Polyether siloxane block copolymer for producing polyurethane foam

Abstract

A method for producing a polyether siloxane block copolymer by hydrosilylation of an α,ω-modified hydrosiloxane and an α,ω-modified di(meth)allyl polyether in the presence of a hydrosilylation catalyst, wherein the reaction is carried out in a solvent mixture containing an aromatic solvent and an alkoxylated alcohol is described.

Description

Technical Field

[0001] The present invention relates to the fields of polyether siloxanes, polyurethanes, and polyurethane foams.

[0002] In particular, the present invention relates to the production of specific polyether siloxane block copolymers, as well as to specific formulations and the use of such formulations in the production of polyurethane foams, preferably rigid polyurethane foams, particularly preferably one-component canned PU foams (construction foams, assembly foams, one-component foams (One-Component-Foam / OCF)) and other rigid polyurethane foams where a high closed-cell content is advantageous (e.g., closed-cell spray foams, packaging foams, roof liner foams, pipe insulation foams, floral foams, thermoformable rigid foams, etc.).

[0003] One-component canned PU foams are known per se. These are polyurethane foams that are foamed by a pressurized propellant gas ejected from a pressurized can. The fields of use are assembly, adhesion, and sealing of windows, door frames, pipes, bushings, etc., as well as filling of brickwork gaps, cavity cracks, and joints. The production of such foams is advantageously carried out by providing a prepolymer from a polyol and an isocyanate (advantageously methylene diphenyl diisocyanate, MDI) in a pressurized can, extruding this prepolymer by a propellant gas (propellant), and curing it by ambient moisture. The polyol isocyanate prepolymer has both reactive isocyanate groups and urethane bonds.

[0004] For any of the above applications, it is important that during the curing process, especially after the curing process, there is little change in the geometric dimensions of the finished one-component PU foam. This dimensional stability, i.e., low shrinkage and low additional expansibility, is achieved by the high closed-cell content of the foam. However, at the same time, the foam should not have significant foam defects such as voids due to this closed-cell content, and it is desirable that the cells of the foam remain fine and no coarsening is observed. Therefore, it is common to add a cell opener to the polyol isocyanate prepolymer in addition to the commonly included foam stabilizer (generally a polyether siloxane), and in particular, polyether siloxane block copolymers have been found to be particularly effective for this application. Generally, these cell openers have a linear [AB] n block structure in which polyether chains and siloxane chains alternate. It is important to have a high molecular weight to obtain a good cell opening effect, and at the same time, it is a challenge to produce such a molecular weight reproducibly.

[0005] Non-hydrolyzable [AB] n polyether siloxanes are known to those skilled in the art. For example, U.S. Patent No. 3,957,842 describes such polymers. The patent describes the production 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] U.S. Patent No. 4,150,048 describes non-hydrolyzable [AB] produced by hydrosilylation of a polyether having two CH 2 =C(R)CH 2 end groups per molecule (where R is a monovalent hydrocarbon group). nA polyether siloxane is described. This is produced using an α,ω-SiH functional siloxane under hydrosilylation reaction conditions in the presence of a platinum catalyst. The resulting linear block copolymer is particularly useful as a surfactant or foam stabilizer for the production of polyurethane foams. During the hydrosilylation reaction, the CH 2 =C(R)CH 2 group has a low tendency to isomerize to form non-reactive species, resulting in an unexpectedly high molecular weight of the copolymer.

[0007] U.S. Patent No. 5,869,727 describes a vacuum process for the production of siloxane oxyalkylene copolymers.

[0008] U.S. Patent Application Publication No. 2019 / 0233646 describes a composition containing a [AB] n polyether siloxane. The composition includes a polyether polysiloxane block copolymer and a liquid organic monool compound, which is either a low-degree-of-polymerization glycol ether compound having terminal hydrogen or an alcohol compound having a branched alkyl group with 12 or more carbon atoms.

[0009] As already mentioned, a high molecular weight is important for providing a high closed-cell content and is thus particularly desirable. If the molecular weight of the cell opener is too low, the cell-opening effect will decrease, and as a result, shrinkage or additional expansion of the foam may occur. However, in addition to the cell opener having the highest possible molecular weight, it is also important that the molecular weight distribution be as narrow as possible. In particular, if the molecular weight distribution tails towards very high molecular weights, it can have an adverse effect. Such tailing can cause the viscosity of the cell opener to become very high, significantly impairing its processability during foam production.

[0010] Accordingly, an object of the present invention was to provide a polyether siloxane block copolymer which is characterized by a particularly high molecular weight and at the same time a very narrow molecular weight distribution, and which advantageously exhibits a particularly efficient effect as a cell opener.

[0011] Surprisingly, it has been found that the use of a specific solvent mixture enables the production of the corresponding polyether siloxane block copolymer, and thus the solution of the above-mentioned problems.

[0012] Accordingly, the subject of the present invention is a compound of formula 1 [Chemical formula] [wherein, 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 30, n = 5 to 200, preferably 10 to 100, particularly preferably 15 to 50, and the group R 1 are, independently of one another, identical or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, preferably having 1 to 10 carbon atoms, and very particularly preferably a methyl group, the group R 2 are, independently of one another, identical or different monovalent aliphatic saturated or unsaturated hydrocarbon groups having 1 to 20 carbon atoms, or H, and particularly preferably a methyl group, the group R 3 are, independently of one another, identical or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, preferably a methyl group, the group R 4 are independently the group R 5 、R 6, R 7 is selected from or H, and the group R 5 is of formula 2 [Chemical formula] is compatible with, and the group R 6 is of formula 3 [Chemical formula] is compatible with, and the group R 7 is of formula 4 [Chemical formula] is compatible with, the subscripts a, b and c and the said group R 2 and R 3 are as defined above] is a process for producing a polyether siloxane block copolymer, which process is carried out by hydrosilylation of an α,ω-modified hydrosiloxane and 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, the reaction is carried out with at least one aromatic solvent of general formula 5 [Chemical formula] [wherein, x = 0 to 20, preferably 0 to 16, y = 0 to 20, preferably 0 to 16, x + y = 6 to 20, preferably 8 to 16] and a compound of formula 6 [Chemical formula] [wherein, j = 0 to 30, preferably 0 to 10, particularly preferably 0, k = 0 to 20, preferably 0 to 10, particularly preferably 0 to 5, l = 1 to 20, preferably 2 to 10, particularly preferably 3 to 5, and the group R 9is a monovalent saturated or unsaturated linear or branched aliphatic hydrocarbon group having 6 to 40 carbon atoms, preferably 8 to 30 carbon atoms, and even more preferably 10 to 22 carbon atoms, and the group R 8 is, independently of one another, the same or different, a monovalent aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, preferably a methyl group], and is carried out in a solvent mixture containing at least one alkoxylated alcohol.

[0013] In the polyoxyalkylene group, polyol or alkoxylated alcohol in the brackets, the arrangement of various oxyalkylene units specified by attaching a lower-case subscript may be random (statistical distribution type), block-like, or may change stepwise, and these options may be arbitrarily mixed for each section. The structural formulas specified are merely simplified illustrations here with respect to the arrangement.

[0014] Therefore, the solvent mixture according to the present invention contains at least two components, namely the aromatic solvent of formula 5 and the alkoxylated alcohol of formula 6, and advantageously consists of these two components.

[0015] In a very particularly preferred embodiment of the present invention, the solvent mixture according to the present invention has the formula 8 [Chemical formula] [wherein, 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 the group R 8 is, independently of one another, the same or different, a monovalent aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, preferably a methyl group], and does not contain a polyether.

[0016] Such a solvent mixture according to the invention, i.e. a solvent mixture comprising at least an aromatic solvent of formula 5 and an alkoxylated alcohol of formula 6 but not comprising a polyether of formula 8, is a very particularly preferred embodiment of the invention.

[0017] The advantage of the process according to the invention is that it not only enables the provision of corresponding polyether siloxane block copolymers which are of high molecular weight and at the same time have as narrow a molecular weight distribution as possible, but also that the formulations obtained with a relatively high active substance content have a relatively low viscosity and thus have considerable processing advantages.

[0018] A further advantage is that the resulting polyether siloxane block copolymers have a high molecular weight and a narrow molecular weight distribution. For example, in particular, a polyether siloxane block copolymer according to formula 1, wherein the weight average molecular weight M w (g / mol) is ≧ 60000, preferably > 80000, more preferably > 90000, especially > 100000, where M w / M n < 4.5, preferably < 4.0, especially < 3.5 can be guaranteed. M n is the number average molecular weight.

[0019] The high molecular weight is particularly advantageous here for the use according to the invention of said polyether siloxane block copolymers as cell openers in the production of polyurethane foams, preferably rigid polyurethane foams (in particular one-component canned PU foams, continuous cell spray foams, packaging foams, roof liner foams, pipe insulation foams, floral foams, thermoformable rigid foams, etc.), because this enables in particular the production of continuous cell foams. In addition to this continuous cell content, a regular foam structure and pore structure as well as a low foam defect rate are achieved. From this point of view, the low viscosity and narrow molecular weight distribution are equally beneficial.

[0020] The polyether siloxane block copolymer itself is known. The term "polyether" includes polyoxyalkylene in the context of the present invention, and particularly polyoxyethylene and polyoxypropylene, as well as polyoxyethylene - polyoxypropylene mixed polyethers are preferred. The distribution of various oxyalkylene units along the polymer main chain can be various. The mixed polyether can be constructed, for example, statistically, in block form or with various gradients between monomer units. Statistical construction means, in this context, that polyoxyethylene units and polyoxypropylene units are distributed in a random order throughout the polyether chain, while a polyether constructed in block form consists of defined polyoxyethylene blocks and polyoxypropylene blocks.

[0021] The term "siloxane" includes, in the context of the present invention, compounds of the class of polyorganosiloxanes, particularly preferably compounds of the class of polydimethylsiloxanes. The term "polyether siloxane block copolymer" includes, in the context of the present invention, polymers constructed with polyether blocks and siloxane blocks arranged alternately.

[0022] The polyether siloxane block copolymer according to the present invention follows Formula 1.

[0023] The term "polyurethane foam" itself is known to those skilled in the art (see, for example, Adam et al., ”Polyurethanes”, Ullmann’s Encyclopedia of Industrial Chemistry - Paragraph 7”, 2012, Wiley VCH-Verlag, Weinheim).

[0024] A preferred composition according to the present invention of a PU foam, preferably a rigid polyurethane foam, comprises the following components: a) The polyether siloxane block copolymer according to the present invention as a cell opener b) A polyol component, c) (Poly) isocyanate component d) Catalyst e) Optionally, a foam stabilizer f) Blowing agent g) Optionally, further additives, preferably fillers, liquid flame retardants, etc. are included.

[0025] The terms polyurethane and polyurethane foam are established technical terms and have long been known to those skilled in the art.

[0026] In the scope of the present invention, polyurethane (PU) is understood to be a product that can be obtained by the reaction of a polyisocyanate component and a polyol component.

[0027] Here, in addition to polyurethane, further functional groups such as uretdione, carbodiimide, isocyanurate, allophanate, biuret, urea and / or uretonimine can also occur. Therefore, in addition to polyurethane, polyisocyanurate, polyurea, and polyisocyanate reaction products containing uretdione groups, carbodiimide groups, allophanate groups, biuret groups and / or uretonimine groups are also understood to be PU in the spirit of the present invention.

[0028] Accordingly, in the scope of the present invention, polyurethane foam (PU foam) is understood to be a foam obtained as a reaction product of a polyisocyanate component and a polyol component. Here too, in addition to what is referred to as polyurethane, further functional groups such as allophanate, biuret, urea, carbodiimide, uretdione, isocyanurate or uretonimine can occur.

[0029] PU rigid foam is an established technical term. The known fundamental difference between soft foam and rigid foam is that soft foam exhibits elastic behavior and thus the deformation is reversible. In contrast, rigid foam is permanently deformed. Detailed information on polyurethane rigid foam is also described in "Kunststoffhandbuch, Band 7, Polyurethane", Carl Hanser Verlag, 3. Auflage 1993, Kapitel 6. The terms foam or foamed body are treated as synonyms in the context of the present invention. This also applies to terms based on this, such as rigid foam or rigid foamed body. Particularly preferred PU foams in the context of the present invention are polyurethane rigid foams, one-component can foams, continuous cell spray foams, packaging foams, roof liner foams, pipe insulation foams, floral foams, thermoformable rigid foams and / or further polyurethane rigid foams where a high continuous cell content is advantageous.

[0030] As the polyol component (b), one or more organic compounds having OH groups, SH groups, NH groups and / or NH 2 groups and having a functionality of 1.8 to 8 can be used. Here, the polyol component includes at least one compound having at least two isocyanate-reactive groups selected from OH groups, SH groups, NH groups and / or NH 2 groups, particularly OH groups.

[0031] For example, a functionality of 1.8 can result from, for example, at least one compound having a relatively high functionality of 2 or more being mixed with at least one compound having a functionality of, for example, 1. This can occur particularly when a polyisocyanate component (c) having a functionality exceeding 2 or an additional crosslinking agent as an optional additive (h) is used.

[0032] Suitable compounds commonly used in manufacturing PU foams are known to those skilled in the art and are described, for example, in "Kunststoffhandbuch, Band 7, Polyurethane", Carl Hanser Verlag, 3. Auflage 1993, Chapter 3.1. Usually, compounds with an OH value in the range of 10 to 1200 mg KOH / g are used.

[0033] Particularly preferred compounds are all polyether polyols and polyester polyols commonly used in the production of polyurethane-based, particularly polyurethane foams.

[0034] Furthermore, polyether polycarbonate polyols, natural oil-based polyols (natural oil-based polyols, NOPs; WO 2005 / 033167, US Patent Application Publication No. 2006 / 0293400, WO 2006 / 094227, WO 2004 / 096882, US Patent Application Publication No. 2002 / 0103091, WO 2006 / 116456, European Patent No. 1678232), filled polyols, prepolymer-based polyols and / or recycled polyols can be used.

[0035] Recycled polyols are polyols obtained from polyurethane by chemical recycling methods such as solvolysis, such as glycolysis, hydrolysis, acidolysis or aminolysis. The use of recycled polyols is a particularly preferred embodiment of the present invention.

[0036] When the poly component contains a polyol isocyanate prepolymer, a preferred embodiment of the present invention exists.

[0037] As the isocyanate or polyisocyanate component (c), one or more polyisocyanates having generally two or more isocyanate groups can be used. The polyisocyanates suitable in the context of the present invention are all organic isocyanates having two or more isocyanate groups, in particular aliphatic, cycloaliphatic, araliphatic and preferably aromatic polyisocyanates which are known per se.

[0038] Examples that can be cited here include alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene group, 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), alicyclic diisocyanates, such as cyclohexane 1,3- and 1,4-diisocyanate, and corresponding isomer mixtures, 4,4'-methylenedicyclohexyl diisocyanate (H12MDI), isophorone diisocyanate (IPDI), 2,4- and 2,6-methylcyclohexyl diisocyanate, and corresponding isomer mixtures, and preferably aromatic diisocyanates and polyisocyanates, such as 2,4- and 2,6-toluene diisocyanate (TDI), and corresponding isomer mixtures, naphthalene diisocyanate, diethyltoluene diisocyanate, 4,4'- or 2,2'- or 2,4'-diphenylmethane diisocyanate (MDI) and polymethylene polyphenyl polyisocyanate (PMDI, "polymeric MDI"). The organic polyisocyanates can be used alone or in the form of their mixtures. Similarly, it is also possible to use corresponding "oligomers" of diisocyanates, such as IPDI trimers based on isocyanurate, biuret or uretdione. Furthermore, it is also possible to use prepolymers based on the above-mentioned isocyanates. Particularly suitable are mixtures of MDI with higher condensation analogues having an average functionality of 2 to 4, known as "polymeric MDI" (also called "crude MDI" or "raw MDI"), and various isomers of TDI in pure form or as isomer mixtures. It is also possible to use so-called modified isocyanates, which are isocyanates modified by incorporating groups such as urethane, uretdione, isocyanurate, allophanate, etc.Examples of particularly suitable isocyanates are described, for example, in European Patent No. 1712578, European Patent No. 1161474, International Publication No. 00 / 58383, US Patent Application Publication No. 2007 / 0072951, European Patent No. 1678232 and International Publication No. 2005 / 085310, and these documents are hereby incorporated by reference in their entirety.

[0039] The preferred ratio of the polyisocyanate component to the polyol component is expressed as an index of the formulation, i.e., the value obtained by multiplying the stoichiometric ratio of the isocyanate groups to the isocyanate-reactive groups (e.g., OH groups, NH groups) by 100, which ranges from 10 to 1000, preferably from 40 to 500. The index 100 represents a molar ratio of reactive groups of 1:1.

[0040] Suitable catalysts (d) that can be used in the production of polyurethanes, especially PU foams, are known to those skilled in the art from the prior art. In the context of the present invention, all compounds that can catalyze the reaction of isocyanate groups with OH groups, NH groups or other isocyanate-reactive groups and / or the reaction of isocyanate groups with each other can be used.

[0041] Here, conventional catalysts known from the prior art can be used, for example, amines (cyclic, acyclic; monoamines, diamines, oligomers having one or more amino groups), ammonium compounds, organometallic compounds and / or metal salts, preferably compounds of tin, iron, bismuth, potassium and / or zinc. In particular, mixtures of such plural compounds can be used as the catalyst.

[0042] 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, and advantageously one or more foam stabilizers are used. As foam stabilizers, in particular, surface-active compounds (surfactants) can be used. Preferably, a foam stabilizer is used. The foam stabilizer can be used to optimize the desired cell structure and the foaming process. In particular within the scope of the present invention, Si-containing compounds that assist in foaming (stabilization, cell adjustment, 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 can be used. The corresponding siloxane structures that can be used in the context of the present invention are described, for example, in the following patent documents, which only describe their use in conventional PU foams (such as molded foams, mattresses, insulation materials, building foams, etc.): Chinese Patent Specification No. 103665385, Chinese Patent Specification No. 103657518, Chinese Patent Specification No. 103055759, Chinese Patent Specification No. 103044687, US Patent Application Publication No. 2008 / 0125503, US Patent Application Publication No. 2015 / 0057384, European Patent Application Publication No. 1520870, European Patent No. 1211279, European Patent No. 0867464, European Patent No. 0867465, European Patent No. 0275563. In addition to surface-active Si-containing compounds, Si-free surfactants can also be used. For example, European Patent Application Publication No. 2295485 describes the use of lecithin as a foam stabilizer for the production of rigid PU foams, and US Patent No. 3746663 describes the use of a vinylpyrrolidone-based structure as a foam stabilizer for the production of rigid PU foams. Further Si-free foam stabilizers are described, for example, in European Patent No. 2511328, German Patent Application Publication No. 1020011007479, German Patent Invention No. 3724716, European Patent No. 0734404, European Patent No. 1985642, German Patent No. 2244350, and US Patent No. 5236961.

[0043] The use of 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 preferably a blowing agent is used. The use of one blowing agent (f) or a combination of two or more blowing agents (f) generally depends on the type of foaming method used, the type of system, and the use of the resulting PU foam. Chemical and / or physical blowing agents, as well as combinations of both, can be used. Depending on the amount of blowing agent used, high-density or low-density foams are produced. For example, foams with a density of 5 kg / m 3 ~900 kg / m 3 , preferably 5~350, particularly preferably 8~200 kg / m 3 and especially 8~150 kg / m 3 can be produced.

[0044] As physical blowing agents, one or more suitable compounds having appropriate boiling points and their mixtures can be used. For example, hydrocarbons having 3, 4 or 5 carbon atoms, preferably cyclopentane, isopentane, n-pentane, hydrofluorocarbons (HFC), preferably HFC 245fa, HFC 134a or HFC 365mfc, hydrochlorofluorocarbons (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.

[0045] Similarly, gaseous blowing agents can be used in a pressurized tank, and any gas suitable in pressurized or pressurized liquefied form can be mentioned, such as hydrocarbons such as butane isomers and propane isomers, dimethyl ether, nitrogen, air and other suitable gases.

[0046] As chemical blowing agents, one or more compounds that react with NCO groups to release gas, such as water or formic acid, or one or more compounds that release gas during the reaction as a result of a temperature increase, such as sodium bicarbonate, can be used.

[0047] As optional additive substances (h), one or more substances known in the prior art and used in the production of polyurethanes, especially PU foams, can be used. For example, crosslinking agents, chain extenders, stabilizers against oxidative degradation (so-called antioxidants), flame retardants, biocides, cell refinement additives, nucleating agents, additional cell openers, solid fillers, antistatic additives, thickeners, dyes, pigments, color pastes, fragrances and / or emulsifiers, etc. can be used.

[0048] As optional flame retardants, the compositions according to the invention can contain one or more known flame retardants suitable for the production of PU foams. For example, halogen-containing or halogen-free organophosphorus compounds, such as triethyl phosphate (TEP), tris(1-chloro-2-propyl) phosphate (TCPP), tris(2-chloroethyl) phosphate (TCEP), dimethylmethanephosphonate (DMMP), dimethylpropanephosphonate (DMPP), ammonium polyphosphate or red phosphorus, chlorinated paraffins, nitrogen-containing compounds, such as melamine, melamine cyanurate or melamine polyphosphate, or halogenated compounds, such as chlorinated and / or brominated polyether polyols and / or polyester polyols. The use of mixtures of various flame retardants is also possible.

[0049] Unless otherwise apparent from the description herein, all preferred or particularly preferred embodiments of the invention can be combined with one or more other preferred or particularly preferred embodiments of the invention.

[0050] The method for manufacturing a PU foam according to the present invention can be carried out by all known methods, for example, by the hand mixing method or preferably using a foaming machine. When carrying out the method using a foaming machine, high-pressure or low-pressure equipment can be used. The method according to the present invention can be carried out batchwise or continuously, and for example, 1K systems, 1.5K systems or 2K systems as described in European Patent Application Publication No. 3717538, US Patent No. 7776934, European Patent No. 1400547 or European Patent No. 2780384 can be used.

[0051] One-component canned PU foams are well known to those skilled in the art from the prior art. The term one-component canned PU foam encompasses, in the context of the entire present invention, polyurethane foams which advantageously are characterized by the presence of a polyol isocyanate prepolymer which can be foamed by being extruded from a pressurized can by a propellant gas.

[0052] Prepolymers which are preferably suitable for this purpose can be obtained, for example, by reacting a polyol and an isocyanate with each other using a suitable catalyst (for example, a foaming catalyst such as 2,2'-dimorpholinyl diethyl ether) or without catalytic action. The final curing of these prepolymers is then carried out, for example, by the action of moisture from the environment.

[0053] Spray foam is a free-rising foam which is applied by spraying or injecting liquid reaction components onto a substrate. The treatment is generally carried out by spray foam equipment, which can be designed as a high-pressure or low-pressure machine and mixes two components (a polyol mixture and an isocyanate) together. The discharge of the foam is usually carried out by a static mixer in the form of a spray gun or a jet gun. However, in principle, the raw materials or the foam can also be discharged from a larger container by gas pressure in the same way as for canned foams. The foam is used for the purpose of thermal insulation and for the construction of walls, roofs and floors and can be of an open-cell type or a closed-cell type depending on the application.

[0054] Packaging forms are used for packaging, protecting, and buffering delicate products. Generally, a low-density continuous foam type foam that firmly wraps the product to be protected and aims to protect it from damage, impact, etc. is used. For this purpose, the foam may be directly foamed in the space between the packaging material and the product.

[0055] A thermoformable rigid polyurethane foam is a rigid polyurethane foam that can be mechanically deformed by applying, for example, heat, water (steam), and pressure after production. Here, the molded product is manufactured from a foam that is initially in a block shape and is cut as needed. Examples include foam for roof liners (also called foam for headliners) and foam for hood liners (foam for trunk lids and claddings).

[0056] A floral foam is a polyurethane foam that is used, for example, in flower arrangements, and is suitable for inserting and storing flowers and other objects into the foam due to its low density, mechanical properties, and high continuous bubble content.

[0057] A pipe insulation foam is a polyurethane foam used for insulating pipes. This pipe insulation foam protects the pipe and the pipe contents from heat loss and low-temperature loss on the one hand, and from mechanical effects on the other hand. In particular, in the field of pipes laid in water, in the sea, and in the deep sea, a high continuous bubble content is often desired for mechanical reasons.

[0058] However, in principle, the cell opener described in the present invention can also be used for all other PU foams where a high continuous bubble content is desired, particularly for applications of rigid PU foams, which, for example, has a direct beneficial effect on the dimensional stability of the foam.

[0059] The measurement of the open-cell content or closed-cell content of rigid polyurethane foam can be advantageously carried out, for example, using a gas pycnometer and preferably in accordance with DIN ISO 4590:2016-12, "Determination of the volume fraction of open cells and volume fraction of closed cells in rigid foams".

[0060] The high open-cell content in the sense of the present invention is understood to mean that the open-cell content is more than 50% of the cells.

[0061] The measurement of the dimensional stability of one-component canned PU foam can be advantageously carried out in accordance with the method of FEICA (European Adhesives and Sealants Industry Association) TM1004:2013.

[0062] The production of the polyether siloxane block copolymer according to the present invention is based on the hydrosilylation reaction known to those skilled in the art and can be carried out by reacting an α,ω-modified hydrosiloxane with an α,ω-modified di(meth)allyl polyether. The chemical reaction underlying this production is known in the technical literature and is described in detail therein (see, for example, Silicones - Chemistry and Technology, Vulkan-Verlag Essen, 1989).

[0063] The present invention will be exemplarily described below, but the present invention is not limited to these exemplary embodiments. When a range, formula or compound class is shown below, these include not only the corresponding ranges or compound groups explicitly mentioned, but also all sub-ranges and subgroups of compounds that can be obtained by extracting individual values (ranges) or compounds. When a document is cited within the scope of this specification, its content, particularly the content regarding the situation in the context in which the document is cited, shall completely constitute a part of the disclosure content of the present invention. When a document is cited within the scope of this specification, its content, particularly the content regarding the situation in the context in which the document is cited, shall completely constitute a part of the disclosure content of the present invention. Unless otherwise specified, percentage data is data in weight percentage units. Mole percentage is abbreviated as m%. When parameters determined by measurement are shown below, unless otherwise specified, the measurement was carried out at a temperature of 25 °C and a pressure of 101325 Pa (standard pressure). When a chemical (composition) formula is used in the present invention, the indicated subscripts may represent not only absolute numbers but also average values. For polymer compounds, the subscripts preferably represent average values. The structural and composition formulas presented in the present invention represent all possible isomers that can be considered by various arrangements of repeating units. Within the scope of the present invention, when compounds such as polyethers, siloxanes or polyethersiloxanes that can have a plurality of various units a plurality of times are described, these can occur in these compounds in a statistical distribution type (statistical oligomers or polymers), in an ordered type (block oligomers or block polymers) or as a gradient distribution.

[0064] The solvent mixture according to the present invention used in the method according to the present invention contains not only the aromatic solvent of formula 5 but also the alkoxylated alcohol of formula 6. When 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, this corresponds to a preferred embodiment of the present invention.

[0065] As reactants, an α,ω-modified hydrosiloxane and an α,ω-modified di(meth)allyl polyether are used in the presence of a hydrosilylation catalyst.

[0066] When the total mass of the aromatic solvent of Formula 5 and the alkoxylated alcohol of Formula 6 and the total mass of the reactants are in a ratio of 7:3 to 1:4, there is a further preferred embodiment of the present invention.

[0067] The α,ω-modified di(meth)allyl polyether is preferably used at a concentration such that the molar ratio of the double bond bonded to the polyether to the Si-H group 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. This also corresponds to a preferred embodiment of the present invention.

[0068] The hydrosilylation according to the present invention is carried out in the presence of a hydrosilylation catalyst. When the hydrosilylation catalyst used in the reaction is selected from the group of platinum catalysts, particularly platinum(0) catalysts, and in particular, a platinum(0) catalyst in the form of a Karstedt catalyst is highly particularly preferred, there is a further preferred embodiment of the present invention.

[0069] Such catalysts are known; see, for example, Lewis et al., ”Platinum Catalysts used in Silicones Industry”, Platinum Metal Review, 1997, 44(23), 66-74).

[0070] The polyether siloxane produced by the method according to the present invention preferably has a weight average molecular weight M of at least 60000 g / mol, preferably at least 80000 g / mol, and particularly preferably at least 90000 g / mol. w and a number average molecular weight M of at least 25000 g / mol, preferably at least 27500 g / mol, and particularly preferably at least 30000 g / mol. Further, M n has, and w / M n It is preferred that the ratio is less than 4.5, preferably less than 4.0, more preferably less than 3.5. The weight average molecular weight M w and the number average molecular weight M n The terms are known to those skilled in the art. These two parameters can preferably be determined by gel permeation chromatography (GPC), and advantageously with polystyrene as the calibration standard. For this purpose, for example, the SECcurity2 GPC system manufactured by PCC can be used with polystyrene as the calibration standard. In particular, the SECcurity1260 GPC system manufactured by PCC can be used, preferably with the following experimental frame parameters: a combination of SDV 1000 / 10000 Å columns, a PSS SECurity1260 RI detector, a mobile phase of THF, and a flow rate of 1 ml / min), with polystyrene (162 - 2520000 g / mol) as the calibration standard.

[0071] The mixture 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.

[0072] Accordingly, a further subject of the invention is a formulation suitable as an additive for the production of polyurethane foams, preferably rigid polyurethane foams, said formulation comprising the following components: (a) Formula 1

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0073] According to a preferred embodiment of the present invention, components (b) and (c) are present in the composition in a mass ratio of 1:2 to 15:1, preferably in a mass ratio of 3:2 to 12:1.

[0074] Furthermore, a composition in which the total mass of (b) and (c) and the total mass of (a) are in a ratio of 8:2 to 1:4 is preferred. This corresponds to a preferred embodiment of the present invention.

[0075] Furthermore, a composition in which the polyether siloxane block copolymer of formula 1 is contained at 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 composition is preferred.

[0076] In a very particularly preferred embodiment of the present invention, the composition according to the present invention has the formula 8 [Chemical formula] [wherein, 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 the radical R 8 is, independently of one another, the same or different monovalent aliphatic or aromatic hydrocarbon radicals having 1 to 20 carbon atoms, preferably a methyl group, and does not contain polyethers.

[0077] As already mentioned, the present invention enables the provision of polyether siloxane block copolymers having a narrow molecular weight distribution and high molecular weight.

[0078] M w (g / mol) is ≧ 60000, preferably > 80000, particularly > 90000, where M w / M n < 4.5, preferably < 4.0, particularly < 3.5. The composition according to the invention comprising a polyether siloxane block copolymer according to formula 1 corresponds to a particularly preferred embodiment of the present invention. As already mentioned above, M w and M n can preferably be determined in the context of the present invention by gel permeation chromatography (GPC), preferably using polystyrene as the calibration standard.

[0079] Furthermore, it may be preferred for the composition according to the invention to still contain a pendant stabilizer as an additional component. The pendant stabilizer is likewise a polyether siloxane here, but has a silicone chain with pendant and / or terminal polyether chains. The polyether chain may be bonded to the silicone chain here via a silicon-carbon bond (Si-C) or a silicon-oxygen-carbon bond (Si-O-C), with a silicon-carbon bond being particularly preferred. In particular here, formula 7

Chemical formula

[0080] As described above, the polyether siloxane block copolymer according to the present invention is an efficient cell opener for producing polyurethane foams, particularly continuous cell type rigid polyurethane foams. Therefore, the use of the formulation according to the present invention as an additive, particularly a cell opening additive or a cell opener, in the production of polyurethane foams, advantageously rigid polyurethane foams, particularly one-component canned PU foams, and particularly the use in combination with the pendant stabilizer according to formula 7 are also the subject of the present invention.

[0081] Therefore, a polyurethane foam, advantageously a rigid polyurethane foam, produced using the formulation according to the present invention described above is also a further subject of the present invention.

[0082] A further subject of the present invention is the use of the polyurethane foam, advantageously the rigid polyurethane foam, according to the present invention described above in the production of foam moldings, spray foams, insulating foams, sealing materials, adhesive materials, heat insulating materials, assembly materials and / or filling materials.

[0083] As described above, the polyether siloxane obtainable by the method according to the invention is characterized by a particularly advantageous molecular weight and a particularly advantageous molecular weight distribution, whereby the polyether siloxane is particularly suitable for use as an additive in the production of polyurethane foams, preferably rigid polyurethane foams. Accordingly, a further main subject of the invention is of formula 1 [Chemical formula] [wherein, 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 30, n = 5 to 200, preferably 10 to 100, particularly preferably 15 to 50, and the group R 1 are, independently of one another, the same or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, preferably having 1 to 10 carbon atoms, and are very particularly preferably methyl groups, the group R 2 are, independently of one another, the same or different monovalent aliphatic saturated or unsaturated hydrocarbon groups having 1 to 20 carbon atoms, or H, with the methyl group being particularly preferred, the group R 3 are, independently of one another, the same or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, preferably methyl groups, the group R 4 is independently selected from the group R 5 , R 6 , R 7 or H, and the group R 5 conforms to formula 2 [Chemical formula] and the group R6 is in accordance with Formula 3 [Chemical formula] and conforms to group R 7 is in accordance with Formula 4 [Chemical formula] and conforms to subscripts a, b and c and group R 2 and R 3 are as defined above, and has a weight-average molecular weight M of at least 60,000 g / mol, preferably at least 80,000 g / mol, particularly preferably at least 90,000 g / mol, and has a number-average molecular weight M of at least 25,000 g / mol, preferably at least 27,500 g / mol, particularly preferably at least 30,000 g / mol. Here, it is particularly preferred that the ratio of M w / M n is less than 4.5, preferably less than 4.0, more preferably less than 3.5. It is a polyether siloxane block copolymer. Preferably, these polyether siloxane block copolymers can be produced by the method according to the present invention described in detail above. w / M n Specifically, when these polyether siloxane block copolymers are produced without using a polyether of Formula 8

[0084] [Chemical formula] [wherein, 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 group R 8 are, independently of each other, the same or different monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, preferably a methyl group] is preferred.

[0085] 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 polyether siloxane-based stabilizer having a siloxane chain with pendant and / or terminal polyether chains, where the polyether chains may be bonded to the silicone chain via a silicon-carbon bond (Si-C) or a silicon-oxygen-carbon bond (Si-O-C), with the silicon-carbon bond being particularly preferred, in particular, pendant Si-C-based polyether siloxanes conforming to formula 7 as already defined above are preferred, and in this connection, the foregoing description is to be fully incorporated by reference, the use.

[0086] Examples The following examples are for the sole purpose of clarifying the invention to those skilled in the art and are not intended to limit the claimed subject matter.

[0087] Materials: a) SiH siloxane A In the following synthesis, the siloxane of general formula a

Chemical formula

[0088] b) Bismetallyl polyether A In the following synthesis, the bismetallyl polyether of general formula b

Chemical formula

[0089] Synthesis examples Example 1: Synthesis in toluene (comparative example) A 500 mL three-necked flask equipped with a KPG stirrer and a reflux condenser was charged with 73 g of bisallyl polyether A. Then, 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 further diluted with 103 g of toluene at intervals to maintain a stirrable state. A transparent gel-like product was obtained. Since it had a very high viscosity, solvent removal by distillation was not possible.

[0090] Example 2: Synthesis in toluene / alkoxylated alcohol (comparative example) A 1000 mL three-necked flask equipped with a KPG stirrer and a reflux condenser was charged with 73 g of bisallyl polyether A. 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. 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. Then, the volatile components were removed under reduced pressure at 130 °C and 1 mbar. A turbid product was obtained.

[0091] Example 3: Synthesis in dodecylbenzene / alkoxylated alcohol A 1000 mL three-necked flask equipped with a KPG stirrer and a reflux condenser was charged with 73 g of bisallyl polyether A. Then, 103 g of dodecylbenzene (CAS No.: 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. 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. Then, the volatile components were removed under reduced pressure at 130 °C and 1 mbar. A highly viscous transparent product was obtained.

[0092]

Table 1

[0093] From the comparison between Example 2 and Example 3, it can be seen that by using dodecylbenzene in combination with alkoxylated alcohol, a transparent product can be produced. Also, dodecylbenzene is not a flammable solvent. From these two points, this is a product with higher suitability as a foam stabilizer.

Claims

1. Formula 1 【Chemistry 1】 [In the formula, a = 0 to 100, b = 0 to 100, c = 0 to 100, a + b + c > 3, d = 1 to 100, n = 5 to 200, group R １ These are monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, independently of each other, and either identical or different. group R ２ These are, independently of each other, identical or different monovalent aliphatic saturated or unsaturated hydrocarbon groups having 1 to 20 carbon atoms, or H. group R ３ These are monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, independently of each other, and identical or different from each other. group R ４ Independently, base R ５ , R ６ , R ７ Alternatively, selected from H, and based on R ５ Equation 2 【Chemistry 2】 is adapted to the group R ６ is of formula 3 【Transformation 3】 Complies with the base R ７ Equation 4 【Chemistry 4】 It conforms to, Subscripts a, b, and c and base R ２ and R ３ A method for producing a polyethersiloxane block copolymer as defined above, wherein the method is carried out by hydrosilylation of an α,ω-modified hydrosiloxane and an α,ω-modified di(meth)allyl polyether in the presence of a hydrosilylation catalyst capable of catalyzing the formation of a SiC bond by the addition of a Si-H group to a (meth)allyl double bond, The above reaction is represented by General Formula 5 【Transformation 5】 [In the formula, x = 0 to 20, y = 0 to 20, At least one aromatic solvent with x + y = 6 to 20, and formula 6 【Transformation 6】 [In the formula, j = 0 to 30, k = 0 to 20, l = 1 to 20, group R ９ This is a monovalent, saturated or unsaturated, linear or branched aliphatic hydrocarbon group having 6 to 40 carbon atoms. group R ８ A method characterized by being carried out in a solvent mixture comprising at least one alkoxylated alcohol, which is a monovalent aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, independently of each other and identical or different from each other.

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.

3. The method according to claim 1 or 2, characterized in that the total mass of the aromatic solvent of formula 5 and the alkoxylated alcohol of formula 6 is in a ratio of 8:2 to 1:4 to the total mass of the reactants.

4. The method according to claim 1 or 2, characterized in that the α,ω-modified di(meth)allyl polyether is used at a concentration such that the molar ratio of the double bond attached to the polyether to the Si-H group attached to the siloxane is in the range of 0.95:1.05 to 1.05:0.

95.

5. The method according to claim 1 or 2, characterized in that the hydrosilylation catalyst used in the reaction is selected from the group of platinum catalysts.

6. A formulation suitable as an additive for the manufacture of polyurethane foam, wherein the formulation comprises the following components: (a) Formula 1 【Transformation 7】 [In the formula, a = 0 to 100, b = 0 to 100, c = 0 to 100, d = 1 to 100, n = 5 to 200, group R １ These are monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, independently of each other, and either identical or different. group R ２ These are, independently of each other, identical or different monovalent aliphatic saturated or unsaturated hydrocarbon groups having 1 to 20 carbon atoms, or H. group R ３ These are monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, independently of each other, and identical or different from each other. group R ４ Independently, base R ５ , R ６ , R ７ Alternatively, selected from H, and based on R ５ Equation 2 【Transformation 8】 Complies with the base R ６ Equation 3 【Chemistry 9】 Complies with the base R ７ Equation 4 【Chemistry 10】 It conforms to, Subscripts a, b, and c and base R ２ and R ３ [As defined above] Polyethersiloxane block copolymer, (b) Formula 5 【Chemistry 11】 [In the formula, x = 0 to 20, y = 0 to 20, Aromatic solvents where x + y = 6 to 20, and (c) Equation 6 【Chemistry 12】 [In the formula, j = 0 to 30, k = 1 to 20, l = 1 to 20, group R ９ This is a monovalent, saturated or unsaturated, linear or branched aliphatic hydrocarbon group having 6 to 40 carbon atoms. group R ８ Alkoxylated alcohols [where each is a monovalent aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, independently of each other, and identical or different] A compound containing the following:

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

4.

8. The polyethersiloxane block copolymer according to formula 1 has an M of ≥ 60000. ｗ It has (g / mol), where M ｗ / M ｎ The formulation according to claim 6, characterized in that it is <4.

5.

9. The formulation according to claim 6, characterized in that at least one pendant polyethersiloxane-based stabilizer is used as an additional component, the stabilizer having a siloxane chain having a pendant and / or terminal polyether chain, and the polyether chain may be bonded to the silicone chain via a silicon-carbon bond (Si-C) or a silicon-oxygen-carbon bond (Si-O-C).

10. Formula 1 【Chemistry 14】 [In the formula, a = 0 to 100, b = 0 to 100, c = 0 to 100, a + b + c > 3, d = 1 to 100, n = 5 to 200, group R １ These are monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, independently of each other, and either identical or different. group R ２ These are, independently of each other, identical or different monovalent aliphatic saturated or unsaturated hydrocarbon groups having 1 to 20 carbon atoms, or H. group R ３ These are monovalent aliphatic or aromatic hydrocarbon groups having 1 to 20 carbon atoms, independently of each other, and identical or different from each other. group R ４ Independently, base R ５ , R ６ , R ７ Alternatively, selected from H, and based on R ５ Equation 2 【Chemistry 15】 Complies with the base R ６ Equation 3 【Chemistry 16】 Complies with the base R ７ Equation 4 【Chemistry 17】 It conforms to, Subscripts a, b, and c and base R ２ and R ３ It conforms to the above definition and has a weight-average molecular weight M of at least 60,000 g / mol. ｗ It has a number average molecular weight of at least 25,000 g / mol M ｎ A polyethersiloxane block copolymer having the following properties.

11. Use of the compound according to any one of claims 6 to 9 and / or the polyethersiloxane block copolymer according to claim 10 as an additive for the manufacture of polyurethane foam.

12. Use of the formulation according to any one of claims 6 to 9 and / or the polyethersiloxane block copolymer according to claim 10 as a cell opener in the production of PU foam.

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

14. A polyurethane foam manufactured using the compound according to any one of claims 6 to 9 and / or the polyethersiloxane block copolymer according to claim 10.

15. Use of the polyurethane foam according to claim 14 in the manufacture of foam molded articles, spray foams, thermal insulation foams, sealing materials, adhesive materials, thermal insulation materials, assembly materials and / or filling materials.

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