula 1 in a=0 to 100, b = 0 to 100, c = 0 to 100, a+b+c>3, d = 1 to 100, n = 5-200, and where R 1 The groups are independently the same or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, And where R 2 The groups are independently identical or different monovalent aliphatic, saturated or unsaturated hydrocarbon groups having 1 to 20 carbon atoms or H, And where R 3 The groups are independently the same or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, And where R 4 The groups are independently selected from R 5 、R 6 、R 7 group or H, where R 5 The group conforms to formula 2 And where R 6 The group conforms to formula 3 And where R 7 The group conforms to formula 4 The coefficients a, b, and c and R 2 and R 3 The group is defined above, and the method is hydrosilylation of an α,ω-modified hydrogensiloxane with an α,ω-modified di(meth)allyl polyether in the presence of a hydrosilylation catalyst capable of catalyzing the formation of SiC bonds by the addition of Si—H groups to (meth)allylic double bonds, It is characterized by: The reaction is carried out in a solvent mixture comprising an aromatic solvent, a polyether of Formula 5 and an alkoxylated alcohol of Formula 6 in g＝0， h=1 to 100, i = 1 to 100, and where R 8 The groups are independently the same or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, in j＝0， k = 0 to 20, l = 1 to 20, and where R 9 The group is a monovalent aliphatic saturated or unsaturated, linear or branched hydrocarbon group having 6 to 40 carbon atoms, And where R 8 The groups are as defined above.

2. The method according to claim 1, characterized in that a=5 to 75, b=5 to 75, c=5 to 75, d = 5 to 50, n＝10-100， R 1 The groups are independently the same or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 10 carbon atoms, R 2 The group is a methyl group, R 3 The group is a methyl group, The aromatic solvent includes toluene, h=2 to 50, i=2 to 50, R 8 The group is a methyl group, k = 0 to 10, l = 2 to 10, and R 9 The radical is a monovalent aliphatic saturated or unsaturated, linear or branched hydrocarbon radical having 8 to 30 carbon atoms.

3. The method according to claim 1, characterized in that a=10 to 50, b=5 to 25, c=5 to 25, d = 7 to 30, n＝15-50， R 1 The group is a methyl group, The aromatic solvent includes alkylbenzene, h=3 to 25, i=3 to 25, k = 0 to 5, l = 3 to 5, R 9 The radical is a monovalent aliphatic saturated or unsaturated, linear or branched hydrocarbon radical having 10 to 22 carbon atoms.

4. The method according to claim 3, characterized in that d＝8-20。 5. The method according to claim 1, characterized in that The polyether of Formula 5 and the alkoxylated alcohol of Formula 6 are used in a mass ratio of 1:4 to 4:

1.

6. The method according to claim 5, characterized in that The polyether of Formula 5 and the alkoxylated alcohol of Formula 6 are used in a mass ratio of 1:3 to 1:

3.

7. The method according to claim 1 or 5, characterized in that Aromatic solvents are used in amounts of >15% by weight, based on the total solvent mixture used.

8. The method according to claim 7, characterized in that Aromatic solvents are used in amounts of >20% by weight, based on the total solvent mixture used.

9. The method according to claim 7, characterized in that Aromatic solvents are used in amounts of >30% by weight, based on the total solvent mixture used.

10. The method according to claim 7, characterized in that The aromatic solvent includes toluene.

11. The method according to claim 7, characterized in that The aromatic solvent includes alkylbenzene.

12. The method according to any one of claims 1 to 6, characterized in that The ratio of the sum of the masses of the polyether of Formula 5 and the alkoxylated alcohol of Formula 6 to the sum of the masses of the reactants is 8:2 to 1:

4.

13. The method according to any one of claims 1 to 6, characterized in that The α,ω-modified di(meth)allyl polyether is used in a concentration such that the molar ratio of polyether-bound double bonds to siloxane-bound Si—H groups is in the range of 0.95:1.05 to 1.05:0.

95.

14. The method according to claim 13, characterized in that The α,ω-modified di(meth)allyl polyether is used in a concentration such that the molar ratio of polyether-bound double bonds to siloxane-bound Si—H groups is in the range of 0.97:1.03 to 1.03:0.

97.

15. The method according to claim 13, characterized in that The α,ω-modified di(meth)allyl polyether is used in a concentration such that the molar ratio of polyether-bound double bonds to siloxane-bound Si—H groups is in the range of 0.99:1.01 to 1.01:0.

99.

16. The method according to any one of claims 1 to 6, characterized in that The hydrosilylation catalyst used in the reaction is selected from platinum catalysts.

17. The method according to any one of claims 1 to 6, characterized in that The hydrosilylation catalyst used in the reaction is selected from platinum (0) catalysts.

18. The method according to any one of claims 1 to 6, characterized in that The hydrosilylation catalyst used in the reaction is selected from platinum (0) catalysts in the form of Karstedt catalysts.

19. A preparation suitable as an additive for the production of polyurethane foams, comprising the following components: (a) Polyether-siloxane block copolymer of formula 1 in a=0 to 100, b = 0 to 100, c = 0 to 100, d = 1 to 100, n = 5-200, and where R 1 The groups are independently the same or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, And where R 2 The groups are independently identical or different monovalent aliphatic, saturated or unsaturated hydrocarbon groups having 1 to 20 carbon atoms or H, And where R 3 The groups are independently the same or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, And where R 4 The groups are independently selected from R 5 、R 6 、R 7 group or H, where R 5 The group conforms to formula 2 And where R 6 The group conforms to formula 3 And where R 7 The group conforms to formula 4 The coefficients a, b, and c and R 2 and R 3 The group is as defined above, (b) Polyether of Formula 5 in g＝0， h=1 to 100, i = 1 to 100, and where R 8 The groups are independently the same or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, (c) Alkoxylated alcohol of formula 6 in j＝0， k = 1 to 20, l = 1 to 20, and where R 9 The group is a monovalent aliphatic saturated or unsaturated, linear or branched hydrocarbon group having 6 to 40 carbon atoms, And where R 8 The groups are as defined above, and (d) optionally an aromatic solvent.

20. The preparation according to claim 19, characterized in that The polyurethane foam is a beating type PU foam. a=5 to 75, b=5 to 75, c=5 to 75, d = 5 to 50, n＝10-100， R 1 The groups are independently the same or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 10 carbon atoms, R 2 The group is a methyl group, R 3 The group is a methyl group, h=2 to 50, i=2 to 50, R 8 The group is a methyl group, k = 2 to 10, l = 2 to 10, R 9 The radical is a monovalent aliphatic saturated or unsaturated, linear or branched hydrocarbon radical having 8 to 30 carbon atoms.

21. The preparation according to claim 19, characterized in that a=10 to 50, b=5 to 25, c=5 to 25, d = 7 to 30, n＝15-50， R 1 The group is a methyl group, h=3 to 25, i=3 to 25, k = 3 to 5, l = 3 to 5, and where R 9 The radical is a monovalent aliphatic saturated or unsaturated, linear or branched hydrocarbon radical having 10 to 22 carbon atoms.

22. The preparation according to claim 19, characterized in that d＝8-20。 23. The preparation according to claim 19, characterized in that Components b) and c) are present in a mass ratio of 1:4 to 4:

1.

24. The preparation according to claim 23, characterized in that Components b) and c) are present in a mass ratio of 1:3 to 3:

1.

25. The preparation according to claim 19 or 24, characterized in that The mass ratio of the sum of b) and c) to a) is 8:2 to 1:

4.

26. The preparation according to any one of claims 19 to 24, characterized in that The polyether-siloxane block copolymer of Formula 1 has an M of ≥60,000. w (g / mol), where M w / M n <3.

1.

27. The preparation according to claim 26, characterized in that The polyether-siloxane block copolymer of Formula 1 has an M of >8000 w (g / mol), M w / M n <3.

0.

28. The preparation according to claim 26, characterized in that The polyether-siloxane block copolymer of Formula 1 has an M of >90,000. w (g / mol), M w / M n <2.

9.

29. The preparation according to claim 26, characterized in that The polyether-siloxane block copolymer of Formula 1 has an M of >100,000. w (g / mol).

30. The preparation according to any one of claims 19 to 24, characterized in that An additional component used is at least one pendant polyether siloxane-based stabilizer having a siloxane chain with pendant and / or terminal polyether chains, wherein the polyether chains can be bonded to the siloxane chain via silicon-carbon bonds (Si—C) or silicon-oxygen-carbon bonds (Si—O—C).

31. The preparation according to claim 30, characterized in that The at least one side chain polyether siloxane-based stabilizer is a side chain Si-C-based polyether siloxane according to Formula 7. in x = 0 to 50, y = 0 to 250, where R 9 The groups are independently the same or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, and wherein R 10 The groups are independently the same or different OH-functional or OH-terminated polyoxyalkylene groups, and wherein R 11 The group corresponds to R 9 or R 10 .

32. The preparation according to claim 31, characterized in that x = 1 to 25, y = 5 to 150, R 9 The groups are independently the same or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 10 carbon atoms, R 10 The groups are independently methyl-terminated or acetyl-terminated polyoxyalkylene groups.

33. The preparation according to claim 31, characterized in that x=2 to 15, y = 5 to 100, R 9 The group is a methyl group, R 10 The group is a polyoxyethylene polyoxypropylene group.

34. The preparation according to any one of claims 19 to 24, obtainable by a process according to any one of claims 1 to 18, optionally with subsequent removal of the toluene.

35. A polyether-siloxane block copolymer according to formula 1, in a=0 to 100, b = 0 to 100, c = 0 to 100, a+b+c>3, d = 1 to 100, n = 5-200, and where R 1 The groups are independently the same or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, And where R 2 The groups are independently identical or different monovalent aliphatic, saturated or unsaturated hydrocarbon groups having 1 to 20 carbon atoms or H, And where R 3 The groups are independently the same or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, And where R 4 The groups are independently selected from R 5 、R 6 、R 7 group or H, where R 5 The group conforms to formula 2 And where R 6 The group conforms to formula 3 And where R 7 The group conforms to formula 4 The coefficients a, b, and c and R 2 and R 3 The group is as defined above, The polyether-siloxane block copolymer has a weight average molar mass M of at least 60,000 g / mol. w and a number-average molar mass M of at least 25,000 g / mol n .

36. The polyether-siloxane block copolymer according to claim 35, prepared by the method according to any one of claims 1 to 18, in a=5 to 75, b=5 to 75, c=5 to 75, d = 5 to 50, n = 10-100, and R 1 The groups are independently the same or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 10 carbon atoms, R 2 The group is a methyl group, R 3 The group is a methyl group, The polyether-siloxane block copolymer has a weight-average molar mass M of at least 70,000 g / mol. w and a number-average molar mass M of at least 27500 g / mol n .

37. The polyether-siloxane block copolymer according to claim 35, in a=10 to 50, b=5 to 25, c=5 to 25, d = 7 to 30, n = 15-50, and R 1 The group is a methyl group, The polyether-siloxane block copolymer has a weight-average molar mass M of at least 80,000 g / mol. w and a number-average molar mass M of at least 30,000 g / mol n .

38. The polyether-siloxane block copolymer according to claim 35, in, d＝8-20， M w / M n The ratio is less than 3.

1.

39. The polyether-siloxane block copolymer according to claim 35, in, M w / M n The ratio is less than 3.

0.

40. The polyether-siloxane block copolymer according to claim 35, in, M w / M n The ratio is less than 2.

9.

41. Use of the preparation according to any one of claims 19 to 34 and / or the polyether-siloxane block copolymer according to any one of claims 35 to 40 as an additive for producing polyurethane foams.

42. The use according to claim 41, wherein the polyurethane foam is a scalable PU foam and the preparation and / or the combination of the polyether-siloxane block copolymer and at least one additional polyether siloxane-based stabilizer is used as an additive for producing the polyurethane foam.

43. The method according to claim 42, wherein the additional polyethersiloxane-based stabilizer comprises a siloxane chain with side and / or terminal polyether chains, wherein the polyether chains can be bonded to the siloxane chain via silicon-carbon bonds (Si-C) or silicon-oxygen-carbon bonds (Si-OC).

44. The use according to claim 42, wherein the additional polyether siloxane-based stabilizer is a Si-C-based polyether siloxane having side chains corresponding to those of formula 7 in x = 0 to 50, y = 0 to 250, where R 9 The groups are independently the same or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, and wherein R 10 The groups are independently the same or different OH-functional or OH-terminated polyoxyalkylene groups, and wherein R 11 The group corresponds to R 9 or R 10 .

45. The use according to claim 44, wherein x = 1 to 25, y = 5 to 150, where R 9 The groups are independently the same or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 10 carbon atoms, and wherein R 10 The groups are independently methyl-terminated or acetyl-terminated polyoxyalkylene groups.

46. ​​The use according to claim 44, wherein x=2 to 15, y = 5 to 100, R 9 The group is a methyl group, R 10 The group is a polyoxyethylene polyoxypropylene group.

47. The method according to claim 41, wherein the polyurethane foam to be produced is a mechanically foamed polyurethane foam containing less than 2% by weight of chemical or physical blowing agents.

48. The method according to claim 47, wherein the polyurethane foam to be produced is a mechanically foamed polyurethane foam containing less than 1% by weight of chemical or physical blowing agents.

49. The method according to claim 47, wherein the polyurethane foam to be produced is a mechanically foamed polyurethane foam containing less than 0.5% by weight of a chemical or physical blowing agent.

50. The method according to claim 47, wherein the polyurethane foam to be produced is a mechanically foamed polyurethane foam containing less than 0.1% by weight of a chemical or physical blowing agent.

51. Polyurethane foam produced using the preparation according to any one of claims 19 to 34 and / or the polyether-siloxane copolymer according to claim 35. The polyurethane foam according to claim 51 , which is a blown PU foam.

53. The polyurethane foam according to claim 51, which is produced according to the conditions of claim 41 or 47.

54. Use of the polyurethane foam according to claim 51 for producing floor coverings, footfall sound insulation or synthetic turf, and for producing textile coatings or sealing materials, gap fillers, shock-absorbing pads or compression pads.

55. The use according to claim 54, wherein the polyurethane foam is a blown PU foam and the floor covering is a carpet.

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