Polyether-siloxane block copolymers for producing polyurethane foams

Abstract

The invention relates to a process for producing polyether-siloxane block copolymers by hydrosilylation of alpha-omega-modified hydrogen siloxanes with alpha-omega-modified di-(meth)allyl polyethers in the presence of a hydrosilylation catalyst, wherein the reaction is carried out in a solvent mixture that comprises aromatic solvents and alkoxylated alcohol.

Description

[0001] Polyether-siloxane block copolymers for the production of polyurethane foams

[0002] The present invention is in the field of polyether siloxanes, polyurethanes and polyurethane foams.

[0003] It relates in particular to the production of special polyether-siloxane block copolymers as well as special formulations and their use for the production of polyurethane foams, preferably rigid polyurethane foam, particularly preferably one-component PU can foam (construction foam, assembly foam, one-component foam / OCF) and other rigid polyurethane foams for which a high degree of open-cell density is advantageous (e.g. open-cell spray foam, packaging foam, roof liner foam, pipe insulation foams, floral foam, thermoformable rigid foams, etc.).

[0004] One-component PU foam is well known. It is a polyurethane foam that is expanded by a pressurized propellant gas from a pressurized can. Applications include the assembly, bonding, and sealing of windows, door frames, pipes, penetrations, etc., as well as the filling of masonry gaps, cavities, cracks, and joints. Such foam is preferably produced by providing a prepolymer of polyol and isocyanate (preferably methylene diphenyl isocyanate, MDI) in the pressurized can, which is expelled by the propellant gas and cures with ambient moisture. Polyol-isocyanate prepolymers contain both reactive isocyanate groups and urethane bonds.

[0005] For all of the above-mentioned applications, it is important that the finished one-component PU foam exhibits minimal change in geometric dimensions during and especially after the curing process. This dimensional stability, i.e., low shrinkage or low post-expansion, is achieved by the foam's high open-cell density. At the same time, however, this open-cell density must not result in any serious foam defects such as voids; instead, the foam cells should remain fine and not exhibit any coarsening. For this reason, it is common practice to add a cell opener to the polyol-isocyanate prepolymer in addition to the foam stabilizer usually present (usually a polyether siloxane). Polyether siloxane block copolymers have proven particularly effective for this application. These cell openers are generally characterized by a linear [AB] nBlock structure consisting of alternating polyether and siloxane chains. A high molecular weight is important for good cell-opening efficacy, but reproducible production of such molecular weights is challenging.

[0006] Non-hydrolyzable [AB] n Polyether siloxanes are known to those skilled in the art. For example, such polymers are described in US Pat. No. 3,957,842. This patent describes the preparation of these structures by hydrosilylation of diallylpolyethers with α,α-SiH-functional siloxanes in toluene. The molecular weight of the resulting polymers is approximately 36,000–56,000 g / mol. US Pat. No. 4,150,048 describes non-hydrolyzable [AB] nPolyethersiloxanes prepared by hydrosilylation of polyethers with two CH2=C(R)CH2 end groups per molecule, where R is a monovalent hydrocarbon group. They are prepared with α,α-SiH-functional siloxanes under hydrosilylation reaction conditions in the presence of a platinum catalyst. The prepared linear block copolymers are particularly useful as surfactants and foam stabilizers for the production of polyurethane foams. The low tendency for isomerization of the CH2=C(R)CH2 group to non-reactive species during the hydrosilylation reaction leads to the unexpectedly high molecular weight of the copolymers.

[0007] US 5869727 describes a vacuum process for the production of siloxane-oxyalkylene copolymers.

[0008] US 20190233646 describes a composition with [AB] n-Polyethersiloxanes. The composition comprises a polyether-polysiloxane block copolymer and a liquid organic monool compound, which is either a glycol ether compound with a low degree of polymerization, a terminal hydrogen, or an alcohol compound with a branched alkyl group having 12 or more carbon atoms.

[0009] As already described, a high molecular weight is important for achieving high cell openness and is therefore particularly desirable. A cell opener with a molecular weight that is too low would lead to a reduced cell-opening effect, causing the foam to shrink or expand. In addition to the highest possible molecular weight of the cell opener, it is also important that the molecular weight distribution is as narrow as possible. Tailing of the molecular weight distribution to very high molecular weights can have particularly detrimental effects. Such tailing can cause the viscosity of the cell opener to become very high, which severely impairs its processability during foam production.

[0010] The object of the present invention was therefore to provide polyether-siloxane block copolymers which are characterized by a particularly high molecular weight with, at the same time, the narrowest possible molecular weight distribution and, associated therewith, advantageously have a particularly efficient activity as cell openers.

[0011] Surprisingly, it was found that the use of a specific solvent mixture enables the preparation of corresponding polyether-siloxane block copolymers and thus the solution of the above-mentioned problem.

[0012] The present invention therefore relates to a process for the preparation of polyether

[0013] Siloxane block copolymers according to formula 1

[0014] Formula 1 , where a = 0 to 100, preferably 5 to 75, particularly preferably 10 to 50, b = 0 to 100, preferably 5 to 75, particularly preferably 5 to 25, c = 0 to 100, preferably 5 to 75, particularly preferably 5 to 25, a + b + c > 3, d = 1 to 100, preferably 5 to 50, particularly preferably 7 to 40, very particularly preferably 12 to

[0015] 30, n = 5 to 200, preferably 10 to 100, particularly preferably 15 to 50 and wherein the radicals R 1 independently of one another are identical or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably having 1 to 10 carbon atoms, very particularly preferably methyl radicals, and wherein the radicals R 2 are independently identical or different monovalent aliphatic saturated or unsaturated hydrocarbon radicals having 1 to 20 carbon atoms or H, with particular preference being given to methyl radicals, and wherein the radicals R 3independently of one another are identical or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably methyl radicals, and wherein the radicals R 4 are independently selected from one of the radicals R 5 , R e , R 7 or H, where the radicals R 5 correspond to formula 2 Formula 2, and where the radicals R e correspond to Formula 3 Formula 3, and where the radicals R 7 correspond to formula 4 where the indices a, b and c, as well as the residues R 2 and R 3as previously defined, by hydrosilylation of alpha-omega modified hydrogen siloxanes with alpha-omega modified di-(meth)allyl polyethers in the presence of a hydrosilylation catalyst which is capable of catalyzing the formation of a SiC bond by addition of a Si-H group to a (meth)allylic double bond, wherein the reaction is carried out in a solvent mixture comprising at least one aromatic solvent of the general formula 5, where x = 0 - 20, preferably 0 - 16 y = 0 - 20, preferably 0 - 16 x + y = 6 - 20, preferably 8 - 16 and at least one alkoxylated alcohol of the formula 6 where j = 0 to 30, preferably 0 to 10, particularly preferably 0, k = 0 to 20, preferably 0 to 10, particularly preferably 0 to 5,

[0016] I = 1 to 20, preferably 2 to 10, particularly preferably 3 to 5 and wherein the radical R 9a monovalent aliphatic saturated or unsaturated, linear or branched hydrocarbon radical having 6 - 40, preferably 8 - 30, more preferably 10 - 22 carbon atoms, and wherein the radicals R 8 are independently identical or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably methyl radicals.

[0017] The sequence of the different oxyalkylene units, which are indicated in square brackets and lowercase indices in the polyoxyalkylene radicals, polyols, or alkoxylated alcohols, can be random (statistically distributed), block-wise, gradually varying, or in any combination of these possibilities. The structural formulas given here are merely a simplified graphic representation with regard to the sequence.

[0018] The solvent mixture according to the invention therefore comprises at least two components, namely aromatic solvent of formula 5 and alkoxylated alcohol of formula 6, preferably it consists of these two components.

[0019] In a particularly preferred embodiment of the invention, the solvent mixture according to the invention does not contain a polyether of the formula 8 where g = 0 to 75, preferably 0 to 50, particularly preferably 0 to 25, h = 1 to 100, preferably 2 to 50, particularly preferably 3 to 25, i = 1 to 100, preferably 2 to 50, particularly preferably 3 to 25 and where the radicals R 8independently of one another, are identical or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably methyl radicals. Such a solvent mixture according to the invention, which thus comprises at least aromatic solvent of formula 5 and alkoxylated alcohol of formula 6, but which is free of polyether of formula 8, corresponds to a particularly preferred embodiment of the invention.

[0020] The advantages of the process according to the invention include not only that it enables the provision of corresponding polyether-siloxane block copolymers with a high molecular weight and, at the same time, the narrowest possible molecular weight, but also that the resulting formulations have a comparatively low viscosity with a comparatively high active ingredient content, and thus have considerable processing advantages.

[0021] A further advantage is that the resulting polyether-siloxane block copolymers exhibit a narrow molecular weight distribution at high molecular weight. In particular, the provision of polyether-siloxane block copolymers according to formula 1 with a weight-average molecular weight M w (g / mol) of > 60000, advantageously > 80000, preferably > 90000, in particular > 100000, where M w / M n < 4.5, preferably < 4.0, in particular < 3.5. M n is the number average molecular weight.

[0022] The high molecular weight is particularly advantageous for the inventive use of the described polyether-siloxane block copolymers as cell openers for the production of polyurethane foams, preferably rigid polyurethane foams (especially one-component PU can foams, open-cell spray foam, packaging foam, roof lining foam, pipe insulation foams, floral foam, thermoformable rigid foams, etc.), because it allows for the production of particularly open-cell foams. In addition to the open-cell structure, a regular foam and pore structure and a low foam defect rate are achieved. The low viscosity and the narrow molecular weight distribution are equally valuable in this regard.

[0023] Polyether-siloxane block copolymers are known per se. For the purposes of the present invention, the term polyether encompasses polyoxyalkylenes, with particular preference being given to polyoxyethylene and polyoxypropylene, as well as polyoxyethylene-polyoxypropylene mixed polyethers. The distribution of various oxyalkylene units along the polymer backbone can vary. Mixed polyethers can, for example, be structured randomly, blockwise, or with different gradients of the monomer units relative to one another. In this context, a random structure means that polyoxyethylene and polyoxypropylene units are distributed in a random order throughout the polyether chain, whereas a blockwise polyether consists of defined polyoxyethylene and polyoxypropylene blocks.

[0024] For the purposes of the present invention as a whole, the term "siloxane" encompasses compounds from the class of polyorganosiloxanes, particularly preferably from the class of polydimethylsiloxanes. For the purposes of the present invention as a whole, the term "polyether-siloxane block copolymers" encompasses polymers composed of alternating polyether and siloxane blocks. The polyether-siloxane block copolymers according to the invention are subject to formula 1.

[0025] The term polyurethane foam is known to the person skilled in the art (see, for example, Adam et al., “Polyurethanes”, Ullmann's Encyclopedia of Industrial Chemistry - Paragraph 7”, 2012, Wiley VCH-Verlag, Weinheim).

[0026] A preferred composition according to the invention of a PU foam, preferably rigid polyurethane foam, contains the following components: a) Polyether-siloxane block copolymer according to the invention as cell opener b) Polyol component c) (Poly)isocyanate component d) Catalyst e) Optionally foam stabilizer f) Blowing agent g) Optionally further additives, preferably fillers, liquid flame retardants, etc.

[0027] The terms polyurethane and polyurethane foam are established technical terms and have long been known to experts.

[0028] In the context of the present invention, polyurethane (PU) is understood in particular to mean a product obtainable by reacting a polyisocyanate component with a polyol component.

[0029] In addition to polyurethane, other functional groups, such as uretdiones, carbodiimides, isocyanurates, allophanates, biurets, ureas, and / or uretimines, can also be formed. Therefore, PU in the context of the present invention includes both polyurethane and polyisocyanurates, polyureas, as well as polyisocyanate reaction products containing uretdione, carbodiimide, allophanate, biuret, and / or uretimine groups.

[0030] Accordingly, polyurethane foam (PU foam) in the context of the present invention refers to a foam obtained as a reaction product of a polyisocyanate component and a polyol component. In addition to the eponymous polyurethane, other functional groups such as allophanates, biurets, ureas, carbodiimides, uretdiones, isocyanurates, or uretimines can also be formed.

[0031] PU rigid foam is a well-established technical term. The well-known and fundamental difference between flexible foam and rigid foam is that flexible foam exhibits elastic behavior and, therefore, deformation is reversible. Rigid foam, on the other hand, is permanently deformed. Further information on polyurethane rigid foams can be found in "Kunststoffhandbuch, Volume 7, Polyurethane," Carl Hanser Verlag, 3rd edition 1993, Chapter 6. The terms "foam" and "cellular material" are used synonymously for the purposes of this invention. This also applies accordingly to related terms such as "rigid foam" and "rigid foam material," etc.Particularly preferred PU foams within the meaning of the present invention are rigid polyurethane foams, one-component can foam, open-cell spray foam, packaging foam, roof lining foam, pipe insulation foam, floral foam, thermoformable rigid foam and / or other rigid polyurethane foams in which a high degree of open cell density is advantageous.

[0032] As polyol component (b), one or more organic compounds having OH groups, SH groups, NH groups and / or NH2 groups, with a functionality of 1.8 to 8, can be used. The polyol component comprises at least one compound having at least two isocyanate-reactive groups selected from OH groups, SH groups, NH groups and / or NH2 groups, in particular OH groups.

[0033] A functionality of, for example, 1.8 can be achieved by mixing at least one compound with a higher functionality, for example, greater than or equal to 2, with at least one compound with a functionality of, for example, 1. This can occur in particular when a polyisocyanate component (c) with a functionality greater than 2 or additional crosslinkers are used as optional additives (h).

[0034] Corresponding compounds that can typically be used in the production of PU foams are known to those skilled in the art and are described, for example, in "Kunststoffhandbuch, Volume 7, Polyurethane," Carl Hanser Verlag, 3rd edition 1993, Chapter 3.1. Compounds with OH numbers in the range of 10 to 1200 mg KOH / g are typically used.

[0035] Particularly preferred compounds are all polyether polyols and polyester polyols commonly used for the production of polyurethane systems, in particular polyurethane foams.

[0036] In addition, polyether polycarbonate polyols, natural oil-based polyols (NOPs; described in WO 2005 / 033167, US 2006 / 0293400, WO 2006 / 094227, WO 2004 / 096882, US 2002 / 0103091, WO 2006 / 116456, EP 1678232), filler polyols, prepolymer-based polyols and / or recycling polyols can be used.

[0037] Recycling polyols are polyols obtained from the chemical recycling of polyurethanes, for example, by solvolysis, such as glycolysis, hydrolysis, acidolysis, or aminolysis. The use of recycling polyols represents a particularly preferred embodiment of the invention.

[0038] A preferred embodiment of the invention is achieved when the polycomponent contains polyol-isocyanate prepolymers. One or more polyisocyanates with two or more isocyanate groups can generally be used as the isocyanate or polyisocyanate component (c). Suitable polyisocyanates for the purposes of this invention are all organic isocyanates with two or more isocyanate groups, in particular the known aliphatic, cycloaliphatic, arylaliphatic, and preferably aromatic polyfunctional isocyanates.

[0039] Examples include alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene radical, such as 1,12-dodecane diisocyanate, 2-ethyltetramethylene-1,4-diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, tetramethylene-1,4-diisocyanate, pentamethylene diisocyanate (PDI) and preferably hexamethylene-1,6-diisocyanate (HMDI), cycloaliphatic diisocyanates such as cyclohexane-1,3- and -1,4-diisocyanate and the corresponding isomer mixtures, 4,4'-methylenedicyclohexyl diisocyanate (H12MDI), isophorone diisocyanate (IPDI), 2,4- and 2,6-methylcyclohexyl diisocyanate and the corresponding isomer mixtures and preferably aromatic di- and polyisocyanates such as 2,4- and 2,6-toluene diisocyanate (TDI) as well as the corresponding isomer mixtures, naphthylene diisocyanate, diethyltoluene diisocyanate, 4,4'- or 2,2'- or 2,4'-diphenylmethane diisocyanate (MDI) and polymethylene polyphenyl polyisocyanates (PMDI, “polymeric MDI”).The organic polyisocyanates can be used individually or in the form of mixtures. Corresponding "oligomers" of diisocyanates can also be used, such as the IPDI trimer based on isocyanurate, biuret, or urethdione. Furthermore, the use of prepolymers based on the above-mentioned isocyanates is possible. Particularly suitable is the mixture known as "polymeric MDI" (also called "crude MDI"), consisting of MDI and more highly condensed analogues with an average functionality of 2 to 4, as well as the various isomers of TDI in pure form or as a mixture of isomers. It is also possible to use isocyanates modified by the incorporation of urethane, uretdione, isocyanurate, allophanate, and other groups, so-called modified isocyanates. Examples of particularly suitable isocyanates include:in EP 1712578, EP 1161474, WO 00 / 58383, US 2007 / 0072951 , EP 1678232 and WO 2005 / 085310, which are incorporated herein by reference.

[0040] A preferred ratio of polyisocyanate component and polyol component, expressed as an index of the formulation, ie as a stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (e.g. OH groups, NH groups) multiplied by 100, is in the range from 10 to 1000, preferably 40 to 500. An index of 100 represents a molar ratio of the reactive groups of 1 to 1.

[0041] Suitable catalysts (d) that can be used for the production of polyurethanes, in particular PU foams, are known to the person skilled in the art from the prior art. For the purposes of the present invention, all compounds capable of catalyzing the reaction of isocyanate groups with OH, NH, or other isocyanate-reactive groups and / or the reaction of isocyanate groups with one another can be used. The usual catalysts known from the prior art can be used here, including, for example, amines (cyclic, acyclic; monoamines, diamines, oligomers with one or more amino groups), ammonium compounds, organometallic compounds and / or metal salts, preferably those of tin, iron, bismuth, potassium and / or zinc. In particular, mixtures of several such compounds can be used as catalysts.

[0042] Foam stabilizers (e) and their use in the production of PU foams are known to the person skilled in the art. The use of foam stabilizers is optional; preferably, one or more foam stabilizers are used. Surface-active compounds (surfactants) can be used as foam stabilizers. Foam stabilizers are preferably used. They can serve to optimize the desired cell structure and the foaming process. Within the scope of this invention, Si-containing compounds can be used in particular, which support foam production (stabilization, cell regulation, cell opening, etc.). These compounds are sufficiently known from the prior art. With particular preference, at least one foam stabilizer based on a polyether siloxane can be used. Corresponding siloxane structures that can be used within the meaning of this invention are, for example,described in the following patent specifications, although their use is only described in classic PU foams (e.g. as molded foam, mattress, insulation material, construction foam, etc.): CN 103665385, CN 103657518, CN 103055759, CN 103044687, US 2008 / 0125503, US 2015 / 0057384, EP 1520870 A1, EP 1211279, EP 0867464, EP 0867465, EP 0275563. In addition to surface-active Si-containing compounds, Si-free surfactants can also be used. For example, EP2295485 A1 describes the use of lecithin, and US Pat. No. 3,746,663 describes the use of vinylpyrrolidone-based structures as foam stabilizers for the production of rigid PU foam. Other Si-free foam stabilizers are described, for example, in EP 2511328 B1, DE 1020011007479 A1, DE 3724716 C1, EP 0734404, EP 1985642, DE 2244350, and US Pat. No. 5,236,961.

[0043] Blowing agents and their use in the production of PU foams are known to those skilled in the art. The use of blowing agents is optional, but blowing agents are preferably used. The use of one or a combination of several blowing agents (f) depends fundamentally on the type of foaming process used, the type of system, and the application of the resulting PU foam. Chemical and / or physical blowing agents, or a combination of both, can be used. Depending on the amount of blowing agent used, a foam with a high or low density is produced. For example, foams with densities of 5 kg / m 3 up to 900 kg / m 3 , preferably 5 to 350, particularly preferably 8 to 200 kg / m 3 , especially 8 to 150 kg / m 3can be produced. One or more of the corresponding compounds with suitable boiling points and mixtures thereof, such as hydrocarbons with 3, 4 or 5 carbon atoms, preferably cyclo-, iso-, n-pentane, fluorocarbons (HFC), preferably HFC 245fa, HFC 134a or HFC 365mfc, chlorofluorocarbons (HCFC), preferably HCFC 141b, hydrofluoroolefins (HFO) or hydrohaloolefins, preferably 1234ze, 1234yf, 1224yd, 1233zd(E) or 1336mzz, esters, preferably methyl formate, ketones, preferably acetone, ethers preferably dimethoxymethane, or chlorinated hydrocarbons, preferably dichloromethane or 1,2-dichloroethane can be used as physical blowing agents.

[0044] Gaseous propellants can also be used in pressure cans, whereby all suitable gases under pressure or in pressure-liquefied form are suitable, for example hydrocarbons such as butane isomers and propane isomers, dimethyl ether, nitrogen, air and other suitable gases.

[0045] As chemical blowing agents, one or more compounds can be used which react with NCO groups to release gases, such as water or formic acid, or which release gases due to the temperature increase during the reaction, such as sodium bicarbonate.

[0046] As optional additives (h), one or more of the substances known from the prior art which are used in the production of polyurethanes, in particular PU foams, can be used, such as crosslinkers, chain extenders, stabilizers against oxidative degradation (so-called antioxidants), flame retardants, biocides, cell-refining additives, nucleating agents, other cell openers, solid fillers, antistatic additives, thickeners, dyes, pigments, color pastes, fragrances and / or emulsifiers, etc.

[0047] As an optional flame retardant, the composition according to the invention can contain one or more of the known flame retardants suitable for the production of PU foams, such as, for example, halogen-containing or halogen-free organic phosphorus-containing compounds, such as, for example, triethyl phosphate (TEP), tris(1-chloro-2-propyl) phosphate (TCPP), tris(2-chloroethyl) phosphate (TCEP), dimethyl methanephosphonate (DMMP), dimethylpropanephosphonate (DMPP), ammonium polyphosphate or red phosphorus, chlorinated paraffins, nitrogen-containing compounds such as, for example, melamine, melamine cyanurate or melamine polyphosphate or halogenated compounds, such as, for example, chlorinated and / or brominated polyether and / or polyester polyols. Mixtures of different flame retardants can also be used.

[0048] Unless otherwise stated in this description, any preferred or particularly preferred embodiment of the invention can be combined with one or more of the other preferred or particularly preferred embodiments of the invention. The process according to the invention for producing PU foams can be carried out by all known methods, e.g. by hand mixing or, preferably, with the aid of foaming machines. If the process is carried out using foaming machines, high-pressure or low-pressure machines can be used. The process according to the invention can be carried out both batchwise and continuously, and 1K, 1.5K or 2K systems as described in EP3717538 A1, US7776934 B2, EP1400547 B1 or EP2780384 B2, for example, can be used.

[0049] One-component PU can foam is well known to those skilled in the art. For the purposes of the present invention, the term "one-component PU can foam" encompasses polyurethane foams that are preferably characterized by the presence of a polyol-isocyanate prepolymer that can be propelled by propellant gases from a pressurized can and thus foamed.

[0050] Prepolymers particularly suitable for this purpose can be obtained, for example, by reacting polyols and isocyanate with suitable catalysts (e.g., blowing catalysts such as 2,2'-dimorpholinyl diethyl ether) or without the use of a catalyst. The final curing of these prepolymers then occurs under the influence of moisture, for example, from the environment.

[0051] Spray foam is a free-flowing foam that is applied to a substrate by spraying or squirting the liquid reactants. It is typically applied using a spray foam machine, which can be a high- or low-pressure machine and combines and mixes the two components (polyol mixture and isocyanate). The foam is typically dispensed using a static mixer in the form of a spray gun. In principle, however, the raw materials or foam can also be dispensed from a larger container using gas pressure, similar to the principle of canned foam. The foam is used for insulation and for structural purposes on walls, roofs, and floors and can be open-cell or closed-cell, depending on the application.

[0052] Packaging foam is used for packaging, protecting, and cushioning delicate goods. It is typically a low-density, open-cell foam that tightly encloses the goods to be protected and protects them from damage, impact, etc. For this purpose, the foam may also be injected directly into the space between the packaging and the goods.

[0053] Thermoformable rigid polyurethane foams are rigid polyurethane foams that are mechanically shaped after production, for example, through the application of heat, water (steam), and pressure. This process creates a molded part from the initially block-shaped foam, which is then trimmed if necessary. Examples include roof liner foam (also called headliner foam) and hood liner foam (foam for trunk linings and trim). Floral foam, used for example for flower arrangements, is a polyurethane foam whose low density, mechanical properties, and high open-cell structure make it suitable for embedding flowers and other objects by inserting them into the foam.

[0054] Pipe insulation foam is a polyurethane foam used to insulate pipes. It protects the pipe and its contents from heat or cold loss, as well as from mechanical stress. Particularly in pipes laid in waterways, the ocean, and the deep sea, a high degree of open-cell density is sometimes desirable for mechanical reasons.

[0055] In principle, however, the cell openers described in this invention can also be used in all other PU foam, in particular PU rigid foam applications, in which a high degree of open cell density is desired, which, for example, has a direct positive effect on the dimensional stability of the foam.

[0056] The measurement of the open-cell or closed-cell content of a rigid polyurethane foam can preferably be carried out according to DIN ISO 4590:2016-12 “Determination of the volume fraction of open and closed cells in rigid foams”, e.g. using a gas pycnometer.

[0057] High open cell density within the meaning of this invention is considered to be an open cell density of more than 50% of the cells.

[0058] The measurement of the dimensional stability of a one-component PU can foam can preferably be carried out according to the method TM 1004:2013 of the FEICA - Association of the European Adhesive & Sealant Industry.

[0059] The preparation of the polyether-siloxane block copolymers according to the invention is based on the hydrosilylation reaction known to those skilled in the art and can be carried out by such a reaction of alpha-omega-modified hydrogen siloxanes with alpha-omega-modified di-(meth)allyl polyethers. The chemical reactions underlying this preparation are known and described in detail in the specialist literature (see, for example, Silicones - Chemistry and Technology, Vulkan-Verlag Essen, 1989).

[0060] The invention is described in more detail below by way of example, without the invention being restricted to these exemplary embodiments. If ranges, formulas or classes of compounds are given below, these are intended to include not only the corresponding ranges or groups of compounds that are explicitly mentioned, but also all sub-ranges and sub-groups of compounds that can be obtained by removing individual values ​​(ranges) or compounds. If documents are cited within the scope of the present description, their content, particularly with regard to the facts in connection with which the document was cited, is intended to be fully incorporated into the disclosure of the present invention. Unless otherwise stated, percentages are in percent by weight. Molar percentages are indicated in abbreviated form as m-%.If parameters determined by measurement are given below, the measurements were carried out at a temperature of 25 °C and a pressure of 101325 Pa (standard pressure), unless stated otherwise. If chemical (molecular) formulas are used in the present invention, the indicated indices can represent both absolute numbers and average values. In the case of polymeric compounds, the indices preferably represent average values. The structure and molecular formulas presented in the present invention are representative of all isomers conceivable by different arrangements of the repeating units. If compounds such as, for example,Polyethers, siloxanes or polyethersiloxanes, which can have different units multiple times, these can occur in these compounds in a statistically distributed manner (statistical oligomer or polymer), ordered (block oligomer or block polymer) or as a gradient distribution.

[0061] The solvent mixture according to the invention, which is used in the process according to the invention, comprises, in addition to aromatic solvent of formula 5, alkoxylated alcohol of formula 6. It corresponds to a preferred embodiment of the present invention if the aromatic solvent of formula 5 and the alkoxylated alcohol of formula 6 are used in a mass ratio of 1 to 2 to 15 to 1, preferably in a mass ratio of 3 to 2 to 12 to 1.

[0062] Alpha-omega modified hydrogen siloxanes and alpha-omega modified di-(meth)allyl polyethers are used as reactants in the presence of a hydrosilylation catalyst.

[0063] If the sum of the masses of aromatic solvent of formula 5 and the alkoxylated alcohol of formula 6 to the sum of the masses of the reactants is in a ratio of 7 to 3 to 1 to 4, then a further preferred embodiment of the invention is present.

[0064] The alpha-omega modified di-(meth)allyl polyether is preferably used in a concentration such that the molar ratio of polyether-bonded double bonds to Si-H groups is in the range from 0.95:1.05 to 1.05:0.95, preferably in the range from 0.97:1.03 to 1.03:0.97, particularly preferably in the range from 0.99:1.01 to 1.01:0.99. This also corresponds to a preferred embodiment of the invention.

[0065] The hydrosilylation according to the invention takes place in the presence of a hydrosilylation catalyst. A further preferred embodiment of the invention is achieved when the hydrosilylation catalyst used for the reaction is selected from the group of platinum catalysts, in particular platinum(0) catalysts, with platinum(0) catalysts in the form of the Karstedt catalyst being particularly preferred.

[0066] Such catalysts are known, see e.g. Lewis et al., “Platinum Catalysts used in Silicones Industry”, Platinum Metal Review, 1997, 44(23), 66-74).

[0067] The polyether siloxanes produced by the process according to the invention preferably have a weight-average molecular weight Mw of at least 60,000 g / mol, preferably of at least 80,000 g / mol, particularly preferably of at least 90,000 g / mol, and a number-average molecular weight Mn of at least 25,000 g / mol, preferably of at least 27,500 g / mol, particularly preferably of at least 30,000 g / mol. Furthermore, it is preferred if the ratio of Mw / Mn is less than 4.5, preferably less than 4.0, more preferably less than 3.5. The terms weight-average molecular weight Mw and number-average molecular weight Mn are known to the person skilled in the art. These two quantities can preferably be determined by gel permeation chromatography (GPC), preferably calibrated against polystyrene. For this purpose, the GPC system SECcurity2 from PCC, calibrated against polystyrene, can be used.In particular, the GPC system SECcurity 1260 from PCC can be used, preferably with the following experimental parameters: column combination SDV 1000 / 10000 Ä, detector PSS SECurity 1260 RI, mobile phase THF, flow rate 1 ml / min), calibrated against polystyrene (162 - 2520000 g / mol).

[0068] The mixtures obtained from the process according to the invention can be used according to the invention for the production of polyurethane foams, in particular rigid polyurethane foams.

[0069] A further subject of the present invention is thus a formulation suitable as an additive for the production of polyurethane foams, preferably rigid polyurethane foam, comprising the components

[0070] (a) Polyether-siloxane block copolymers according to formula 1

[0071] Formula 1, where a = 0 to 100, preferably 5 to 75, particularly preferably 10 to 50, b = 0 to 100, preferably 5 to 75, particularly preferably 5 to 25, c = 0 to 100, preferably 5 to 75, particularly preferably 5 to 25, d = 1 to 100, preferably 5 to 50, particularly preferably 7 to 40, very particularly preferably 12 - 30, n = 5 - 200, preferably 10 - 100, particularly preferably 15 - 50 and where the radicals R 1 independently of one another are identical or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably having 1 to 10 carbon atoms, very particularly preferably methyl radicals, and wherein the radicals R 2 are independently identical or different monovalent aliphatic saturated or unsaturated hydrocarbon radicals having 1 to 20 carbon atoms or H, with particular preference being given to methyl radicals, and wherein the radicals R 3independently of one another are identical or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably methyl radicals, and wherein the radicals R 4 are independently selected from one of the radicals R 5 , R e , R 7 or H, where the radicals R 5 correspond to formula 2 and where the radicals R e correspond to Formula 3 and where the radicals R 7 correspond to formula 4 where the indices a, b and c, as well as the residues R 2 and R 3 as previously defined,

[0072] (b) at least one aromatic solvent of general formula 5, where x = 0 - 20, preferably 0 - 16 y = 0 - 20, preferably 0 - 16 x + y = 6 - 20, preferably 8 - 16, and

[0073] (c) at least one alkoxylated alcohol of formula 6 Formula 6, where j = 0 to 30, preferably 0 to 10, particularly preferably 0 to 5, k = 1 to 20, preferably 2 to 10, particularly preferably 3 to 5, l = 1 to 20, preferably 2 to 10, particularly preferably 3 to 5 and where the radical R 9 a monovalent aliphatic saturated or unsaturated, linear or branched hydrocarbon radical having 6 - 40, preferably 8 - 30, more preferably 10 - 22 carbon atoms and wherein the radicals R 8 independently of one another, are identical or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably methyl radicals. According to a preferred embodiment of the invention, components (b) and (c) are present in the formulation in a mass ratio of 1:2 to 15:1, preferably in a mass ratio of 3:2 to 12:1.

[0074] Furthermore, formulations are preferred in which the sum of the masses of (b) and (c) to (a) is in a ratio of 8 to 2 to 1 to 4. This corresponds to a preferred embodiment of the invention.

[0075] Furthermore, formulations are preferred in which the polyether-siloxane block copolymer of formula 1 is present in a concentration of at least 20% by weight, preferably of at least 25% by weight, more preferably of at least 30% by weight, based on the total formulation.

[0076] In a particularly preferred embodiment of the invention, the inventive

[0077] Formulation no polyether of formula 8 where g = 0 to 75, preferably 0 to 50, particularly preferably 0 to 25, h = 1 to 100, preferably 2 to 50, particularly preferably 3 to 25, i = 1 to 100, preferably 2 to 50, particularly preferably 3 to 25 and where the radicals R 8are independently identical or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably methyl radicals.

[0078] The present invention enables, as already stated, the provision of polyether-siloxane block copolymers which have high molecular weights with a narrow molecular weight distribution.

[0079] A formulation according to the invention with polyether-siloxane block copolymers according to formula 1 with an M w (g / mol) of > 60000, preferably > 80000, in particular > 90000, where M w / M n < 4.5, preferably <4.0, in particular <3.5, corresponds to a particularly preferred embodiment of the invention. As already described above, M w and M n In the context of this invention, preferably by gel permeation chromatography (GPC), preferably calibrated against polystyrene.

[0080] Furthermore, it may be preferred if the formulation according to the invention also comprises a pendant stabilizer as an additional component. Pendant stabilizers here are also polyethersiloxanes, but they have a silicone chain that carries pendant and / or terminal polyether chains. The polyether chains can be bonded to the silicone chain either via a silicon-carbon linkage (Si-C) or a silicon-oxygen-carbon linkage (Si-OC), with silicon-carbon linkages being particularly preferred. In particular, those pendant Si-C-based polyethersiloxanes are preferred which correspond to formula 7, where x = 0 to 50, preferably 1 to 25, particularly preferably 2 to 15, y = 0 to 250, preferably 5 to 150, particularly preferably 5 to 100, where the radicals R 9independently of one another are identical or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably having 1 to 10 carbon atoms, very particularly preferably methyl radicals, and wherein the radicals R 10 independently of one another are identical or different OH-functional or terminated, preferably methyl- or acetyl-terminated polyoxyalkylene radicals, preferably polyoxyethylenepolyoxypropylene radicals, and wherein the radicals R 11 either R 9 or R 10 are equivalent to.

[0081] Since, as described above, the polyether-siloxane block copolymers according to the invention are efficient cell openers for the production of polyurethane foams, in particular open-cell rigid polyurethane foams, the use of the formulations according to the invention as additives, in particular as cell-opening additives or cell openers, in the production of polyurethane foams, preferably rigid polyurethane foams and in particular one-component PU can foams is also a subject of the present invention, in particular in combination with a pendant stabilizer according to formula 7.

[0082] A further subject matter of this invention is therefore also a polyurethane foam, preferably rigid polyurethane foam, produced using a formulation according to the invention as described above.

[0083] The use of a polyurethane foam according to the invention, preferably rigid polyurethane foam, as described above, for producing foam moldings, spray foam, insulating foam, sealants, adhesives, insulating compounds, assembly compounds and / or fillers is a further subject of the invention. As already described above, the polyether siloxanes obtainable by the process according to the invention are characterized by a particularly advantageous molecular weight and a particularly advantageous molecular weight distribution, making them particularly suitable for use as an additive for the production of polyurethane foams, preferably rigid polyurethane foams. The present invention therefore further relates to polyether siloxane block copolymers which correspond to formula 1

[0084] Formula 1, where a = 0 to 100, preferably 5 to 75, particularly preferably 10 to 50, b = 0 to 100, preferably 5 to 75, particularly preferably 5 to 25, c = 0 to 100, preferably 5 to 75, particularly preferably 5 to 25, a + b + c > 3, d = 1 to 100, preferably 5 to 50, particularly preferably 7 to 40, very particularly preferably 12 - 30, n = 5 - 200, preferably 10 - 100, particularly preferably 15 - 50 and where the radicals R 1 independently of one another are identical or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably having 1 to 10 carbon atoms, very particularly preferably methyl radicals, and wherein the radicals R 2 are independently identical or different monovalent aliphatic saturated or unsaturated hydrocarbon radicals having 1 to 20 carbon atoms or H, with particular preference being given to methyl radicals, and wherein the radicals R 3independently of one another are identical or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably methyl radicals, and wherein the radicals R 4 are independently selected from one of the radicals R 5 , R e , R 7 or H, where the radicals R 5 correspond to formula 2 and where the radicals R e correspond to Formula 3 and where the radicals R 7 correspond to formula 4 where the indices a, b and c, as well as the residues R 2 and R 3as defined above, and which have a weight-average molecular weight Mw of at least 60,000 g / mol, preferably of at least 80,000 g / mol, particularly preferably of at least 90,000 g / mol, and a number-average molecular weight Mn of at least 25,000 g / mol, preferably of at least 27,500 g / mol, particularly preferably of at least 30,000 g / mol, with particular preference for the ratio Mw / Mn being less than 4.5, preferably less than 4.0, more preferably less than 3.5. These polyether-siloxane block copolymers can preferably be prepared by the process according to the invention, as described in detail above.

[0085] In particular, it is preferred if these polyether-siloxane block copolymers are prepared without the use of polyethers of formula 8, Formula 8, where g = 0 to 75, preferably 0 to 50, particularly preferably 0 to 25, h = 1 to 100, preferably 2 to 50, particularly preferably 3 to 25, i = 1 to 100, preferably 2 to 50, particularly preferably 3 to 25 and where the radicals R 8 are independently identical or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably methyl radicals.

[0086] Another subject of the present invention is the use of these polyether-siloxane block copolymers according to the invention as additives for the production of polyurethane foams, preferably rigid polyurethane foams, in particular in combination with at least one additional polyethersiloxane-based stabilizer which has a siloxane chain carrying pendant and / or terminal polyether chains, wherein the polyether chains can be bonded to the silicone chain either via a silicon-carbon linkage (Si-C) or a silicon-oxygen-carbon linkage (Si-OC), wherein silicon-carbon linkages are particularly preferred and wherein in particular those pendant Si-C-based polyethersiloxanes are preferred which correspond to formula 7, as already defined above, wherein in this context reference is made in full to the preceding description.

[0087] Examples

[0088] The following examples serve solely to illustrate this invention to the person skilled in the art and do not represent any limitation of the claimed subject matter.

[0089] Materials: a) SiH-Siloxane A

[0090] In the following syntheses, a siloxane of the general formula a was used.

[0091] Formula a: SiH siloxane A. b) Bismethallyl polyether A

[0092] In the following syntheses, a bismethallyl polyether of general formula b was used.

[0093] Formula bi bismethallyl polyether A

[0094] Synthesis examples

[0095] Example 1: Synthesis in toluene (comparative example)

[0096] 73 g of bisallyl polyether A were placed in a 500 mL three-necked flask equipped with a precision glass stirrer and reflux condenser. 103 g of toluene and 30 g of SiH siloxane A were then added. The reaction mixture was heated to 80 °C. 10 ppm of Pt in the form of the Karstedt catalyst solution were then added. The reaction mixture was heated to 95 °C and stirred at this temperature for 3 hours. A gel-like product formed, which was diluted intermittently with another 103 g of toluene to maintain stirrability. A clear gel-like product was obtained. Due to the very high viscosity, the solvent could not be removed by distillation. Example 2: Synthesis in Toluene / Alkoxylated Alcohol (Comparative Example)

[0097] 73 g of bisallyl polyether A were placed in a 1000 mL three-neck flask equipped with a precision glass stirrer and reflux condenser. Then, 103 g of toluene, 103 g of Varonic® APM T (myristyl alcohol propoxylate), and 30 g of SiH siloxane A were added. The reaction mixture was heated to 80 °C. Subsequently, 10 ppm of Pt in the form of Karstedt catalyst solution were added. The reaction mixture was heated to 95 °C and stirred at this temperature for 3 hours. The volatiles were then removed under vacuum at 130 °C and 1 mbar. A cloudy product was obtained.

[0098] Example 3: Synthesis in dodecylbenzene / alkoxylated alcohol

[0099] 73 g of bisallyl polyether A were placed in a 1000 mL three-neck flask equipped with a precision glass stirrer and reflux condenser. Then, 103 g of dodecylbenzene (CAS number: 123-01-3), 103 g of Varonic® APM T (myristyl alcohol propoxylate), and 30 g of SiH siloxane A were added. The reaction mixture was heated to 80 °C. Then, 10 ppm of Pt in the form of the Karstedt catalyst solution were added. The reaction mixture was heated to 95 °C and stirred at this temperature for 3 hours. The volatile components were then removed under vacuum at 130 °C and 1 mbar. A highly viscous, clear product was obtained.

[0100] Table 1 : Experimental overview

[0101] A comparison of examples 2 and 3 shows that the use of dodecylbenzene in combination with an alkoxylated alcohol enables the production of clear products. Furthermore, dodecylbenzene is not a highly flammable solvent. Due to these two factors, this product is more suitable as a foam stabilizer.

Claims

Patent claims 1. Process for the preparation of polyether-siloxane block copolymers according to formula 1 Formula 1, where a = 0 to 100, preferably 5 to 75, particularly preferably 10 to 50, b = 0 to 100, preferably 5 to 75, particularly preferably 5 to 25, c = 0 to 100, preferably 5 to 75, particularly preferably 5 to 25, a + b + c > 3, d = 1 to 100, preferably 5 to 50, particularly preferably 7 to 40, most preferably 12 to 30, n = 5 to 200, preferably 10 to 100, particularly preferably 15 to 50 and wherein the residues R 1 The monovalent or different monovalent aliphatic or aromatic hydrocarbon residues with 1 to 20 carbon atoms, preferably with 1 to 10 carbon atoms, most preferably methyl residues, are independent of one another, and wherein the residues R 2are independently identical or different monovalent aliphatic saturated or unsaturated hydrocarbon residues with 1 to 20 carbon atoms or H, wherein methyl residues are particularly preferred, and wherein the residues R 3 independently of one another are identical or different monovalent aliphatic or aromatic hydrocarbon residues with 1 to 20 carbon atoms, preferably methyl residues, and wherein the residues R 4 are independently selected from one of the remainders R 5 , R e , R 7 or H, where the remainders are R 5 correspond to formula 2 Formula 2, and wherein the remainders R e correspond to formula 3 and wherein the remainders R 7 correspond to formula 4 where the indices a, b and c, as well as the remainders R 2 and R 3as previously defined, by hydrosilylation of alpha-omega modified hydrogen siloxanes with alpha-omega modified di-(meth)allyl polyethers in the presence of a hydrosilylation catalyst which is capable of catalyzing the formation of a SiC bond by the addition of a Si-H group to a (meth)allylic double bond, characterized in that the reaction is carried out in a solvent mixture comprising at least one aromatic solvent of general formula 5, where x = 0 - 20, preferably 0 - 16, y = 0 - 20, preferably 0 - 16, x + y = 6 - 20, preferably 8 - 16, and at least one alkoxylated alcohol of formula 6 where j = 0 to 30, preferably 0 to 10, particularly preferably 0, k = 0 to 20, preferably 0 to 10, particularly preferably 0 to 5, I = 1 to 20, preferably 2 to 10, particularly preferably 3 to 5 and where the remainder R 9a monovalent aliphatic saturated or unsaturated, linear or branched hydrocarbon residue with 6-40, preferably with 8-30, particularly preferably with 10-22 carbon atoms, and wherein the residues R 8The process consists of identical or different monovalent aliphatic or aromatic hydrocarbon residues with 1 to 20 carbon atoms, preferably methyl groups. The process according to claim 1 is characterized in that the aromatic solvent of formula 5 and the alkoxylated alcohol of formula 6 are used in a mass ratio of 1:2 to 15:1, preferably in a mass ratio of 3:2 to 12:

1. The process according to any one of claims 1 to 2 is characterized in that the sum of the masses of the aromatic solvent of formula 5 and the alkoxylated alcohol of formula 6 to the sum of the masses of the reactants is in a ratio of 8:2 to 1:4.A process according to any one of claims 1 to 3, characterized in that the alpha-omega modified di-(meth)allyl polyether is used in such a concentration 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, preferably in the range of 0.97 : 1.03 to 1.03 : 0.97, and particularly preferably in the range of 0.99 : 1.01 to 1.01 : 0.

99. A process according to any one of claims 1 to 4, characterized in that the hydrosilylation catalyst used for the reaction is selected from the group of platinum catalysts, in particular platinum(0) catalysts, wherein platinum(0) catalysts in the form of the Karstedt catalyst are particularly preferred. Formulation suitable as an additive for the production of polyurethane foams, preferably rigid polyurethane foams, comprising the components. (a) Polyether-siloxane block copolymers according to formula 1 Formula 1, where a = 0 to 100, preferably 5 to 75, particularly preferably 10 to 50, b = 0 to 100, preferably 5 to 75, particularly preferably 5 to 25, c = 0 to 100, preferably 5 to 75, particularly preferably 5 to 25, d = 1 to 100, preferably 5 to 50, particularly preferably 7 to 40, most preferably 12 - 30, n = 5 - 200, preferably 10 - 100, particularly preferably 15 - 50 and wherein the residues R 1 The monovalent or different monovalent aliphatic or aromatic hydrocarbon residues with 1 to 20 carbon atoms, preferably with 1 to 10 carbon atoms, most preferably methyl residues, are independent of one another, and wherein the residues R 2 are independently identical or different monovalent aliphatic saturated or unsaturated hydrocarbon residues with 1 to 20 carbon atoms or H, wherein methyl residues are particularly preferred, and wherein the residues R 3independently of one another are identical or different monovalent aliphatic or aromatic hydrocarbon residues with 1 to 20 carbon atoms, preferably methyl residues, and wherein the residues R 4 are independently selected from one of the remainders R 5 , R e , R 7 or H, where the remainders are R 5 correspond to formula 2 and wherein the remainders R e correspond to formula 3 where the indices a, b and c, as well as the remainders R 2 and R 3 as defined previously, (b) Aromatic solvent of formula 5 where x = 0 - 20, preferably 0 - 16; y = 0 - 20, preferably 0 - 16; x + y = 6 - 20, preferably 8 - 16; and (c) alkoxylated alcohol of formula 6 where j = 0 to 30, preferably 0 to 10, particularly preferably 0 to 5, k = 1 to 20, preferably 2 to 10, particularly preferably 3 to 5, I = 1 to 20, preferably 2 to 10, particularly preferably 3 to 5 and wherein the remainder is R 9 a monovalent aliphatic saturated or unsaturated, linear or branched hydrocarbon residue with 6-40, preferably with 8-30, more preferably with 10-22 carbon atoms, and wherein the residues R 8 The formulation consists of identical or different monovalent aliphatic or aromatic hydrocarbon residues with 1 to 20 carbon atoms, preferably methyl groups. A formulation according to claim 6, characterized in that the sum of the masses of (b) and (c) to (a) is in a ratio of 8:2 to 1:

4. A formulation according to claim 6 or 7, characterized in that the polyether-siloxane block copolymer according to formula 1 comprises an M w (g / mol) of > 60000, advantageously > 80000, preferably > 90000, in particular > 100000, wherein M w / M n< 4.5, preferably < 4.0, in particular < 3.

5. Formulation according to any one of claims 6 to 8, characterized in that at least one lateral polyethersiloxane-based stabilizer is used as an additional component, which has a siloxane chain carrying lateral and / or terminal polyether chains, wherein the polyether chains can be bonded to the silicon chain via either a silicon-carbon linkage (Si-C) or a silicon-oxygen-carbon linkage (Si-OC), wherein silicon-carbon linkages are particularly preferred, and wherein lateral Si-C-based polyethersiloxanes corresponding to formula 7 are particularly preferred. where x = 0 to 50, preferably 1 to 25, particularly preferably 2 to 15, y = 0 to 250, preferably 5 to 150, particularly preferably 5 to 100, wherein the remainders R 9The monovalent or different monovalent aliphatic or aromatic hydrocarbon residues with 1 to 20 carbon atoms, preferably with 1 to 10 carbon atoms, most preferably methyl residues, are independent of one another, and wherein the residues R 10 are independently identical or different OH-functional or terminated, preferably methyl- or acetyl-terminated polyoxyalkylene residues, preferably polyoxyethylene-polyoxypropylene residues, and wherein the residues R 11 either R 9 or R 10 correspond to a polyether-siloxane block copolymer, preferably produced according to a process according to any one of claims 1-5, which corresponds to formula 1. Formula 1, where a = 0 to 100, preferably 5 to 75, particularly preferably 10 to 50, b = 0 to 100, preferably 5 to 75, particularly preferably 5 to 25, c = 0 to 100, preferably 5 to 75, particularly preferably 5 to 25, a + b + c > 3, d = 1 to 100, preferably 5 to 50, particularly preferably 7 to 30, most preferably 8 - 20, n = 5 - 200, preferably 10 - 100, particularly preferably 15 - 50 and wherein the residues R 1 The monovalent or different monovalent aliphatic or aromatic hydrocarbon residues with 1 to 20 carbon atoms, preferably with 1 to 10 carbon atoms, most preferably methyl residues, are independent of one another, and wherein the residues R 2 are independently identical or different monovalent aliphatic saturated or unsaturated hydrocarbon residues with 1 to 20 carbon atoms or H, wherein methyl residues are particularly preferred, and where the remainders R 3independently of one another are identical or different monovalent aliphatic or aromatic hydrocarbon residues with 1 to 20 carbon atoms, preferably methyl residues, and wherein the residues R 4 are independently selected from one of the remainders R 5 , R e , R 7 or H, where the remainders are R 5 correspond to formula 2 and wherein the remainders R e correspond to formula 3 and wherein the remainders R 7 correspond to formula 4 where the indices a, b and c, as well as the remainders R 2 and R 3as previously defined, and which has a weight-average molecular weight Mw of at least 60,000 g / mol, preferably at least 80,000 g / mol, particularly preferably at least 90,000 g / mol, and a number-average molecular weight Mn of at least 25,000 g / mol, preferably at least 27,500 g / mol, particularly preferably at least 30,000 g / mol, wherein it is particularly preferred if the ratio of Mw / Mn is less than 4.5, preferably less than 4.0, more preferably less than 3.

5. Use of formulations according to one of claims 6 to 9 and / or one Polyether-siloxane block copolymers according to claim 10 as an additive for the production of Polyurethane foams, preferably rigid polyurethane foams, particularly in combination with at least one additional polyethersiloxane-based stabilizer, which has a siloxane chain carrying lateral and / or terminal polyether chains, wherein the polyether chains can be bonded to the silicone chain via either a silicon-carbon linkage (Si-C) or a silicon-oxygen-carbon linkage (Si-OC), wherein silicon-carbon linkages are particularly preferred, and wherein lateral Si-C-based polyethersiloxanes corresponding to formula 7 are particularly preferred. where x = 0 to 50, preferably 1 to 25, particularly preferably 2 to 15, y = 0 to 250, preferably 5 to 150, particularly preferably 5 to 100, wherein the remainders R 9The monovalent or different monovalent aliphatic or aromatic hydrocarbon residues with 1 to 20 carbon atoms, preferably with 1 to 10 carbon atoms, most preferably methyl residues, are independent of one another, and wherein the residues R 10 are independently identical or different OH-functional or terminated, preferably methyl- or acetyl-terminated polyoxyalkylene residues, preferably polyoxyethylene-polyoxypropylene residues, and wherein the residues R 11 either R 9 or R 10 are equivalent to. Use of formulations according to any one of claims 6 to 9 and / or a polyether siloxane block copolymer according to claim 10 as a cell opener in the production of PU foam, preferably rigid PU foam. Use according to claim 12, wherein the polyurethane rigid foam to be produced is a one-component PU canned foam. Polyurethane foam, preferably rigid polyurethane foam, produced using a formulation according to one of claims 6 to 9 and / or a polyether siloxane block copolymer according to claim 10, in particular according to the specifications of at least one of claims 11 to 13. Use of a polyurethane foam, preferably rigid polyurethane foam, according to claim 14 for the production of foam molded bodies, spray foam, insulating foam, sealants, adhesives, insulating compounds, assembly compounds, and / or filling compounds.

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