Polyether-siloxane block copolymers for producing polyurethane foams

Abstract

The present invention describes a process for preparing polyether-siloxane block copolymers by hydrosilylation of an alpha, omega-modified hydrogenated siloxane with an alpha, omega-modified di (meth) allyl polyether in the presence of a hydrosilylation catalyst, in which the reaction is carried out in a solvent mixture comprising an aromatic solvent and an alkoxylated alcohol.

Description

[0001] The invention belongs to the field of polyether siloxanes, polyurethanes and polyurethane foams.

[0002] The present invention more particularly relates to the production of specific polyether-siloxane block copolymers and to specific formulations and to their use for the production of polyurethane foams, preferably rigid polyurethane foams, more preferably one-component canned PU foams (construction foams, assembly foams, one-component foams / OCF) and other rigid polyurethane foams in which a high cell content is advantageous (e.g. open-cell spray foams, packaging foams, headliner foams, pipe insulation foams, floral foams, thermoformable rigid foams).

[0003] One-component canned PU foam is known per se. It is a polyurethane foam foamed by pressurized propellant gas from a pressurized tank. Fields of use are the assembly, bonding and sealing of windows, door frames, pipes, bushings, etc., and the filling of gaps in brickwork, cavities, cracks and joints. This foam is preferably produced by providing a prepolymer formed from a polyol and an isocyanate (preferably methylene diphenyl isocyanate, MDI) in a pressurized tank, which is pushed out by the propellant gas (propellant) and cured by ambient moisture. The polyol-isocyanate prepolymer has reactive isocyanate groups and urethane bonds.

[0004] For all of the above-mentioned applications, it is important that the finished one-component PU foam shows little change in its geometric dimensions during and especially after the curing process. This dimensional stability is achieved by the high open-cell content of the foam, i.e. low shrinkage or low post-expansion. At the same time, due to this open-cell content, the foam must not have any significant foam defects in the form of cavities; for this purpose, the cells of the foam should remain fine and not have any coarsening. For this purpose, cell openers are usually added to the polyol-isocyanate prepolymers together with the usually present foam stabilizers (usually polyether siloxanes), and polyether-siloxane block copolymers in particular have been found to be particularly effective for this application. Usually, these cell openers are in the form of alternating linear [AB] chains of polyether chains and siloxane chains. n The block structure is characteristic. For good cell opening effect, high molecular weight is important; at the same time, the reproducible production of such molecular weight is a challenge.

[0005] Non-hydrolyzable [AB] n Polyether siloxanes are known to those skilled in the art. For example, US 3957842 describes such polymers. The patent describes the preparation of these structures by hydrosilylation of diallyl polyethers with α,ω-SiH-functional siloxanes in toluene. The molecular weight of the resulting polymer is about 36 000-56 000 g / mol.

[0006] US 4150048 describes non-hydrolyzable [AB]n Polyether siloxanes prepared by hydrosilylation of polyethers having two CH2=C(R)CH2 terminal groups per molecule, wherein R is a monovalent hydrocarbon group. They are prepared from α,ω-SiH-functional siloxanes under hydrosilylation reaction conditions in the presence of a platinum catalyst. The linear block copolymers prepared 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 produce non-reactive species during the hydrosilylation reaction results in unexpectedly high molecular weights of the copolymers.

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

[0008] US20190233646 describes a method comprising [AB] n The invention discloses a composition of polyether siloxane, which comprises a polyether-polysiloxane block copolymer and a liquid organic monool compound, wherein the liquid organic monool compound is a glycol ether compound having a certain degree of polymerization and terminal hydrogen, or an alcohol compound having a branched alkyl group with 12 or more carbon atoms.

[0009] As already described, high molar mass is important and therefore particularly desirable for providing a high open cell content. Too low a molar mass of the cell opener will lead to a reduced cell opening effect, as a result of which the foam will further shrink or expand. However, in addition to the maximum molecular weight of the cell opener, it is also important that the molar mass distribution is as narrow as possible. In particular, the tailing of the molar mass distribution towards very high molar masses can have an adverse effect. This tailing can make the viscosity of the cell opener very high, which greatly impairs its processability during foam production.

[0010] The problem addressed by the present invention is therefore to provide polyether-siloxane block copolymers which are distinguished by a particularly high molecular weight with a very narrow molar mass distribution and, in connection therewith, have a particularly effective efficacy as cell openers.

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

[0012] The present invention therefore 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 40, most preferably 12 to 30,

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

[0021] Where R 1 The radicals are each independently identical or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, particularly preferably methyl, and

[0022] Where R 2 The radicals are independently identical or different monovalent aliphatic, saturated or unsaturated hydrocarbon radicals having 1 to 20 carbon atoms or OH, particularly preferably methyl, and

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

[0024] Where R 4 The groups are independently selected from R 5 , R 6 , R 7 group and H, where R 5 Group conformity

[0025] Formula 2

[0026]

[0027] And where R 6 The group conforms to formula 3

[0028]

[0029] And where R 7 The group conforms to formula 4

[0030]

[0031] where the subscripts a, b, and c and R 2 and R 3The groups are as defined above, the method being carried out by hydrosilylation of an α,ω-modified hydrosiloxane 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 addition of Si—H groups to (meth)allyl double bonds,

[0032] The reaction is carried out in a solvent mixture, wherein the solvent mixture comprises at least one aromatic solvent of formula 5

[0033]

[0034] in

[0035] x=0-20, preferably 0-16,

[0036] y = 0-20, preferably 0-16,

[0037] x+y=6-20, preferably 8-16,

[0038] and at least one alkoxylated alcohol of formula 6

[0039]

[0040] in

[0041] j=0 to 30, preferably 0 to 10, more preferably 0,

[0042] k=0 to 20, preferably 0 to 10, more preferably 0 to 5,

[0043] l=1 to 20, preferably 2 to 10, more preferably 3 to 5, and

[0044] Where R 9 The radical is a monovalent aliphatic saturated or unsaturated, straight-chain or branched hydrocarbon radical having 6 to 40, preferably 8 to 30, even more preferably 10 to 22 carbon atoms, and

[0045] Where R 8 The radicals are independently the same or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably methyl.

[0046] The sequence of the different oxyalkylene units specified between square brackets and with lowercase subscripts in the polyoxyalkylene group, polyol or alkoxylated alcohol may be random (statistically distributed), blockwise, gradually changing, or any mixture of these options in the segment. The structural formula specified here is only a simplified graphical representation related to the sequence.

[0047] The solvent mixture according to the invention therefore comprises at least two components: an aromatic solvent of the formula 5 and an alkoxylated alcohol of the formula 6; it preferably consists of these two components.

[0048] In a very particularly preferred embodiment of the present invention, the solvent mixture according to the invention does not contain any polyethers of the formula 8:

[0049]

[0050] in

[0051] g=0 to 75, preferably 0 to 50, more preferably 0 to 25,

[0052] h=1 to 100, preferably 2 to 50, more preferably 3 to 25,

[0053] i=1 to 100, preferably 2 to 50, more preferably 3 to 25, and

[0054] Where R 8 The radicals are independently the same or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably methyl.

[0055] Such a solvent mixture according to the invention which comprises at least an aromatic solvent of the formula 5 and an alkoxylated alcohol of the formula 6, but no polyether of the formula 8, is therefore a very particularly preferred embodiment of the invention.

[0056] The advantage of the process according to the invention is not only that it enables corresponding polyether-siloxane block copolymers to be provided with high molecular weight and simultaneously very narrow molar mass distribution, but also that the resulting formulations with relatively high active ingredient contents have relatively low viscosities and thus considerable processing advantages.

[0057] A further advantage is that the resulting polyether-siloxane block copolymers with high molecular weight have a narrow molar mass distribution. Thus, in particular, it is possible to ensure that the weight-average molecular weight 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 <4.5, preferably <4.0, especially <3.5. n is the number average molar mass.

[0058] For the use according to the invention of the polyether-siloxane block copolymers described as cell openers for the production of polyurethane foams, preferably rigid polyurethane foams (especially one-component canned PU foams, open-cell spray foams, packaging foams, headliner foams, pipe insulation foams, floral foams, thermoformable rigid foams, etc.), high molar masses are particularly advantageous in this context, since these can be used in particular for the production of open-cell foams. In addition to the open-cell content, a regular foam and cell structure and a low foam defect rate are achieved. From this point of view, low viscosities and narrow molar mass distributions are also valuable.

[0059] Polyether-siloxane block copolymers are known per se. In the context of the entire present invention, the term "polyether" encompasses polyoxyalkylenes, particularly preferably polyoxyethylene and polyoxypropylene and also polyoxyethylene-polyoxypropylene copolyethers. The distribution of the various oxyalkylene units along the polymer backbone may be different. Mixed polyethers may be constructed, for example, statistically, in blocks or in different gradients of monomer units relative to one another. Statistical construction in this context means that the polyoxyethylene and polyoxypropylene units are distributed in a random order in the polyether chain, while block-structured polyethers consist of defined polyoxyethylene and polyoxypropylene blocks.

[0060] Throughout the context of the present invention, the term siloxane comprises compounds from the class of polyorganosiloxanes, polydimethylsiloxanes being particularly preferred. Throughout the context of the present invention, the term polyether-siloxane block copolymer comprises polymers composed of alternating polyether and siloxane blocks.

[0061] The polyether-siloxane block copolymer of the present invention conforms to Formula 1.

[0062] The term polyurethane foam itself 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).

[0063] Preferred compositions according to the invention of PU foams, preferably rigid polyurethane foams, contain the following ingredients:

[0064] a) The polyether-siloxane block copolymer of the present invention as a cell opener

[0065] b) Polyol component

[0066] c) (Poly)isocyanate component

[0067] d) Catalyst

[0068] e) Optional foam stabilizer

[0069] f) Foaming agent

[0070] g) other additives which may be present, preferably fillers, liquid flame retardants, etc.

[0071] The terms "polyurethane" and "polyurethane foam" are established technical terms that have long been known to those skilled in the art.

[0072] Polyurethane (PU) in the context of the present invention is understood to mean in particular the products obtainable by reaction of a polyisocyanate component with a polyol component.

[0073] In addition to polyurethanes, other functional groups may also be formed in the reaction, for example uretdione, carbodiimide, isocyanurate, allophanate, biuret, urea and / or uretonimines. For the purposes of the present invention, PU is therefore understood not only to mean polyurethanes, but also polyisocyanurates, polyureas and polyisocyanate reaction products containing uretdione, carbodiimide, allophanate, biuret and / or uretonimines groups.

[0074] Therefore, polyurethane foam (PU foam) in the context of the present invention is understood to mean the foam obtained as the reaction product of a polyisocyanate component and a polyol component. In addition to the polyurethane of the same name, other functional groups can also be formed here, examples being allophanates, biuret, urea, carbodiimide, uretdione, isocyanurate or uretonimine.

[0075] Rigid PU foam is an established technical term. The known basic difference between flexible foam and rigid foam is that flexible foam displays elastic properties and deformation is therefore reversible. In contrast, rigid foam deforms permanently. Further details on rigid polyurethane foam can also be found in "Kunststoffhandbuch, Band 7, Polyurethane [Plastics Handbook, volume 7, Polyurethanes]", Carl Hanser Verlag, 3rd Edition 1993, Chapter 6.

[0076] In the context of the present invention, particularly preferred PU foams are rigid polyurethane foams, one-component pot foams, open-cell spray foams, packaging foams, headliner foams, pipe insulation foams, floral foams, thermoformable rigid foams and / or other rigid polyurethane foams in which a high open-cell content is advantageous.

[0077] The polyol component (b) used may be one or more organic compounds containing OH groups, SH groups, NH groups and / or NH2 groups and having a functionality of 1.8 to 8. 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, especially OH groups.

[0078] A functionality of, for example, 1.8 may result from the mixing of at least one compound having a relatively high functionality (e.g. greater than or equal to 2) with at least one compound having, for example, a functionality of 1. This may occur in particular when a polyisocyanate component (c) having a functionality of greater than 2 or an additional crosslinker is used as an optionally present additive (h).

[0079] Suitable compounds which can usually be used in the production of PU foams are known to the person skilled in the art and are described, for example, in "Kunststoffhandbuch, Band 7, Polyurethane [Plastics Handbook, volume 7, Polyurethanes]", Carl Hanser Verlag, 3rd Edition 1993, Chapter 3.1. Compounds having an OH number in the range of 10 to 1200 mg KOH / g are usually used.

[0080] Particularly preferred compounds are all polyether polyols and polyester polyols which are usually used for producing polyurethane systems, in particular polyurethane foams.

[0081] Furthermore, polyether polycarbonate polyols, polyols based on natural oils (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), filled polyols, prepolymer based polyols and / or recycled polyols may be used.

[0082] Recycled polyols are polyols obtained by chemical recovery of polyurethanes, for example by solvolysis, such as glycolysis, hydrolysis, acidolysis or aminolysis. The use of recycled polyols constitutes a particularly preferred embodiment of the present invention.

[0083] When the polyol component comprises a polyol-isocyanate prepolymer, this is a preferred embodiment of the present invention.

[0084] The isocyanate or polyisocyanate component (c) used may generally be one or more polyisocyanates having two or more isocyanate groups. Suitable polyisocyanates for the purposes of the present invention are all organic isocyanates having two or more isocyanate groups, in particular the aliphatic, cycloaliphatic, arylaliphatic and preferably aromatic polyfunctional isocyanates known per se.

[0085] Examples which may be mentioned here are alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene group, for example dodecane-1,12-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, methylenedicyclohexyl 4,4'-diisocyanate and the corresponding isomer mixtures. -diisocyanates (H12MDI), isophorone diisocyanate (IPDI), methylcyclohexyl 2,4- and 2,6-diisocyanates and the corresponding isomer mixtures, and preferred aromatic diisocyanates and polyisocyanates such as toluene 2,4- and 2,6-diisocyanates (TDI) and the corresponding isomer mixtures, naphthalene diisocyanate, diethyltoluene diisocyanate, diphenylmethane 4,4'- or 2,2'- or 2,4'-diisocyanate (MDI) and polymethylene polyphenyl polyisocyanate (PMDI, "polymeric MDI"). Organic polyisocyanates can be used alone or in the form of mixtures thereof. It is likewise possible to use the corresponding "oligomers" of diisocyanates, such as IPDI trimers based on isocyanurates, biuret or uretdione. In addition, prepolymers based on the above-mentioned isocyanates can be used. Mixtures of MDI and more highly condensed analogs having an average functionality of 2 to 4, which are known as polymeric MDI (also known as "crude MDI"), as well as the various isomers or isomer mixtures of TDI in pure form, are particularly suitable. Isocyanates modified by incorporation of urethane, uretdione, isocyanurate, allophanate and other groups, known as modified isocyanates, may also be used. Examples of particularly suitable isocyanates are also detailed in, for example, EP 1712578, EP 1161474, WO 00 / 58383, US 2007 / 0072951, EP 1678232 and WO 2005 / 085310, which are incorporated herein by reference in their entirety.

[0086] The preferred ratio of the polyisocyanate component and the polyol component is expressed as an index of the formulation, i.e. the stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (e.g. OH groups, NH groups) multiplied by 100, in the range of 10 to 1000 and preferably 40 to 500. An index of 100 indicates a molar ratio of reactive groups of 1:1.

[0087] Suitable catalysts (d) which 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. In the context of the present invention, useful compounds are all compounds which are able to catalyze the reaction of isocyanate groups with OH groups, NH groups or other isocyanate-reactive groups and / or the reaction of isocyanate groups with one another.

[0088] Conventional 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, the catalyst used can be a mixture of two or more such compounds.

[0089] Foam stabilizers (e) and their use in the production of PU foams are known to those skilled in the art. The use of foam stabilizers is optional; preferably one or more foam stabilizers are used. Useable foam stabilizers are in particular surface-active compounds (surfactants). Foam stabilizers are preferably used. They can be used to optimize the desired cell structure and foaming process. In the context of the present invention, in particular Si-containing compounds that assist foam generation (stabilization, cell regulation, cell opening, etc.) can be used. These compounds are well known from the prior art. Particularly preferably, at least one foam stabilizer based on polyether siloxane is used. Corresponding siloxane structures that can be used in the context of the present invention are described, for example, in the following patent documents, although these documents only describe the use in conventional PU foams (e.g., as molded foams, mattresses, insulation materials, building foams, etc.): CN 103665385, CN 103657518, CN 103055759, CN 103044687, US 2008 / 0125503, US 2015 / 0057384, EP 1520870 A1, EP 1211279, EP 0867464, EP0867465, EP 0275563. In addition to surface-active silicon-containing compounds, Si-free surfactants can also be used. For example, EP 2295485 A1 describes the use of lecithin, and US 3746663 describes the use of vinylpyrrolidone-based structures as foam stabilizers for the production of rigid PU foams. 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.

[0090] Blowing agents and their use in the production of PU foams are known to the person skilled in the art. The use of blowing agents is optional; preferably, blowing agents are used. The use of a blowing agent (f) or a combination of two or more blowing agents (f) depends in principle on the nature of the foaming process used, the nature of the system and the use of the PU foam obtained. Chemical and / or physical blowing agents can be used, as well as combinations of these two. Depending on the amount of blowing agent used, foams with high or low density are produced. For example, a foam with a density of 5 kg / m 3 Up to 900kg / m 3 , preferably 5 to 350 kg / m 3 , particularly preferably 8 to 200 kg / m 3 , especially 8 to 150 kg / m 3 of bubbles.

[0091] Physical blowing agents that can be used are one or more compounds with a suitable boiling point and mixtures thereof, for example hydrocarbons with 3, 4 or 5 carbon atoms, preferably cyclopentane, isopentane and n-pentane, hydrofluorocarbons (HFCs), preferably HFC 245fa, HFC 134a or HFC 365mfc, hydrochlorofluorocarbons (HCFCs), preferably HCFC 141b, hydrofluoroolefins (HFOs) 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.

[0092] Likewise, it is also possible to use gaseous blowing agents in pressurized cylinders, useful examples of which include all gases suitable for this purpose under pressure or in pressure-liquefied form, for example hydrocarbons such as butane isomers and propane isomers, dimethyl ether, nitrogen, air and other suitable gases.

[0093] The chemical blowing agents used may be one or more compounds which react with NCO groups and release gas, such as water or formic acid, or compounds which release gas during the reaction as a result of the increase in temperature, such as sodium bicarbonate.

[0094] The optional additives (h) used may be one or more substances known from the prior art and used for the production of polyurethanes, especially PU foams, such as crosslinkers, chain extenders, stabilizers against oxidative degradation (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.

[0095] As optional flame retardants, the composition according to the invention may contain one or more known flame retardants suitable for the production of PU foams, for example halogen-containing or halogen-free organic phosphorus-containing compounds, for example triethyl phosphate (TEP), tris(1-chloro-2-propyl) phosphate (TCPP), tris(2-chloroethyl) phosphate (TCEP), dimethyl methylphosphonate (DMMP), dimethyl propylphosphonate (DMPP), ammonium polyphosphate (APP) or red phosphorus, chlorinated paraffins, nitrogen-containing compounds, for example melamine, melamine cyanurate or melamine polyphosphate, or halogenated compounds, for example chlorinated and / or brominated polyether polyols and / or polyester polyols. Mixtures of different flame retardants can also be used.

[0096] Unless it is clear to the contrary from the present description, any preferred or particularly preferred embodiment of the present invention may be combined with one or more other preferred or particularly preferred embodiments of the present invention.

[0097] The method for producing PU foam according to the invention can be carried out by any known method, for example by manual mixing or preferably by means of a foaming machine. If the method is carried out using a foaming machine, high-pressure or low-pressure machines can be used. The method according to the invention can be carried out intermittently or continuously and can use, for example, 1K, 1.5K or 2K systems as described in EP3717538 A1, US7776934 B2, EP1400547 B1 or EP2780384B2.

[0098] One-component canned PU foams are known to the person skilled in the art from the prior art. Throughout the context of the present invention, the term "one-component canned PU foam" encompasses polyurethane foams which are preferably characterized by the presence of a polyol-isocyanate prepolymer which can be blown out of a pressurized can by a propellant gas and thus foamed.

[0099] Suitable polymers preferably used for this purpose are obtainable, for example, by reacting polyols and isocyanates with one another with the aid of suitable catalysts (e.g. blowing catalysts such as 2,2-dimorpholinyl diethyl ether) or without the action of catalysts. The final curing of these prepolymers is then carried out, for example, under the action of moisture from the environment.

[0100] Spray foam is a free-rising foam that is applied to a substrate by spraying a liquid reaction component onto the substrate. Processing is usually carried out by a spray foam machine, which can be implemented as a high-pressure or low-pressure machine and combines and mixes the two components (polyol mixture and isocyanate). The foam is usually discharged by means of a static mixer in the form of a spray gun. In principle, the raw material or foam can also be discharged from a larger container by gas pressure, similar to the principle of canned foam. The foam is used for thermal insulation purposes and for structural purposes in walls, roofs, floors, and can be open-cell or closed-cell depending on the application.

[0101] Packaging foams are used for packaging, protection and cushioning of sensitive items. Low-density open-cell foams are usually used, which are intended to tightly enclose the items to be protected and protect them from damage, impacts, etc. For this purpose, the foam is also optionally foamed directly into the space between the packaging and the item.

[0102] Thermoformable rigid polyurethane foams are rigid polyurethane foams that are mechanically deformed after production, for example by application of heat, water / steam and pressure. Foams that are initially in block form and optionally cut to size are used to produce shaped articles. Examples are headliner foams and hood liner foams (foams for tailgates and cladding).

[0103] Floral foam, for example, for arranging flowers and the like, is a polyurethane foam suitable for accommodating flowers and other objects by inserting them into the foam due to its low density, mechanical properties and high open cell content.

[0104] Pipe insulation foam is a polyurethane foam used for pipe insulation. It protects the pipe or the pipe contents firstly from heat or freezing losses and secondly from mechanical influences. Especially in the field of pipelines laid in water bodies, at sea and in the deep sea, a high open cell content is desirable in some cases for mechanical reasons.

[0105] In principle, however, the cell openers described in the present invention can also be used for all other PU foam applications, in particular rigid PU foam applications, in which a high open cell content is required, which has a direct positive influence, for example, on the dimensional stability of the foam.

[0106] The open cell content / closed cell content of the rigid polyurethane foam can preferably be determined in accordance with DIN ISO 4590:2016-12, “Rigid cellular plastics—Determination of the volume percentage of open cells and of closed cells”, for example using a gas pycnometer.

[0107] In the context of the present invention, a high open cell content is considered to be an open cell content of more than 50% of the cells.

[0108] The dimensional stability of the one-component potted PU foam can preferably be measured by the method TM 1004:2013 of FEICA—Association of the European Adhesive & Sealant Industry.

[0109] The preparation of the polyether-siloxane block copolymers according to the invention is based on a hydrosilylation reaction known to those skilled in the art and can be achieved by such a reaction of α,ω-modified hydrosiloxanes with α,ω-modified di(meth)allyl polyethers. The chemical reactions forming the basis for such preparation are known in the technical literature and are extensively described therein (see, for example, Silicones-Chemistry and Technology, Vulkan-Verlag Essen, 1989).

[0110] The present invention is further described below and by way of example, but it is not intended to limit the present invention to these exemplary embodiments. In the case of the following specified range, formula or compound class, these are intended not only to include the corresponding range or group of the compound explicitly mentioned, but also to include all sub-ranges and sub-groups of the compound that can be obtained by extracting a single value (range) or compound. In the case of citing a document in the context of this specification, its entirety, especially with respect to the subject matter forming the context of citing the document, is intended to form a part of the disclosure of the present invention. Unless otherwise stated, percentages are weight percentages. Molar percentages are expressed in the abbreviation form of m%. Unless otherwise stated, in the case of parameters determined by measurement reported below, the measurements are carried out at a temperature of 25 ° C and a pressure of 101 325Pa (standard pressure). In the case of using a chemical (empirical) formula in the present invention, the specified subscript can be not only an absolute number, but also an average value. For polymer compounds, the subscript preferably represents an average value. The structural formula and empirical formula proposed in the present invention represent all isomers that may be produced by different arrangements of repeating units. Where compounds such as polyethers, siloxanes or polyether siloxanes are described many times in the context of the present invention which may have different units, these may occur in these compounds in a statistical distribution (statistical oligomers or polymers), in ordered form (block oligomers or block polymers) or in a gradient distribution.

[0111] The solvent mixture according to the invention used in the process according to the invention comprises not only the aromatic solvent of formula 5 but also the alkoxylated alcohol of formula 6. In a preferred embodiment of the invention, 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.

[0112] The reactants used are α,ω-modified hydrogenated siloxane and α,ω-modified di(methyl)allyl polyether, and are used in the presence of a hydrosilylation catalyst.

[0113] When the ratio of the sum of the mass of the aromatic solvent of Formula 5 and the alkoxylated alcohol of Formula 6 to the sum of the mass of the reactants is 7:3 to 1:4, this is another preferred embodiment of the present invention.

[0114] The α,ω-modified di(meth)allyl polyether is 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, more preferably in the range of 0.99:1.01 to 1.01:0.99. This is also a preferred embodiment of the present invention.

[0115] The hydrosilylation according to the invention is carried out in the presence of a hydrosilylation catalyst. It is another preferred embodiment of the invention when the hydrosilylation catalyst used for the reaction is selected from platinum catalysts, especially platinum (0) catalysts, very particularly preferably platinum (0) catalysts in the form of Karstedt catalysts.

[0116] Such catalysts are known; see, for example, Lewis et al., "Platinum Catalysts used in Silicones Industry", Platinum Metal Review, 1997, 44(23), 66-74.

[0117] The weight average molar mass Mw of the polyether siloxane prepared by the process according to the invention is preferably at least 60000 g / mol, preferably at least 80 000 g / mol, more preferably at least 90 000 g / mol, and the number average molar mass Mn is at least 25000, preferably at least 27 500 g / mol, more preferably at least 30 000 g / mol. It is further preferred when 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 molar mass Mw" and "number average molar mass Mn" are known to those skilled in the art. These two parameters can preferably be determined by gel permeation chromatography (GPC), preferably calibrated relative to polystyrene. For this purpose, for example, a SECcurity2 GPC system from PCC can be used, calibrated relative to polystyrene. In particular, a PCC SECcurity 1260 GPC system can be used, preferably with the following experimental framework parameters: SDV Column combination, PSS SECurity 1260RI detector, mobile phase: THF, flow rate: 1 ml / min), calibrated against polystyrene (162-2 520 000 g / mol).

[0118] The mixture obtained by the process according to the invention can be used according to the invention for producing polyurethane foams, in particular rigid polyurethane foams.

[0119] The present invention therefore further provides a formulation suitable for use as an additive for producing polyurethane foams, preferably rigid polyurethane foams, comprising the following components:

[0120] (a) Polyether-siloxane block copolymer of formula 1

[0121]

[0122] in

[0123] a=0 to 100, preferably 5 to 75, more preferably 10 to 50,

[0124] b=0 to 100, preferably 5 to 75, more preferably 5 to 25,

[0125] c=0 to 100, preferably 5 to 75, more preferably 5 to 25,

[0126] d=1 to 100, preferably 5 to 50, more preferably 7 to 40, most preferably 12 to 30,

[0127] n=5-200, preferably 10-100, more preferably 15-50, and

[0128] Where R 1 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, most preferably methyl,

[0129] 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 OH, particularly preferably methyl,

[0130] 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,

[0131] And where R 4 The groups are independently selected from R 5 , R 6 , R 7 group and H, where R 5 The group conforms to formula 2

[0132]

[0133] And where R 6 The group conforms to formula 3

[0134]

[0135] And where R 7 The group conforms to formula 4

[0136]

[0137] where the subscripts a, b, and c and R 2 and R 3 The group is as defined above,

[0138] (b) at least one aromatic solvent of the general formula 5

[0139]

[0140] in

[0141] x=0-20, preferably 0-16,

[0142] y = 0-20, preferably 0-16,

[0143] x+y=6-20, preferably 8-16,

[0144] and

[0145] (c) at least one alkoxylated alcohol of formula 6

[0146]

[0147] in

[0148] j=0 to 30, preferably 0 to 10, more preferably 0 to 5,

[0149] k=1 to 20, preferably 2 to 10, more preferably 3 to 5,

[0150] l=1 to 20, preferably 2 to 10, more preferably 3 to 5, and

[0151] Where R 9 The group is a monovalent aliphatic saturated or unsaturated, linear or branched hydrocarbon group having 6 to 40, preferably 8 to 30, even more preferably 10 to 22 carbon atoms, and wherein R 8 The radicals are independently the same or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably methyl.

[0152] In a preferred embodiment of the present 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.

[0153] Furthermore, preference is given to formulations in which the ratio of the sum of the masses of (b) and (c) to (a) is from 8:2 to 1:4. This corresponds to a preferred embodiment of the present invention.

[0154] Furthermore, preference is given to formulations in which the polyether-siloxane block copolymer of the 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 total formulation.

[0155] In a very particularly preferred embodiment of the invention, the formulations according to the invention do not contain any polyethers of the formula 8:

[0156]

[0157] in

[0158] g=0 to 75, preferably 0 to 50, more preferably 0 to 2,

[0159] h=1 to 100, preferably 2 to 50, more preferably 3 to 25,

[0160] i=1 to 100, preferably 2 to 50, more preferably 3 to 25, and

[0161] Where R 8 The radicals are independently the same or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably methyl.

[0162] As already stated, the present invention makes it possible to provide polyether-siloxane block copolymers having a high molecular weight and a narrow molar mass distribution.

[0163] A particularly preferred embodiment of the present invention is a formulation according to the invention comprising M w (g / mol) ≥ 60,000, preferably > 80,000, especially > 90,000, of the polyether-siloxane block copolymer of formula 1, wherein M w / M n <4.5, preferably <4.0, especially <3.5. As already described further, M in the context of the present invention w and M n It can preferably be determined by gel permeation chromatography (GPC), preferably calibrated against polystyrene.

[0164] Furthermore, it may be preferred when the formulation according to the invention also comprises a pendent stabilizer as an additional component. Here, the pendent stabilizer is likewise a polyether siloxane, but a polyether siloxane having a silicone chain with side and / or terminal polyether chains. The polyether chain can be bonded to the silicone chain via a silicon-carbon bond (Si-C) or a silicon-oxygen-carbon bond (Si-OC), particularly preferably via a silicon-carbon bond. Particularly preferred here are those pendent Si-C-based polyethersiloxanes that conform to formula 7:

[0165]

[0166] in

[0167] x=0 to 50, preferably 1 to 25, more preferably 2 to 15,

[0168] y=0 to 250, preferably 5 to 150, more preferably 5 to 100,

[0169] Where R 9The 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 methyl, and wherein R 10 The groups are independently identical or different OH-functional or 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 .

[0170] As described above, since the polyether-siloxane block copolymers according to the invention are effective cell openers for producing polyurethane foams, especially open-cell rigid polyurethane foams, the present invention also provides the use of the formulations according to the invention as additives, especially as cell opening additives or cell openers, in the production of polyurethane foams, preferably rigid polyurethane foams and especially one-component potted PU foams, especially in combination with side-linked stabilizers of formula 7.

[0171] The present invention therefore further provides polyurethane foams, preferably rigid polyurethane foams, produced using the formulations according to the invention as described above.

[0172] The present invention further provides the use of a polyurethane foam, preferably a rigid polyurethane foam, according to the invention as described above for producing foam moldings, spray foams, insulating foams, sealing compounds, adhesive compounds, insulating compounds, assembly compounds and / or filler compounds.

[0173] As described above, the polyether siloxanes obtainable by the process according to the invention are notable for particularly favorable molar masses and particularly favorable molar mass distributions, which means that they are particularly suitable as additives for producing polyurethane foams, preferably rigid polyurethane foams. The present invention therefore further provides polyether-siloxane block copolymers according to formula 1

[0174]

[0175] in

[0176] a=0 to 100, preferably 5 to 75, more preferably 10 to 50,

[0177] b=0 to 100, preferably 5 to 75, more preferably 5 to 25,

[0178] c=0 to 100, preferably 5 to 75, more preferably 5 to 25,

[0179] a+b+c>3,

[0180] d=1 to 100, preferably 5 to 50, more preferably 7 to 40, most preferably 12 to 30,

[0181] n=5-200, preferably 10-100, more preferably 15-50, and

[0182] Where R 1 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, most preferably methyl,

[0183] 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 OH, particularly preferably methyl,

[0184] 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,

[0185] And where R 4 The groups are independently selected from R 5 , R 6 , R 7 group and H, where R 5 The group conforms to formula 2

[0186]

[0187] And where R 6 The group conforms to formula 3

[0188]

[0189] And where R 7 The group conforms to formula 4

[0190]

[0191] where the subscripts a, b, and c and R 2 and R 3 The group is as defined above,

[0192] The polyether-siloxane block copolymer has a weight average molar mass Mw of at least 60 000 g / mol, preferably at least 80 000 g / mol, more preferably at least 90 000 g / mol, and a number average molar mass Mn of at least 25 000, preferably at least 27500 g / mol, more preferably at least 30 000 g / mol, and it is particularly preferred when Mw / Mn is 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.

[0193] In particular, when these polyether-siloxane block copolymers are prepared without using the polyether of Formula 8, it is preferred

[0194]

[0195] in

[0196] g=0 to 75, preferably 0 to 50, more preferably 0 to 2,

[0197] h=1 to 100, preferably 2 to 50, more preferably 3 to 25,

[0198] i=1 to 100, preferably 2 to 50, more preferably 3 to 25, and

[0199] Where R 8 The radicals are independently the same or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably methyl.

[0200] The invention further provides 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 having a siloxane chain with side and / or terminal polyether chains, wherein the polyether chain can be bonded to the silicone chain via a silicon-carbon bond (Si-C) or a silicon-oxygen-carbon bond (Si-OC), particularly preferably via a silicon-carbon bond, and particularly preferred are those side-bonded Si-C-based polyethersiloxanes corresponding to formula 7 as already defined above,

[0201] The context fully refers to the previous description. Example

[0202] The following examples are intended only to illustrate the present invention to those skilled in the art and do not constitute any kind of limitation to the claimed subject matter.

[0203] Material:

[0204] a) SiH Siloxane A

[0205] In the following synthesis, a siloxane of the general formula a was used.

[0206]

[0207] b) Bis(meth)allyl polyether A

[0208] In the following synthesis, bismethallyl polyether of formula b was used.

[0209]

[0210] Synthesis Example

[0211] Example 1: Synthesis in Toluene (Comparative Example)

[0212] A 500 ml three-necked flask with a precision glass stirrer and a reflux condenser was initially charged with 73 g of bismethylallyl polyether A. Subsequently, 103 g of toluene and 30 g of SiH siloxane A were added. The reaction mixture was heated to 80° C. Thereafter, 10 ppm of Pt was 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. A gel-like product was obtained, which was diluted with another 103 g of toluene in between to keep it stirrable. A transparent gel-like product was obtained. Because the viscosity was very high, the solvent could not be removed by distillation.

[0213] Example 2: Synthesis in Toluene / Alkoxylated Alcohol (Comparative Example)

[0214] A 1000 ml three-necked flask with a precision glass stirrer and a reflux condenser was initially charged with 73 g of bismethylallyl polyether A. Subsequently, 103 g of toluene, 103 g of APM T (myristyl alcohol propoxylate) and 30 g of SiH siloxane A. The reaction mixture was heated to 80° C. Thereafter, 10 ppm of Pt were 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 volatile components were then removed at 130° C. and a reduced pressure of 1 mbar. A turbid product was obtained.

[0215] Example 3: Synthesis in dodecylbenzene / alkoxylated alcohol

[0216] A 1000 ml three-necked flask with a precision glass stirrer and a reflux condenser was initially charged with 73 g of bismethylallyl polyether A. Subsequently, 103 g of dodecylbenzene (CAS No.: 123-01-3), 103 g of APM T (myristyl alcohol propoxylate) and 30 g of SiH siloxane A. The reaction mixture was heated to 80° C. Thereafter, 10 ppm of Pt were 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 volatile components were then removed at 130° C. and a reduced pressure of 1 mbar. A highly viscous, transparent product was obtained.

[0217] Table 1: Overview of the experiment

[0218]

[0219] Comparison of Examples 2 and 3 shows that the use of dodecylbenzene in combination with alkoxylated alcohols can produce a transparent product. In addition, dodecylbenzene is not a flammable solvent. Because of these two points, the product has better applicability as a foam stabilizer.

Claims

1. Method for preparing polyether-siloxane block copolymer of formula 1 in a=0 to 100, preferably 5 to 75, more preferably 10 to 50, b=0 to 100, preferably 5 to 75, more preferably 5 to 25, c=0 to 100, preferably 5 to 75, more preferably 5 to 25, a+b+c>3, d=1 to 100, preferably 5 to 50, more preferably 7 to 40, most preferably 12 to 30, n=5 to 200, preferably 10 to 100, more preferably 15 to 50, and Where R 1 The radicals are independently identical or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, particularly preferably methyl, 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 OH, particularly preferably methyl, 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, and Where R 4 The groups are independently selected from R 5 , R 6 , R 7 group and 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 where the subscripts a, b, and c and R 2 and R 3 The groups are as defined above, the method being carried out by hydrosilylation of an α,ω-modified hydrosiloxane 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 addition of Si—H groups to (meth)allyl double bonds, It is characterized in that The reaction is carried out in a solvent mixture comprising at least one aromatic solvent of the general formula 5 in 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 in j=0 to 30, preferably 0 to 10, more preferably 0, k=0 to 20, preferably 0 to 10, more preferably 0 to 5, l=1 to 20, preferably 2 to 10, more preferably 3 to 5, and Where R 9 The radical is a monovalent aliphatic saturated or unsaturated, straight-chain or branched hydrocarbon radical having 6 to 40, preferably 8 to 30, particularly preferably 10 to 22 carbon atoms, and Where R 8 The radicals are independently the same or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably methyl.

2. The method according to claim 1, 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, and preferably in a mass ratio of 3:2 to 12:

1.

3. The method according to any one of claims 1 to 2, characterized in that The ratio of the total mass of the aromatic solvent of Formula 5 and the alkoxylated alcohol of Formula 6 to the total mass of the reactants is 8:2 to 1:

4.

4. The method according to any one of claims 1 to 3, characterized in that The α,ω-modified di(meth)allyl polyether is used in a concentration such that the molar ratio of polyether-bonded double bonds to siloxane-bonded 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.

5. The method according to any one of claims 1 to 4, characterized in that The hydrosilylation catalyst used for the reaction is selected from platinum catalysts, in particular platinum(0) catalysts, very particularly preferably platinum(0) catalysts in the form of Karstedt catalysts.

6. A formulation suitable for use as an additive for the production of polyurethane foams, preferably rigid polyurethane foams, comprising the following components: (a) Polyether-siloxane block copolymer of formula 1 in a=0 to 100, preferably 5 to 75, more preferably 10 to 50, b=0 to 100, preferably 5 to 75, more preferably 5 to 25, c=0 to 100, preferably 5 to 75, more preferably 5 to 25, d=1 to 100, preferably 5 to 50, more preferably 7 to 40, most preferably 12 to 30, n=5-200, preferably 10-100, more preferably 15-50, and Where R 1 The radicals are each independently identical or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, particularly preferably methyl, 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 OH, particularly preferably methyl, 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, and Where R 4 The groups are independently selected from R 5 , R 6 , R 7 group and 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 where the subscripts a, b, and c and R 2 and R 3 The group is as defined above, (b) Aromatic solvent of formula 5 in 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 in j=0 to 30, preferably 0 to 10, more preferably 0 to 5, k=1 to 20, preferably 2 to 10, more preferably 3 to 5, l=1 to 20, preferably 2 to 10, more preferably 3 to 5, and Where R 9 The radical is a monovalent aliphatic saturated or unsaturated, straight-chain or branched hydrocarbon radical having 6 to 40, preferably 8 to 30, even more preferably 10 to 22 carbon atoms, and Where R 8 The radicals are independently the same or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably methyl.

7. The formulation according to claim 6, characterized in that The ratio of the sum of the masses of (b) and (c) to (a) is 8:2 to 1:

4.

8. The formulation according to any one of claims 6 and 7, characterized in that The polyether-siloxane block copolymer of Formula 1 has M w (g / mol) ≥ 60 000, advantageously > 80 000, preferably > 90 000, especially > 100 000, wherein M w / M n <4.5, preferably <4.0, especially <3.

5.

9. The formulation according to any one of claims 6 to 8, characterized in that The additional component used is at least one side-linked polyether siloxane-based stabilizer having a siloxane chain with a side chain and / or a terminal polyether chain, wherein the polyether chain can be bonded to the silicone chain via a silicon-carbon bond (Si-C) or a silicon-oxygen-carbon bond (Si-OC), particularly preferably via a silicon-carbon bond, and particularly preferably those side-linked Si-C-based polyether siloxanes conforming to Formula 7, in x=0 to 50, preferably 1 to 25, more preferably 2 to 15, y=0 to 250, preferably 5 to 150, more preferably 5 to 100, 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 methyl, and wherein R 10 The groups are independently identical or different OH-functional or 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 .

10. A polyether-siloxane block copolymer according to formula 1, which is preferably prepared by the method according to any one of claims 1 to 5 in a=0 to 100, preferably 5 to 75, more preferably 10 to 50, b=0 to 100, preferably 5 to 75, more preferably 5 to 25, c=0 to 100, preferably 5 to 75, more preferably 5 to 25, a+b+c>3, d=1 to 100, preferably 5 to 50, more preferably 7 to 30, most preferably 8 to 20, n=5-200, preferably 10-100, more preferably 15-50, and Where R 1 The radicals are each independently identical or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, particularly preferably methyl, 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 OH, particularly preferably methyl, 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, and Where R 4 The groups are independently selected from R 5 , R 6 , R 7 group and one of 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 where the subscripts 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 Mw of at least 60,000 g / mol, preferably at least 80,000 g / mol, more preferably at least 90,000 g / mol, and a number average molar mass Mn of at least 25,000, preferably at least 27,500 g / mol, more preferably at least 30,000 g / mol, and it is particularly preferred when the ratio of Mw / Mn is less than 4.5, preferably less than 4.0, more preferably less than 3.

5.

11. Use of the formulation according to any one of claims 6 to 9 and / or the polyether-siloxane block copolymer according to claim 10 as an additive for the production of polyurethane foams, preferably rigid polyurethane foams, in particular in combination with at least one additional polyether siloxane-based stabilizer having a siloxane chain with side and / or terminal polyether chains, wherein the polyether chain can be bonded to the silicone chain via a silicon-carbon bond (Si-C) or a silicon-oxygen-carbon bond (Si-OC), particularly preferably via a silicon-carbon bond, and particularly preferred are those side-linked Si-C-based polyether siloxanes that conform to formula 7, in x=0 to 50, preferably 1 to 25, more preferably 2 to 15, y=0 to 250, preferably 5 to 150, more preferably 5 to 100, 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 methyl, and wherein R 10 The groups are independently identical or different OH-functional or 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 .

12. Use of the formulation according to any one of claims 6 to 9 and / or the polyether-siloxane block copolymer according to claim 10 as a cell opener for producing PU foams, preferably rigid PU foams.

13. The use according to claim 12, wherein the rigid polyurethane foam to be produced is a one-component canned PU foam.

14. Polyurethane foam, preferably rigid polyurethane foam, produced using the formulation according to any one of claims 6 to 9 and / or the polyether-siloxane block copolymer according to claim 10, in particular according to the provisions of any one of claims 11 to 13.

15. Use of the polyurethane foam, preferably rigid polyurethane foam, according to claim 14 for producing foam moldings, spray foams, insulating foams, sealing compounds, adhesive compounds, insulation compounds, assembly compounds and / or filler compounds.

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