Siloxane-functionalized compounds, their manufacture, and their use in polyurethane foams

Abstract

This disclosure relates to polyurethane foams and surface-active foam stabilizers added thereto. In particular, the present invention relates to polyurethane foams employing siloxane-functional compounds, which provide foams with excellent physical properties characterized by exceptionally low volatile organic compound emissions, wherein the siloxane-functional compound comprises at least two trisiloxane units bonded to a polyether-functional backbone. Methods for producing siloxane-functional compounds, as well as their use in the preparation of polyurethane foams, are also provided.

Description

[Technical Field]

[0001] This invention relates to siloxane-functional compounds, compositions containing the same, their use in the manufacture of polyurethane foam, related methods, and polyurethane foam and articles containing the same. Siloxane-functional compounds as additives can, in particular, provide polyurethane foam with very low volatile organic compound emissions and excellent physical properties.

[0002] Background technology Polyurethane foams are typically produced by reacting compounds containing two or more active hydrogen groups, particularly polyols and organic polyisocyanates, in the presence of blowing agents and, optionally, further additives such as surfactants, foam stabilizers, and catalysts. Two main reactions are facilitated by catalysts in the reactants during the preparation, polymerization, and foaming of the polyurethane foam. These reactions must proceed simultaneously and competitively balanced during the process to obtain a polyurethane foam with the desired physical properties.

[0003] Due to their physical properties, polyurethane foam is used in a very wide range of applications. A particularly important market for various types of polyurethane foam is the automotive industry. Polyurethane foam is typically used in automobiles, for example, as roof lining, door cladding, punched sun visors, steering wheels, and seat systems.

[0004] In the manufacture of polyurethane foam, one or more additives, such as siloxanes, with surface-active properties are often used. Such siloxanes are characterized by a wide variety of structural properties, as their role in foaming can vary significantly. For example, foam shrinkage should be avoided. On the other hand, sufficient continuity of bubbles is intended when the foam reaches its maximum expansion, which also positively influences the foam's shrinkage tendency. Furthermore, the foamed mixture, especially in the case of molded foams, often has to cover complex flow channels, and the foam structure must not have defects after foaming is complete. To this end, the foam's distribution and flow characteristics must be optimized.

[0005] One option for providing foam compositions with good flow properties is to utilize relatively short-chain linear siloxanes with fewer than 15 repeating units as surface-active foam stabilizers. However, a frequent problem with the use of such surface-active foam stabilizers is that unreacted low molecular weight stabilizers are volatile and can cause undesirable emissions from polyurethane foam, which subsequently deposit as an oily film on, for example, car windows. Furthermore, in recent years, the requirements that automotive manufacturers set for foam suppliers have become significantly stricter, particularly regarding emission specifications. While previously the focus was solely on the fogging behavior of foam (e.g., DIN75 201 for determining the fogging behavior of materials for automotive interior materials), today the content of volatile organic compounds (VOCs) is also subject to analytical determination (e.g., Volkswagen Central Standard 55 031, Daimler Chrysler PB VWT709, and VDA276 and 278). Therefore, to meet the stringent requirements of automotive manufacturers, it is desirable to provide foam stabilizers that minimize or even avoid these emissions.

[0006] Various siloxane-containing surfactant foam stabilizers are known in the literature. For example, European Patent Application Publication No. 1095968 describes the production of a low-temperature curing foam using polydimethylsiloxane, which has a particularly narrow chain length distribution and consists of over 90% siloxanes with chain lengths N=7 to 9. These siloxanes do not participate in the polymerization reaction, and therefore their surfactant properties are retained until the end of foaming. However, using such highly volatile polydimethylsiloxanes can lead to the problem of these substances being released from the foam later, which is undesirable, especially in automotive applications.

[0007] U.S. Patent Application Publication No. 2007 / 0072951 describes siloxanes comprising one siloxane unit and at least one silanol functional group, as well as their use as surfactants in the manufacture of polyurethane low-temperature curing foams. However, most silanol-functionalized siloxanes result in closed-cell foams that are prone to shrinkage.

[0008] Furthermore, German Patent Application Publication No. 3234462 describes a process for preparing highly elastic, low-temperature curing polyurethane foam using a polyether-modified siloxane containing siloxane blocks with 4 to 25 silicon atoms and 1.5 to 10 polyether blocks bonded to the siloxane blocks. The polyether units include oxyethylene (EO) units and oxypropylene (PO) units. Polyether-modified siloxanes containing fewer than 1.5 blocks per molecule are not described. Such polyethersiloxanes have the disadvantage of providing a narrow processing window and, in the case of MDI cold foams, can easily result in over-stabilized or closed-cell foams that tend to shrink.

[0009] International Publication No. WO 2010 / 081601 describes the preparation of polyurethane cold foams using linear siloxanes containing one siloxane unit and, in addition to Si-alkyl substitution in the chain, exactly one further organic modifying group bonded to the terminal silicon atom. Such siloxanes are also called alpha-siloxanes. A decisive disadvantage of alpha-siloxanes is that they are not available in pure form or are only very difficult to obtain, and generally they always contain a certain proportion of non-functionalized volatile polydimethylsiloxane.

[0010] German Patent Application Publication No. DE 10 2019 200 446 describes polyether-modified siloxanes having one siloxane unit and at least two OH groups, and a process for using them in the preparation of polyurethane foams using a near-critical or supercritical fluid, preferably supercritical CO2.

[0011] U.S. Patent Application Publication No. US 2019 / 110470 describes a low-foam surfactant composition comprising (a) a di-trisiloxane alkoxylate component of general formula (I) and (b) a mono-trisiloxane alkoxylate component of general formula (II). The general formula of compound (I) is (R 1 R 2 R 3 SiO)2(R 4 )Si-R 5 -Si(R 6 )(OSiR 7 R 8 R 9 )(wherein R 1 ~R 4 and R 6 ~R 9 are alkyl groups, R 5(I is a divalent polyalkylene oxide). Di-trisiloxane alkoxylate (I) is prepared in the presence of a hydrosilylated platinum catalyst by hydrosilylation of a trisiloxane compound MD+M having one SiH group with a polyether compound whose ends are sealed with allyl groups. D3 mentions that trisiloxane component (I) can be used for coating such coatings based on polyurethane resins. However, this document does not mention the use of di-trisiloxane component (I) in compositions for the preparation of polyurethane foams.

[0012] As a result, there is still a need for improved surface-active foam stabilizers that mitigate or avoid the shortcomings or disadvantages of the conventional technologies described above. In particular, an object of the present invention is to provide a surface-active foam stabilizer that enables the formation of high-quality polyurethane foams that have low or no VOC emissions, are open-celled, have little or no tendency to shrink, and exhibit excellent physical properties.

[0013] Summary of the Invention Surprisingly, it has been found that such an objective can be achieved by a siloxane-functional compound comprising at least two trisiloxane units bonded to a polyether-functional backbone, characterized by being represented by formula (1) of claim 1. The present invention also provides a siloxane composition comprising one or more of the siloxane-functional compounds of the present invention and optionally one or more further silicon-containing and / or silicon-free foam stabilizers.

[0014] The present invention also relates to the use of such siloxane-functionalized compounds or compositions containing them as additives in the manufacture of polyurethane foam.

[0015] Furthermore, the present invention also relates to a composition for preparing polyurethane foam, a) At least one isocyanate-reactive compound having at least two reactive groups on average per molecule on the isocyanate group, b) At least one polyisocyanate having at least two isocyanate groups on average per molecule, c) At least one foaming agent, d) at least one catalyst, e) At least one siloxane-functional compound or siloxane composition as described above and in more detail below. The present invention provides a composition containing [a certain substance].

[0016] The present invention provides a method for preparing a polyurethane foam, further comprising the steps of: (i) providing a composition comprising at least one isocyanate-reactive compound having an average of at least two isocyanate-reactive groups; a siloxane-functional compound or siloxane composition as described above and in more detail below; at least one blowing agent; at least one catalyst; and optionally one or more further additives; (ii) contacting the composition with a polyisocyanate or a mixture of polyisocyanates having an average of at least two isocyanate groups per molecule; and (iii) curing the composition under conditions of forming a polyurethane foam.

[0017] Furthermore, the present invention also relates to polyurethane foams prepared, for example, according to the above-described method for preparing polyurethane foams, in the presence of at least one siloxane-functional compound of the present invention, and articles comprising the polyurethane foams disclosed herein.

[0018] The present invention also relates to a method for preparing the siloxane-functionalized compounds of the present invention. This method comprises the step of reacting a polyether containing at least two carbon-carbon double bonds reactive to Si-H bonds with a hydrogen siloxane in the presence of a catalyst suitable for hydrosilylation, wherein the hydrogen siloxane is a hydrogen trisiloxane, a hydrogen tetrasiloxane, or a mixture thereof.

[0019] Advantageously, the siloxane-functionalized compounds, as defined in Appendix Claim 1, used as additives in compositions for manufacturing polyurethane foams, particularly molded foams, can positively influence the processing, physical, and emission properties of the polyurethane foams. For example, the siloxane-functionalized compounds of the present invention can provide a wide processing window for foam preparation, typically resulting in open-cell foams that are less prone to shrinkage. Furthermore, in contrast to linear siloxane compounds, which have also been used in the prior art for good distribution of polyurethane foam within molds, the siloxane-functionalized compounds according to the present invention can result in very low emissions in common emission tests such as VDA278, and can completely avoid emissions of silicon-containing compounds within the measurement accuracy. As a result, the foams of the present invention can be particularly useful for automotive interior applications, as they can reduce, if not completely eliminate, oil film deposits on windshields that obstruct the driver's view.

[0020] Modes for carrying out the invention The present invention is described further below by example, but is not limited to these exemplary embodiments. Where ranges, general formulas, or classes of compounds are given below, these should include not only the corresponding ranges or groups of compounds explicitly mentioned, but also all subranges and subgroups of compounds that can be obtained by removing individual values ​​(ranges) or compounds. For example, the range "1 to 10" is intended to include all subranges between the listed minimum value 1 and the listed maximum value 10 and all subranges including them, i.e., all subranges starting with a minimum value of 1 or more and ending with a maximum value of 10 or less, and all subranges in between, e.g., 1 to 6.3, or 5.5 to 10, or 2.7 to 6.1. Any endpoint of a range and / or numbers within those ranges can be combined within the scope of this disclosure. Where references are cited in the context of this specification, their contents should be entirely within the disclosure of the present invention, particularly in relation to the facts in the context in which the references are cited. Unless otherwise specified, parts and percentages are parts by weight and percentages by weight. Where parameters determined by measurement are specified below, unless otherwise specified, measurements were performed at room temperature (e.g., 20 ± 5°C, especially 20°C) and atmospheric pressure (e.g., 101.3 ± 5 kPa, especially 101 kPa). When chemical (or Japanese) formulas are used in this invention, the indicated index can represent both absolute and average values. In the case of polymer compounds, the index typically represents the average value. In this invention, the expressed structures and empirical formulas represent all possible isomers due to different arrangements of repeating units. Within the scope of this invention, where oligomers or polymer compounds such as polyethers, siloxanes, or polyethersiloxanes are described, they may have several different units, which may be randomly distributed (statistical oligomers or polymers), regularly arranged (block oligomers or block polymers), or occur as a gradient distribution in these compounds.

[0021] Unless otherwise indicated, the numerical parameters and ranges described in the following specification and the appended claims are approximations. Therefore, unless explicitly stated otherwise, all numbers, including those representing values, ranges, quantities, or percentages, can be read as if they begin with the word "about," even if the term does not appear explicitly. Although the broad ranges and parameters of the present invention are approximations, the numerical values ​​shown in specific embodiments are reported as accurately as possible. However, every numerical value contains errors that inevitably arise from the standard deviation in each measurement.

[0022] As used herein, the term “comprising” is understood to be open-ended and not to exclude the existence of any additional undescribed or unlisted elements, materials, components, or method steps. The terms “including,” “containing,” and similar terms are understood to be synonymous with “comprising.” As used herein, the term “consisting of” is understood to exclude the existence of any unspecified elements, components, or method steps. Although this disclosure is described using the term “comprising,” “consisting of,” or “consisting essentially of,” are also included in the scope of this disclosure.

[0023] As used herein, the singular forms "a," "an," and "the" refer to multiple objects unless otherwise explicitly indicated by the context.

[0024] As already described above, the present invention relates to a siloxane-functional compound comprising at least two trisiloxane units bonded to a polyether-functional skeleton, characterized in that the siloxane-functional compound is represented by formula (1) of claim 1.

[0025] As understood herein, a trisiloxane unit refers to a unit having three silicon atoms linked to one another by siloxane bonds, i.e., Si-O-Si bonds, some or preferably all of the silicon atoms being further substituted by one or more organic groups, such as linear or branched, saturated or unsaturated hydrocarbyl or heteroatom-containing organic groups, provided that one silicon atom is linked to a polyether functional skeleton. A trisiloxane unit can be described by the empirical formula -Si3O2R7 (wherein R represents the aforementioned organic group, particularly exemplified by alkyl groups). In a preferred embodiment of the present invention, some of the organic groups R of at least two trisiloxane units are alkyl groups, preferably methyl or ethyl groups. In a more preferred embodiment of the present invention, all alkyl residues R of at least two trisiloxane units are methyl groups, i.e., the trisiloxane unit is a heptamethylsiloxane unit. A heptamethylsiloxane unit can be illustrated by the following two structural formulas: [ka]

[0026] The linkage of trisiloxane units to the polyether functional framework is via silicon-carbon bonds. This allows each trisiloxane unit to be individually linked to the polyether functional framework via the terminal silicon atom of each trisiloxane unit or the central silicon atom of each trisiloxane unit. Preferably, all trisiloxane units in the siloxane functional compound are linked to the polyether functional framework via the central silicon atom of each trisiloxane unit. In a particularly preferred embodiment of the present invention, at least one of the trisiloxane units in the siloxane functional compound is a 1,1,1,3,5,5,5-heptamethyltrisiloxane unit. In a more preferred embodiment, all trisiloxane units in the siloxane functional compound are 1,1,1,3,5,5,5-heptamethyltrisiloxane units.

[0027] The siloxane-functionalized compounds of the present invention may contain one or more isocyanate-reactive functional groups. An isocyanate-reactive group is a functional group that can react with an isocyanate group in the event of covalent bond formation. Typical examples of isocyanate-reactive groups are amine groups, such as primary and secondary amine groups, and hydroxyl groups. The siloxane-functionalized compounds may contain combinations of amine and hydroxyl groups. One or more isocyanate-reactive functional groups are typically bonded to the polyether-functionalized skeleton of the siloxane-functionalized compound. The presence of one or more isocyanate-reactive functional groups causes the siloxane-functionalized compounds of the present invention to be incorporated into the polyurethane network when included in a composition for preparing polyurethane foam. In this way, the emission of the siloxane-functionalized compound from the polyurethane material can be avoided. Alternatively, the molecular structure of the siloxane-functionalized compounds of the present invention may not contain isocyanate-reactive functional groups, for example, primary amines, secondary amines, and / or hydroxyl groups. In this case, the siloxane-functionalized compound is not incorporated into the polyurethane structure and is therefore not consumed during the polymerization reaction. Nevertheless, the siloxane-functionalized compounds of the present invention are not volatile enough to evaporate under typical application conditions, such as those reflected in VDA Method 278, and typically undesirable stabilizer-related emissions from the resulting polyurethane material are reduced or absent. This makes the silicon compounds of the present invention particularly attractive for automotive applications.

[0028] The siloxane-functionalized compounds of the present invention can be characterized by their boiling point. The boiling point of the siloxane-functionalized compounds may be at least 245°C, preferably at least 280°C, or more preferably at least 310°C.

[0029] The siloxane-functionalized compounds of the present invention can be characterized by their number-average molecular weight (Mn). Mn can be determined, for example, preferably by gel permeation chromatography according to ISO 13885-1:2020. In a preferred embodiment of the present invention, the siloxane-functionalized compound has a number-average molecular weight Mn of at least 600 g / mol, preferably at least 800 g / mol, more preferably at least 1000 g / mol, and / or up to 4000 g / mol, preferably up to 3200 g / mol, or more preferably up to 3000 g / mol. The number-average molecular weight Mn of the siloxane-functionalized compound may be between any of the listed values, for example, 600 g / mol to 4000 g / mol, preferably 800 g / mol to 3200 g / mol, or more preferably 1000 g / mol to 3000 g / mol, and the number-average molecular weight Mn is determined by gel permeation chromatography.

[0030] As already stated, siloxane-functional compounds contain a polyether-functional skeleton. As understood herein, the term “polyether” means that the molecular structure of the main chain contains at least two ether moieties, i.e., a carbon-oxygen-carbon structure. The polyether-functional skeleton may contain additional heteroatoms, such as sulfur atoms, in addition to carbon atoms, hydrogen atoms, and oxygen atoms. The polyether-functional skeleton may be linear or branched and may contain cyclic units. The polyether-functional skeleton may contain, for example, one or more linear or branched hydrocarbyl or heteroatom-containing organic moieties, e.g., linear or branched C2-C2 100The polyether functional skeleton may contain hydrocarbyl or heteroatom-containing organic moieties. The polyether functional skeleton may contain one or more cyclic, aromatic and / or non-aromatic moieties, such as five-membered or six-membered cyclic moieties. In one embodiment of the present invention, at least some of the at least two ether moieties of the polyether functional skeleton are derived from ethylene oxide, propylene oxide and / or butylene oxide. For example, the polyether functional skeleton may be a copolymer in which repeating units can be derived from one or more epoxides such as ethylene oxide, propylene oxide, butylene oxide and / or allyl glycidyl ether.

[0031] The present invention is illustrated by structural formulas representing the entire siloxane-functional compound. Accordingly, according to one particularly preferred embodiment of the present invention, the siloxane-functional compound is of formula (1) [ka] (In the formula, R PO = [ka] R BO = [ka] h=1~2, i = 0 to 20, preferably 0 to 10, more preferably 0 to 5. j = 0 to 20, preferably 0 to 10, more preferably 0 to 5. k = 0 to 20, preferably 0 to 10, more preferably 0 to 5. Preferably, h+i+j+k≧1, The order of the units having indices h, i, j, and k in equation (1) is arbitrary, and the units may be in the form of blocks or statistically distributed in the structure of equation (1). R 12 =Each is individually selected from H or CH3, R 13=Each is individually selected from H or CH3, R 14 =Each individually represents OH, hydrogen, CH3, C2H5, CH2OH, or CH2-O-[CH2-CH2O] l [CH2-CH(CH3)O] m [CH2-CH(C2H5)O] n -R 16 Selected from, R 14 The order of the units having indices l, m, and n is arbitrary, and the units can be arranged in block units or in a statistically distributed manner. R 15 =Each is individually selected from hydrogen, CH3, C2H5, or CH2OH, R 16 =Each individually, hydrogen, CH3, and CH2-CH2-CH2-X 3 Or CH2-C(CH3)H-CH2-X 4 Selected from, l = 0 to 10, more comfortable 1 to 5. m = 0 to 10, comfort 0 to 5, n = 0 to 10, comfort level 1 to 5. X 1 , X 2 , X 3 and X 4 Each of these corresponds individually to an alkyltrisiloxane unit, preferably a heptamethyltrisiloxane unit, and more preferably a 1,1,1,3,5,5,5-heptamethyltrisiloxane unit. It is represented by [this].

[0032] Structural elements having indices h, i, j, and k are linked via oxygen-carbon bonds, and the order of structural elements in the polyether functional backbone is arbitrary. Furthermore, the units of structural elements having indices h, i, j, and k may be arranged as blocks, i.e., block polymer units, or they may be statistically distributed, i.e., distributed as statistical polymer units. Indices h, i, j, and k indicate the actual number of units present in the compound, i.e., whether only one compound species exists, or, in typical cases, the average of units averaged across all representative examples of the compound.

[0033] In one embodiment of the siloxane-functional compound according to the present invention, i=0, j=0, and k=0 That is the case.

[0034] In another embodiment of the siloxane-functionalized compound according to the present invention, h=1, i=0, j=0, k=0, R 12 =H, R 13 =H, R 14 =CH-O[CH2-CH2O] l [CH2-CH(CH3)O] m [CH2-CH(C2H5)O] n -R 16 , R 14 The order of the units having indices l, m, and n is arbitrary, and the units can be arranged in block units or in a statistically distributed manner. R 15 =C2H5, R 16 = Hydrogen, l = 0 to 10, more comfortable 1 to 5. m = 0 to 10, comfort 0 to 5, n = 0 to 10, comfort level 1 to 5. X 1 and X2 Each of these corresponds individually to an alkyltrisiloxane unit, preferably a heptamethyltrisiloxane unit, and more preferably a 1,1,1,3,5,5,5-heptamethyltrisiloxane unit.

[0035] In further embodiments of the siloxane-functionalized compounds according to the present invention, R 14 =CH-O[CH2-CH2O] l [CH2-CH(CH3)O] m [CH2-CH(C2H5)O] n -R 16 , R 14 The order of the units having indices l, m, and n is arbitrary, and the units can be arranged in block units or in a statistically distributed manner. l = 0 to 10, m=0~5, n = 0 to 10 That is the case.

[0036] In yet another embodiment of the siloxane-functionalized compound according to the present invention, R 14 =CH-O[CH2-CH2O] l [CH2-CH(CH3)O] m [CH2-CH(C2H5)O] n -R 16 , R 14 The order of the units having indices l, m, and n is arbitrary, and the units can be arranged in block units or in a statistically distributed manner. l=1~5, m=0~5, n=1~5 That is the case.

[0037] In preferred embodiments, the siloxane-functional compound according to the present invention is [ka] That is the case.

[0038] The siloxane-functionalized compounds of the present invention can be obtained by a method comprising the step of reacting a polyether containing at least two carbon-carbon double bonds reactive to the Si-H bond, i.e., a precursor of a polyether-functional skeleton, such as those described herein, with a hydrogen siloxane in the presence of a catalyst suitable for hydrosilylation, where the hydrogen siloxane is a hydrogen trisiloxane, a hydrogen tetrasiloxane, or a mixture thereof. In the siloxane-functionalized compounds thus obtained, the residues of the polyether containing at least two carbon-carbon double bonds reactive to the Si-H bond represent the polyether-functional skeleton. The hydrosilylation reaction itself is well known to those skilled in the art and will not be described in further detail herein. Catalysts suitable for hydrosilylation include, for example, Pt(0) or rhodium.

[0039] A particularly preferred hydrogen trisiloxane for preparing the siloxane-functionalized compounds of the present invention is 1,1,1,3,5,5,5-heptamethyltrisiloxane (HMTS). When industrial HMTS is used (which is a preferred option), it may also contain 1,1,1,3,5,7,7,7-octamethyltetrasiloxane (OMTS) as a by-product. Thus, the siloxane-functionalized compounds obtained according to the present invention may contain a small portion of octamethyltetrasiloxane units in addition to the major portion of heptamethyltrisiloxane.

[0040] Polyethers containing at least two carbon-carbon double bonds reactive to the Si-H bond can be prepared as described above herein. In a particularly preferred embodiment of the present invention, a polyether containing at least two carbon-carbon double bonds reactive to the Si-H bond is obtained by reacting an alcohol containing two carbon-carbon double bonds, preferably trimethylolpropanediallyl ether, with one or more epoxides preferably selected from ethylene oxide, propylene oxide, and butylene oxide. In an equally preferred alternative embodiment of the present invention, a polyether containing at least two carbon-carbon double bonds reactive to the Si-H bond is prepared by reacting an alcohol containing one carbon-carbon double bond, preferably allyl alcohol, with one or more epoxides preferably selected from ethylene oxide, propylene oxide, and butylene oxide, and then reacting with a compound containing one carbon-carbon double bond and one epoxide group, preferably allyl glycidyl ether, in the presence of one or more catalysts, each in which the reaction may be catalytic.

[0041] The present invention also provides a siloxane composition comprising one or more siloxane-functional compounds disclosed herein. The siloxane composition may include, for example, at least one siloxane-functional compound comprising a polyether-functional skeleton derived from a polyether of formula (1), and / or siloxane-functional compounds according to formulas (2) and / or (3). Furthermore, the siloxane composition may further comprise at least one siloxane-functional compound previously disclosed herein, in which case one or more trisiloxane units are replaced by tetrasiloxane units. Such tetrasiloxane units may include octamethyltetrasiloxane units, preferably 1,1,1,3,5,7,7,7-octamethyltetrasiloxane units. The tetrasiloxane units may also originate from the use of industrial mixtures of hydrogen siloxanes, such as industrial 1,1,1,3,5,5,5-heptamethyltrisiloxane (HMTS), in the preparation of the siloxane-functional compounds of the present invention. In this case, the use of industrial HTMS is advantageous because it eliminates the need for costly separation of hydrogen siloxane species.

[0042] In addition to the siloxane functional compounds described above, the siloxane composition may include at least one further silicon-containing foam stabilizer and / or at least one silicon-free foam stabilizer known in the art. Suitable examples include nonionic surfactants such as alcohol alkoxylates. A specific example of a conventional further silicon-containing foam stabilizer is the TEGOSTAB® product line from Evonik GmbH in Germany. One particularly suitable further foam stabilizer is TEGOSTAB® B 8734 LF 2.

[0043] The total amount of additional silicon-containing and silicon-free foam stabilizers in the siloxane composition can vary, if present. Typically, the total amount of additional silicon-containing and silicon-free foam stabilizers in the siloxane composition is as low as 50% by weight or less, for example 40% by weight or less, preferably 30% by weight or less, more preferably 25% by weight or less, or even more preferably 20% by weight or less, or 10% by weight or less, or about 0% by weight, based on the total weight of foam stabilizers in the siloxane composition. The total weight of foam stabilizers in the siloxane composition may include, for example, the amount of the siloxane functional compound of the present invention and its possible by-products, in addition to the amount of additional silicon-containing and silicon-free foam stabilizers.

[0044] The amount of the siloxane functional compound of the present invention (including its possible by-products) based on the total amount of foam stabilizers in the siloxane composition can vary, for example, at least 10% by weight, for example at least 20% by weight, or at least 30% by weight, or preferably at least 50% by weight, or more preferably at least 70% by weight, or even more preferably at least 90% by weight, or at least 95% by weight, or at least 99% by weight, or up to 100% by weight. The amount of the siloxane functional compound of the present invention (including its possible by-products) based on the total amount of foam stabilizers can be less than 100% by weight, for example less than 99% by weight, or less than 95% by weight, or less than 90% by weight, or less than 70% by weight, or less than 50% by weight, or less than 30% by weight, or less than 20% by weight, or less than 10% by weight. The proportion of the siloxane functional compound of the present invention (including its possible by-products), based on the total amount of foam stabilizers in the siloxane composition, may be between any of the listed values, for example, 10% to 100% by weight, or 20% to 90% by weight, or 30% to 70% by weight, or 40% to 60% by weight.

[0045] Furthermore, the siloxane composition of the present invention may contain further additives known in the art. For example, the siloxane composition may contain one or more solvents. The one or more solvents may be organic solvents in particular. Examples of suitable organic solvents include monofunctional polyether alcohols such as Synalox 100-15B by DOW or Carpol BP 07100 by Carpenter. By adding one or more solvents to the siloxane composition, the foam stabilizer can be diluted, thereby improving the meterability or miscibility of the siloxane composition to reaction matrices, such as compositions for preparing polyurethane foam. The siloxane composition of the present invention may contain, for example, 10% or more by weight of one or more solvents, for example, 20% or more by weight, or 30% or more by weight, or 40% or more by weight, or 50% or more by weight, or 60% or more by weight, or 70% or more by weight, or 80% or more by weight, or even 90% or more by weight, based on the total weight of the siloxane composition.

[0046] As already stated above, the siloxane-functional compounds disclosed herein are particularly suitable for use in the preparation of polyurethane foams. Accordingly, the present invention also relates to the use of the siloxane-functional compounds of the present invention or the siloxane compositions previously disclosed herein as additives in the production of polyurethane foams. Thus, the siloxane-functional compounds of the present invention can be used in the preparation of low-temperature curing and high-temperature curing foams, molded high-temperature or low-temperature curing foams, and foams prepared according to the slab stock method, and are particularly preferred for use in low-temperature curing molded foams, which are also known in the art as high-rebound (HR) molded foams. Furthermore, the siloxane-functional compounds of the present invention are generally useful in the preparation of flexible, semi-rigid, and rigid polyurethane foams.

[0047] The siloxane-functionalized compounds of the present invention can have advantageous properties for controlling the physical properties of the resulting polyurethane foam. The physical properties of the foam can be tested, for example, by crush force measurement. Crush force measurement generally examines the open-cell nature of the foam. For example, in the manufacture of automotive seat cushions, the open-cell nature of the foam is an important parameter for ensuring the dimensional stability of the molded product and preventing shrinkage after demolding. Polyurethane foam manufactured in the presence of one or more of the siloxane-functionalized compounds of the present invention can be characterized by relatively high intrinsic stability, as reflected by the FTC1 value obtained from crush force measurements further specified below. At the same time, the foam according to the present invention is typically characterized by a low tendency to shrink upon cooling. Furthermore, in particular, good stabilization against the effects of shear force allows the resulting foam to be very well-tuned and typically exhibit defect-free peripheral zones and skin. In addition, the siloxane-functionalized compounds of the present invention can provide effective control of cell size and cell size distribution, and can avoid an increase in the proportion of closed cells in the resulting foam. Importantly, the siloxane-functionalized compounds of the present invention do not tend to volatilize from the resulting polyurethane foam, and therefore can provide foam products with low or no emissions in commonly applied emission tests.

[0048] Therefore, the present invention also relates to a composition for preparing polyurethane foam, (a) at least one isocyanate-reactive compound having at least two reactive groups on average per molecule on the isocyanate group, (b) at least one polyisocyanate having at least two isocyanate groups on average per molecule, (c) at least one foaming agent, (d) at least one catalyst, and (e) At least one siloxane-functional compound or siloxane composition of the present invention This relates to a composition containing the following:

[0049] In a composition for preparing polyurethane foam, components (a) to (d) may include conventionally known substances. For example, components and substances disclosed in European Patent Application No. 0048984 may be used.

[0050] Typically, polyols are used as isocyanate-reactive compounds having at least two reactive groups per molecule on average, for example, at least two hydroxyl groups, attached to an isocyanate group. Polyols for the production of polyurethane foams are known to those skilled in the art. Preferred polyols are polyether polyols and polyester polyols, which are commonly used in the production of polyurethane foams. Polyether polyols are obtained by reacting a polyhydric alcohol or amine with an alkylene oxide. Polyester polyols are based on esters of polyhydric carboxylic acids (usually phthalic acid or terephthalic acid) and polyhydric alcohols (mainly glycols). Preferred examples of commercially available polyether triols include Arcol® 1374 and Desmophen® 10 WF 15 from Covestro GmbH in Germany.

[0051] Polyisocyanates for manufacturing polyurethane foam are also known in themselves. Polyisocyanates suitable for the purposes of the present invention include all polyfunctional organic isocyanates, such as 4,4'-diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI), and isophorone diisocyanate (IPDI). Prepolymer isocyanates are also particularly suitable. Suitable examples of commercially available polyisocyanates include SUPRASEC® 2447 from Huntsman Corporation in the United States and DESMODUR® T 80 from Covestro in Germany.

[0052] The ratio of isocyanate groups to isocyanate-reactive groups in the composition of the present invention is expressed as an NCO index, preferably in the range of 40 to 500, preferably 60 to 350, and particularly preferably 80 to 120. The NCO index represents the ratio of the amount of isocyanate groups actually used to the amount of isocyanate-reactive groups in the composition required for the stoichiometric reaction between the NCO groups and the active hydrogen groups of the polyol and other components in the composition that have active hydrogen groups. To obtain the index, the actual ratio [isocyanate groups] / [isocyanate-reactive groups] is then multiplied by 100. Thus, an NCO index of 100 represents a 1:1 molar ratio of reactive groups.

[0053] In the sense of the present invention, all conventionally used catalysts known to those skilled in the art that catalyze the polyurethane reaction between polyisocyanate and polyol, also known as a gel reaction, are suitable as catalysts for producing polyurethane foam.

[0054] Examples of suitable catalysts include, but are not limited to, the following classes of tertiary amine compounds: triethylenediamine, 1,4-diazabicyclo[2.2.2]octane-2-methanol, diethanolamine, N-[2-[2-(dimethylamino)ethoxy]ethyl]-N-methyl-1,3-propanediamine, 2-[[2-(2-(dimethylamino)ethoxy)ethyl]methylamino]ethanol, 1,1'-[(3-{bis[3-(dimethylamino)propyl]amino}propyl)imino]dipropane-2-ol, [3-(dimethylamino)propyl]urea, 1,3-bis[3-(dimethylamino)propyl]urea and / or general structure (1a) and / or structure (1b). [ka] (In the formula, X is oxygen, nitrogen, hydroxyl, structural NR) III Or NR III R IV The amino group or urea group (N(R V )C(O)N(R VI ) or N(R VII )C(O)NRVI R VII ) contains, and Y is an amino group NR VIII R IX or alkoxy group OR IX Includes R I,II It comprises identical or different linear or cyclic aliphatic or aromatic hydrocarbon groups having 1 to 8 carbon atoms, which may be functionalized with an OH group and / or contain hydrogen, R III-IX (These may be functionalized with an OH group, an NH or NH2 group, and / or contain hydrogen, and comprise identical or different linear or cyclic aliphatic or aromatic hydrocarbon groups having 1 to 8 carbon atoms, where m=0 to 4, preferably 2 or 3, n=2 to 6, preferably 2 or 3, i=0 to 3, preferably 0 to 2), [ka] (In the formula, R X The group comprises identical or different groups consisting of a linear, branched, or cyclic, aliphatic or aromatic hydrocarbon group having 1 to 18 carbon atoms that can be substituted with hydrogen and / or 0 to 1 hydroxyl groups and 0 to 1 NH2 groups, where Z is oxygen, NR X (or including CH2) Amine catalyst.

[0055] Further classes of suitable catalysts that may be preferred in the implementation of the present invention are metal compounds of metals Sn, Bi, Zn, Al, or K, particularly Sn, Zn, or Bi. Metal compounds can be divided into the following subgroups: organometallic compounds, organometallic salts, organic metal salts, and inorganic metal salts.

[0056] The expression "metalorganic or organometallic compounds" particularly encompasses the use of metal compounds having a direct carbon-metal bond for the purposes of this invention, and is also referred to here as metalorganic (e.g., tin organyl) or organometallic / organometallic compounds (e.g., organotin compounds). The expression "organometallic or metalorganic salts" particularly encompasses the use of metalorganic or organometallic compounds having salt properties for the purposes of this invention, i.e., ionic compounds in which the anion or cation is essentially organometallic (e.g., organotin oxides, organotin chlorides, or organotin carboxylates). The expression "organometallic salt" particularly encompasses the use of metal compounds that are metal salts (e.g., tin(II) carboxylate) that do not have a direct carbon-metal bond and at the same time either the anion or cation is an organic compound. For the purposes of this invention, the expression "inorganic metal salt" particularly includes the use of metal compounds or metal salts that are not organic compounds, such as metal chlorides (e.g., tin(II) chloride), but rather anions and cations.

[0057] Suitable organic and organometallic metal salts for use preferably contain alkoxides, mercaptanic acids, or carboxylate anions, such as acetates, 2-ethylhexanoate, octanoate, isononanoate, decanoate, neodecanoate, ricinoleate, laurate, and / or oleate, particularly preferably 2-ethylhexanoate, ricinoleate, neodecanoate, or isononanoate.

[0058] As a general principle, metal-containing catalysts suitable for use are preferably selected such that they do not have unpleasant inherent odors and are inherently toxicologically safe, and that the resulting polyurethane systems, particularly polyurethane foams, have the lowest possible level of catalyst-related emissions.

[0059] For compositions used to prepare polyurethane floss foam, thermal latent catalysts, i.e., catalysts that exhibit their effectiveness only above a specific activation temperature and thus cause the foam to cure more slowly, are particularly suitable.

[0060] Suitable catalysts for compositions used to prepare polyurethane foam include gel catalysts.

[0061] In a preferred embodiment of the present invention, the siloxane-functional compound or siloxane composition of the present invention is used in combination with a tertiary amine catalyst according to structure (1a) to prepare a polyurethane foam, the latter comprising at least one reactive group for isocyanate groups, particularly a hydroxyl (OH) group or an amino (NH,NH2) group.

[0062] It may also be preferable to combine one or more metal compounds, such as those described herein, with one or more amine catalysts of formula (1a) and / or (1b).

[0063] Particularly suitable catalysts include the DABCO® and Polycat® series catalysts from Evonik® of Germany, such as DABCO® DMEA (amine catalyst), DABCO® NE 300, and DABCO® NE 1550.

[0064] The amount of catalyst in a composition for preparing polyurethane foam can vary and may depend, in particular, on the properties and function of the catalyst. For example, the total amount of catalyst in the composition may be 10 pphp or less, for example 5 pphp or less, or preferably 2 pphp or less, or more preferably 1 pphp or less, or 0.001 pphp or more, for example 0.01 pphp or more, or 0.1 pphp or more, or 0.5 pphp or more. The total amount of catalyst may be between any of the listed values, for example 10 pphp to 0.001 pphp, or preferably 0.01 pphp to 5 pphp, or more preferably 0.1 pphp to 1 pphp. The unit pphp refers to parts (grams) per 100 g of polyol.

[0065] Foaming can be achieved by employing one or more blowing agents in appropriate amounts in a composition for preparing polyurethane foam. Blowing agents are generally known in the art and include, for example, water, methylene chloride, liquefied gases, or other inert gases such as nitrogen, carbon dioxide (which may be added by itself), iso- and cyclopentanes, methane, helium, and argon. Suitable liquefied gases include aliphatic and alicyclic fluorocarbons that vaporize below the temperature of the foam mass. Such gases may be at least partially fluorinated and otherwise halogenated. Suitable fluorocarbon blowing agents for use in the foamed compositions of the present invention for preparing rigid polyurethane foam include trichloromonofluoromethane, dichlorodifluoromethane, 1,1-dichloro-l-fluoroethane, 1,1,1-trifluoro-2-fluoro-3,3-difluoro-4,4,4-trifluorobutane, hexafluorocyclobutane, octafluorocyclobutane, and hydrofluoroolefins. Another useful class of blowing agents includes thermally unstable compounds that release gas upon heating, such as N,N'-dimethyl-N,N'-dinitrosoterephthalamide. A particularly preferred blowing agent is water, which reacts with the polyisocyanate compound in the composition under the formation of carbon dioxide. The amount of blowing agent in the composition can vary. For example, the total amount of blowing agent in the composition may be 10 pphp or less, for example preferably 7 pphp or less, or more preferably 5 pphp or less, or 0.1 pphp or more, for example preferably 1 pphp or more, or preferably 2 pphp or more. The total amount of blowing agent may be between any of the listed values, for example 0.1 to 10 pphp, or preferably 1 pphp to 7 pphp, or more preferably 2 pphp to 5 pphp.

[0066] In addition to the components described herein, compositions for preparing polyurethane foam may also contain, as necessary, other additives and auxiliaries conventionally used in the art. For example, a composition for preparing polyurethane foam may contain one or more additives selected from the group including, for example, dyes, pigments, fillers, antistatic additives, crosslinking agents, chain extenders, bubble openers, nucleating agents, thickeners, fragrances, bubble expanders, plasticizers, curing accelerators, additives to prevent low-temperature flow, aldehyde scavengers, additives to enhance the resistance of polyurethane foam to hydrolysis, compatibilizers (emulsifiers), adhesion promoters, and hydrophobic additives. The total amount of additives and auxiliaries can vary and may be 10 pphp or less, for example, 8 pphp or less, or 5 pphp or less, or 3 pphp or less.

[0067] The amount of at least one siloxane-functional compound or siloxane composition of the present invention in a composition for preparing polyurethane foam can vary. The amount may be, for example, at least 0.0001% by weight or more, for example 0.001% by weight or more, or 0.01% by weight or more, based on the total weight of the composition. The amount may be 10% by weight or less, for example 5% by weight or less, or 2% by weight or less, based on the total weight of the composition. At least one siloxane-functional compound or siloxane composition of the present invention may be present in the composition in an amount between any of the listed values, for example, 0.0001% by weight to 10% by weight, or preferably 0.001% by weight to 5% by weight, or more preferably 0.01% by weight to 2% by weight, based on the total weight of the composition.

[0068] Alternatively, the amount of at least one siloxane-functional compound of the present invention in a composition for preparing polyurethane foam can be expressed in parts (grams) per 100 g of polyol, which is abbreviated as pphp. In a preferred embodiment of the present invention, the amount of at least one siloxane-functional compound of the present invention may be at least 0.001 pphp, for example at least 0.005 pphp, or at least 0.01 pphp, or at least 0.02 pphp, or at least 0.03 pphp, or at least 0.05 pphp, and / or up to 1.5 pphp, for example at most 1.0 pphp, or at most 0.5 pphp, or at most 0.1 pphp, or at most 0.05 pphp. The amount of at least one siloxane-functional compound may be between any of the listed values, for example 0.001 pphp to 1.5 pphp, or preferably 0.005 pphp to 0.1 pphp. If a composition contains two or more of the siloxane-functional compounds of the present invention, the above amount refers to the sum of the amounts of the individual siloxane-functional compounds in each composition for preparing the polyurethane foam, and therefore the total amount of the siloxane-functional compounds of the present invention.

[0069] The composition for preparing polyurethane foam may optionally contain one or more additional silicon-containing foam stabilizers and / or one or more silicon-free foam stabilizers, which are different from the siloxane-functionalized compounds of the present invention. The total amount of additional silicon-containing and silicon-free foam stabilizers in the composition, if present, can vary, for example, at least 0.05 pphp, e.g., at least 0.07 pphp, or at least 0.1 pphp, or at least 0.2 pphp, or at least 0.3 pphp, or at least 0.5 pphp, and / or up to 1.5 pphp, e.g., up to 1.4 pphp, or up to 1.3 pphp, or up to 1.2 pphp. The total amount of additional silicon-containing and silicon-free foam stabilizers in the composition may be between any of the listed values, for example, 0.05 pphp to 1.5 pphp, or 0.05 pphp to 0.2 pphp. However, preferably, the composition for preparing polyurethane comprises only one or more of the siloxane-functional compounds of the present invention and does not contain further silicon-containing and silicon-free foam stabilizers that have been conventionally applied.

[0070] The compositions for preparing polyurethane foam may also include the siloxane compositions of the present invention as described herein. The siloxane compositions may include one or more of the siloxane functional compounds of the present invention and their possible by-products, and optionally one or more further silicon-containing and silicon-free foam stabilizers as described above. The amount of the siloxane composition in the polyurethane composition can vary, for example, at least 0.05 pphp, for example at least 0.07 pphp, or at least 0.1 pphp, or at least 0.2 pphp, or at least 0.3 pphp, or at least 0.5 pphp, and / or up to 1.5 pphp, for example up to 1.4 pphp, or up to 1.3 pphp, or up to 1.2 pphp. The amount of the siloxane composition in the composition for preparing polyurethane foam may be between any of the listed values, for example, 0.05 pphp to 1.5 pphp, or 0.05 pphp to 0.2 pphp. If the siloxane composition contains one or more solvents, the amount of each solvent is not considered in the calculation of the amount of the siloxane composition in the polyurethane composition.

[0071] The polyurethane foam according to the present invention is (i) Providing a composition comprising at least one isocyanate-reactive compound having at least two reactive groups on average to an isocyanate group, a siloxane-functional compound of the present invention or a siloxane composition of the present invention, at least one blowing agent, at least one catalyst, and optionally one or more further additives, (ii) The step of contacting the composition with a polyisocyanate or a mixture of polyisocyanates having at least two isocyanate groups on average per molecule, (iii) A step of curing the composition under the formation of a polyurethane foam. It can be prepared by a method that includes [a specific component].

[0072] The manufacture of polyurethane foam can, in principle, be carried out by conventional methods as described in the prior art. The preparation of polyurethane foam is known to those skilled in the art. A comprehensive overview can be found, for example, in G. Oertel, Polyurethane Handbook, 2nd edition, Hanser / Gardner Publications Inc., Cincinnati, Ohio, 1994, pp. 177-247. Further details of possible starting materials, catalysts, and auxiliaries and additives can be found, for example, in Kunststoffhandbuch [Plastics Handbook], volume 7, Polyurethane [Polyurethanes], Carl-Hanser-Verlag Munich, 1st edition 1966, 2nd edition 1983 and 3rd edition 1993.

[0073] Furthermore, it should be understood that the method steps defined herein do not follow a fixed time series. Therefore, curing may have already occurred when the composition comes into contact with the polyisocyanate.

[0074] In a preferred embodiment of the present invention, a method for preparing a polyurethane foam is a method for preparing a molded polyurethane foam. For this purpose, the method may include the step of transferring a composition containing polyisocyanate to a mold before the composition is cured. The mold may be preheated to a temperature of 40°C to 60°C or higher.

[0075] The present invention also relates to a polyurethane foam prepared preferably according to the methods previously disclosed herein, in the presence of at least one siloxane-functional compound of the present invention. Thus, the polyurethane foam of the present invention can be a flexible polyurethane foam, a rigid polyurethane foam, a semi-rigid polyurethane foam, a molded polyurethane foam, a high-rebound polyurethane foam, a viscoelastic foam, a hyper-soft polyurethane foam, or a monofilament foam. In a preferred embodiment of the present invention, the polyurethane foam of the present invention is a molded polyurethane foam.

[0076] The polyurethane foam of the present invention can be characterized by its emission characteristics, which are determined according to VDA standard 278 and the thermal desorption analysis methods described in the experimental section below. In a preferred embodiment of the present invention, the polyurethane foam has a VOC (volatile organic compound) value of 40 ppm or less, e.g., 30 ppm or less, or 20 ppm or less, or 10 ppm or less, or 5 ppm or less, or even 0 ppm, according to VDA 278. The polyurethane foam may have a FOG value of 250 ppm or less, e.g., 200 ppm or less, or 150 ppm or less, or 100 ppm or less, or 50 ppm or less, or 20 ppm or less, or 10 ppm or less, reflecting the proportion of condensable substances according to VDA 278.

[0077] The polyurethane foam of the present invention can be characterized in particular by its low emission of silicon-containing species. The emission of silicon-containing substances can be described by the silicon-containing volatile organic compound value (silicon-containing VOC value) and the proportion of condensable silicon-containing substances (silicon-containing FOG value), which are determined according to the VDA method 278 and the methods described in the experimental section below. In a particularly preferred embodiment of the present invention, the silicon-containing VOC value of the polyurethane foam of the present invention is 10 ppm or less, for example 7 ppm or less, or preferably 5 ppm or less, or even 0 ppm. The proportion of condensable silicon-containing substances (silicon-containing FOG value) may be 10 ppm or less, for example 7 ppm or less, or preferably 5 ppm or less, or even 0 ppm.

[0078] The polyurethane foam according to the present invention can be characterized by the number of bubbles per cm, i.e., the bubble count, as determined in accordance with DIN EN15702:2009-04. Thus, the value of the bubble count may be at least 7.0, e.g., at least 8.0, or at least 9.5 and / or up to 12.0, e.g., up to 11.5, or up to 11.0. The value of the bubble count may be between any of the enumerated values, e.g., 7.0 to 12.0, or 8.0 to 11.0.

[0079] Furthermore, the polyurethane foam according to the present invention is preferably distinguished by its intrinsic stability or crush hardness, which is reflected by an FTC1 value (in Newtons) determined according to the crush force measurements described in the following experimental sections of this specification. The FTC1 value of the polyurethane foam according to the present invention is preferably at least 900N, for example at least 950N, or at least 1000N, or at least 1050N, or at least 1100N. The FTC1 value is typically up to 1500N, for example at least 1450N, or at least 1400N. The FTC1 value may be between any of the listed values, for example 900N to 1500N, or 1000N to 1400N.

[0080] The present invention also relates to articles made of or containing the polyurethane foam of the present invention. In a preferred embodiment of the present invention, articles are refrigerator insulation, insulation panels, sandwich elements, pipe insulation, spray foam, one-component or 1.5-component can foam, imitation wood, modeling foam, packaging foam, mattresses, furniture cushioning, automotive seat cushioning, airplane or train seat cushioning, headrests, armrests, instrument panels, automotive interior trim, automotive headlining, sound-absorbing materials, steering wheels, shoe soles, carpet backing foam, filter foam, sealing foam, sealants, adhesives, or coatings. In a more preferred embodiment of the present invention, articles are automotive seat cushioning, instrument panels, sound-absorbing materials, headrests, armrests, automotive headlining, or steering wheels. Even more preferably, articles are automotive seat cushioning materials. The polyurethane foam of the present invention can also be used in the manufacture of articles such as those described herein.

[0081] Aspects of the present invention include, but are not limited to, the following numbered clauses.

[0082] 1. A siloxane-functional compound containing at least two trisiloxane units bonded to a polyether-functional skeleton.

[0083] 2. The siloxane-functional compound according to Clause 1, wherein at least one of the trisiloxane units comprises a heptamethyltrisiloxane unit, preferably a 1,1,1,3,5,5,5-heptamethyltrisiloxane unit.

[0084] 3. The siloxane-functional compound according to clause 1 or 2, wherein at least two trisiloxane units are individually bonded to a polyether-functional backbone via Si-C bonds.

[0085] 4. The siloxane-functional compound according to any one of the clauses 1 to 3, wherein the molecular structure of the siloxane-functional compound does not contain an isocyanate-reactive functional group, or the molecular structure of the siloxane-functional compound contains at least one isocyanate-reactive functional group, preferably at least one hydroxyl group.

[0086] 5. A siloxane-functional compound according to any one of the clauses 1 to 4, wherein the polyether-functional skeleton comprises two or more ether moieties derived from ethylene oxide, propylene oxide, and / or butylene oxide.

[0087] 6. The siloxane-functionalized compound has a number-average molecular weight (M) in the range of 600 g / mol to 4000 g / mol, preferably 800 g / mol to 3200 g / mol, or more preferably 1000 g / mol to 3000 g / mol. n A siloxane-functional compound according to any one of clauses 1 to 5, having the following characteristics:

[0088] 7. The polyether-functionalized skeleton can be converted to a siloxane-functionalized compound by hydrosilylation using hydrogen trisiloxane, general formula (1) M r M' s D g D' p (Formula (1)), (where M=X-(O 1 / 2 Preferably [ka] M'=X'-(O 1 / 2 ) D=Y-(O 1 / 2 )2, preferably each individually [ka] or [ka] Selected from, D'=Y'-(O 1 / 2)2, preferably each individually [ka] or [ka] Selected from, r = 0 to 2, preferably 1 or 2. s = 0 to 2, preferably 0 or 1. g = 0 to 65, preferably 0 to 35, more preferably 1 to 15. p = 0 to 10, preferably 0 to 5, more preferably 0 to 3. Each X is individually selected from monovalent linear or branched hydrocarbyl moieties having 1 to 20 carbon atoms with a carbon-carbon double bond that is reactive to the Si-H bond. X' = ​​each individually represents a hydrogen atom, a monovalent linear or branched ethylenically saturated hydrocarbyl moiety having 1 to 20 carbon atoms, C6H5, or C(O)-R 2 Preferably selected from hydrogen or a monovalent linear or branched ethylenically saturated hydrocarbyl moiety having 1 to 8 carbon atoms, more preferably selected from hydrogen or a monovalent linear or branched ethylenically saturated hydrocarbyl moiety having 1 to 4 carbon atoms. Y = Each is individually selected from the ethylenically saturated organyl moiety of a divalent straight or branched chain having two or more carbon atoms. Y' = Each is individually selected from divalent linear or branched organyl moieties having two or more carbon atoms, each possessing a carbon-carbon double bond reactive to the Si-H bond. R 1 Each element is individually selected from hydrogen or an alkyl group having 1 to 10 carbon atoms, preferably hydrogen or methyl, and more preferably hydrogen. R 2 Each of these is individually selected from hydrogen, CH3, C2H5, CH2C6H5, or C(O)CH3. R 3= each individually, OH, hydrogen, CH3, C2H5, CH2OH, or CH2-O-[CH2-CH2O] a [CH2-CH(CH3)O] b [CH2-CH(C2H5)O] c -R 5 selected from, R 3 The order of the units having indices a, b, and c in R 4 = each individually, selected from hydrogen, CH3, C2H5, or CH2OH, R 8 = each individually, selected from hydrogen, CH3, C2H5, or CH2OH, R 10 = each individually, selected from hydrogen, CH3, C2H5, or CH2OH, R 5 = each individually, selected from hydrogen or CH3, R 6 =CH2-O-[CH2-CH2O] d [CH2-CH(CH3)O] e [CH2-CH(C2H5)O] f -R 7 、R 6 The order of the units having indices d, e, and f in R 9 =CH2-O-[CH2-CH2O] x [CH2-CH(CH3)O] y [CH2-CH(C2H5)O] z -R 11 、R 9 The order of the units having indices x, y, and z in R 7 = each individually, selected from hydrogen, CH2-CH=CH2 or CH2-C(CH3)=CH2, R 11Each is individually selected from hydrogen, CH2-CH=CH2, or CH2-C(CH3)=CH2. a = 0 to 10, comfort level 1 to 5. b = 0 to 10, more comfortably 0 to 5. c = 0 to 10, moreover 1 to 5, d = 0 to 10, comfort level 1 to 5. e = 0 to 10, comfortable 0 to 5. f = 0 to 10, more preferably 1 to 5. x = 0 to 10, comfort level 1 to 5. y = 0 to 10, more preferably 0 to 5. z = 0 to 10, comfort level 1 to 5. However, r+p≧2, However, g+p≧1, preferably ≧3, (However, s+r=2) A siloxane-functional compound according to any one of the clauses 1 to 6, derived from a polyether containing at least two carbon-carbon double bonds, represented by [formula].

[0089] 8. In formula (1), M [ka] D = Each individually, [ka] or [ka] Selected from, D' = Each individually, [ka] or [ka] A siloxane compound selected from the siloxane compounds described in Clause 7.

[0090] 9.Equation (2) [ka] (In the formula, R PO = [ka] R BO = [ka] h = 0 to 2, preferably 0 or 1. i = 0 to 20, preferably 0 to 10, more preferably 0 to 5. j = 0 to 20, preferably 0 to 10, more preferably 0 to 5. k = 0 to 20, preferably 0 to 10, more preferably 0 to 5. Preferably h+i+j+k≧1, more preferably h+i+j+k>3. The order of the units having indices h, i, j, and k in equation (2) is arbitrary, and the units may be in the form of blocks or statistically distributed in the structure of equation (2). R 12 =Each is individually selected from H or CH3, R 13 =Each is individually selected from H or CH3, R 14 =Each of these is OH, hydrogen, CH3, C2H5, CH2OH, or CH2-O-[CH2-CH2O] l [CH2-CH(CH3)O] m [CH2-CH(C2H5)O] n -R 16 Selected from, R 14 The order of the units having indices l, m, and n is arbitrary, and the units can be arranged in block units or in a statistically distributed manner. R 15 =Each is individually selected from hydrogen, CH3, C2H5, or CH2OH, R 16 =Each individually, hydrogen, CH3, and CH2-CH2-CH2-X3 Or CH2-C(CH3)H-CH2-X 4 Selected from, l = 0 to 10, more comfortable 1 to 5. m = 0 to 10, comfort 0 to 5, n = 0 to 10, comfort level 1 to 5. X 1 , X 2 , X 3 , and X 4 Each of these corresponds individually to an alkyltrisiloxane unit, preferably a heptamethyltrisiloxane unit, and more preferably a 1,1,1,3,5,5,5-heptamethyltrisiloxane unit. A siloxane-functional compound as described in any of clauses 1 to 8, represented by [the specified symbol].

[0091] 10.In formula (1), M [ka] D= [ka] p=0, r=2, s=0, g=1, R 1 = Hydrogen, R 3 =Each one is CH2-O-[CH2-CH2O] a [CH2-CH(CH3)O] b [CH2-CH(C2H5)O] c -R 5 Selected from, R 3 The order of the units having indices a, b, and c is arbitrary, and the units can be arranged in block units or in a statistically distributed manner. R 4 =C2H5, R 5 = Hydrogen, a = 0 to 5, b = 0 to 5, c = 0 to 5, a+b+c≧3 Siloxane-functionalized compounds as described in Clause 7 or 8.

[0092] 11.Equation (3) [ka] (In the formula, o = 1 to 10, preferably 1 to 5, more preferably 1 to 2. q = 0 to 20, preferably 0 to 10, more preferably 0 to 5. t = 0 to 20, preferably 0 to 10, more preferably 0 to 5, u = 0 to 20, preferably 0 to 10, more preferably 0 to 5. The order of the units having indices o, q, t, and u in equation (3) is arbitrary, and the units may be in block form or statistically distributed in the structure of equation (3). R 17 =Each individually, hydrogen, alkyl having 1 to 16 carbon atoms, CH2-CH2-CH2-X 6 CH2-C(CH3)H-CH2-X 7 , C6H5, or C(O)-R 19 Preferably H, an alkyl group having 1 to 8 carbon atoms, CH2-CH2-CH2-X 6 Or CH2-C(CH3)H-CH2-X 7 , more H, CH2-CH2-CH2-X 6 Or CH2-C(CH3)H-CH2-X 7 Selected from, R 18 =Each individually, hydrogen, alkyl having 1 to 16 carbon atoms, CH2-CH2-CH2-X 6 CH2-C(CH3)H-CH2-X 7 , C6H5, or C(O)-R 19 Preferably H, an alkyl group having 1 to 8 carbon atoms, CH2-CH2-CH2-X 6 Or CH2-C(CH3)H-CH2-X 7 , more H, CH2-CH2-CH2-X 6 Or CH2-C(CH3)H-CH2-X7 Selected from, R 19 Each of these is individually selected from hydrogen, CH3, C2H5, CH2C6H5, or C(O)CH3. X 5 ~X 7 Each of these corresponds individually to an alkyltrisiloxane unit, preferably a heptamethyltrisiloxane unit, more preferably a 1,1,1,3,5,5,5-heptamethyltrisiloxane unit, and R 17 and R 18 If the total does not contain siloxane units, then o≧2, and R 17 and R 18 (If they together contain one siloxane unit, then o≧1) A siloxane-functional compound as described in any of clauses 1 to 8, represented by [the specified symbol].

[0093] 12.In formula (1), M [ka] D = Each individually, [ka] or [ka] Selected from, D'= [ka] X' = ​​Hydrogen plate r=1, s=1, g=1~15, p=1~3, R 1 = Hydrogen, R 9 =CH2-O-[CH2-CH2O] x [CH2-CH(CH3)O] y [CH2-CH(C2H5)O] z -R11 , R 9 The order of the units having indices x, y, and z is arbitrary, and the units can be arranged in block units or in a statistically distributed manner. R 10 = Hydrogen, R 11 =CH2-C(CH3)=CH2, x = 0 ~ 5, y=0~5, z = 0 to 5. Siloxane-functionalized compounds as described in Clause 7 or 8.

[0094] 13. A siloxane-functional compound according to any one of clauses 7, 8, 10, or 12, wherein the polyether of formula (1) containing at least two carbon-carbon double bonds is obtained by reacting an alcohol having at least one carbon-carbon double bond reactive to a Si-H bond with one or more epoxides and optionally a compound containing a carbon-carbon double bond reactive to a Si-H bond and an epoxy group.

[0095] 14. The reaction is carried out in the presence of one or more catalytic amounts of the siloxane-functional compound described in Clause 13.

[0096] 15. The siloxane-functionalized compound according to Clause 13 or 14, wherein the alcohol having at least one reactive carbon-carbon double bond in the Si-H bond is selected from (meth)allyl alcohol and trimethylolpropanediallyl ether.

[0097] 16. One or more epoxides are selected from ethylene oxide, propylene oxide, and 1,2-butylene oxide, and are siloxane-functional compounds as described in any of clauses 13 to 15.

[0098] 17. A siloxane-functional compound according to any one of the clauses 13 to 16, wherein the compound containing a reactive carbon-carbon double bond and an epoxy group in the Si-H bond is an allyl glycidyl ether.

[0099] 18. A siloxane composition comprising one or more siloxane-functionalized compounds described in Clauses 1 to 17, and optionally one or more further silicon-containing and / or silicon-free foam stabilizers.

[0100] 19. The siloxane composition according to Clause 18, further comprising one or more siloxane-functionalized compounds as defined in Clauses 1 to 17, wherein one or more trisiloxane units are replaced by tetrasiloxane units, and at least one of the tetrasiloxane units optionally comprises an octamethyltetrasiloxane unit, preferably a 1,1,1,3,5,7,7,7-octamethyltetrasiloxane unit.

[0101] 20. A composition for preparing polyurethane foam, a) At least one isocyanate-reactive compound having at least two reactive groups on average per molecule on the isocyanate group, b) At least one polyisocyanate having at least two isocyanate groups on average per molecule, c) At least one foaming agent, d) at least one catalyst, e) at least one siloxane-functionalized compound as described in any of clauses 1 to 17 or a siloxane composition as described in clause 18 or 19, and f) Depending on the case, one or more additives selected from the group including dyes, pigments, fillers, antistatic additives, crosslinking agents, chain extenders, bubble openers, nucleating agents, thickeners, fragrances, bubble expanders, plasticizers, curing accelerators, additives to prevent low-temperature flow, aldehyde scavengers, additives to enhance the resistance of polyurethane foam to hydrolysis, compatibilizers (emulsifiers), adhesion promoters, and hydrophobic additives. A composition containing the following:

[0102] 21. The composition according to Clause 20, wherein at least one siloxane-functional compound or siloxane composition is present in the composition in an amount of 0.0001% to 10% by weight, preferably 0.001% to 5% by weight, or more preferably 0.01% to 2% by weight, based on the total weight of the composition.

[0103] 22. A method for preparing polyurethane foam, - A step of providing a composition comprising at least one isocyanate-reactive compound having at least two reactive groups on average on an isocyanate group, at least one siloxane-functional compound according to any one of the clauses 1 to 17 or a siloxane composition according to clause 18 or 19, at least one blowing agent, at least one catalyst, and optionally one or more further additives, - The step of contacting the composition with a polyisocyanate or a mixture of polyisocyanates having at least two isocyanate groups on average per molecule, - A step of curing the composition under the formation of a polyurethane foam. Methods that include...

[0104] 23. A polyurethane foam prepared preferably according to the method described in Clause 22, in the presence of at least one siloxane-functional compound described in any of Clauses 1 to 17, wherein the polyurethane foam is preferably a flexible polyurethane foam, a rigid polyurethane foam, a semi-rigid polyurethane foam, a molded polyurethane foam, a high-rebound polyurethane foam, a viscoelastic foam, a hyper-soft polyurethane foam, or an integral foam, more preferably a molded polyurethane foam.

[0105] 24. A silicon-containing volatile organic compound (silicon-containing VOC) value of 10 ppm or less, preferably 5 ppm or less, determined according to VDA standard 278. - The percentage of condensable silicon-containing material (Si content FOG value) is determined in accordance with VDA standard 278, and is 10 ppm or less, preferably 5 ppm or less. A polyurethane foam as described in Clause 23, representing one or both of the above.

[0106] 25. Articles comprising polyurethane foam as described in Clause 23 or 24, preferably refrigerator insulation, insulation panels, sandwich elements, pipe insulation, spray foam, one-component or 1.5-component can foam, imitation wood, modeling foam, packaging foam, mattresses, furniture cushioning, automotive seat cushioning, airplane or train seat cushioning, headrests, armrests, instrument panels, automotive interior trim, automotive headlinings, sound-absorbing materials, steering wheels, shoe soles, carpet backing foam, filter foam, sealing foam, sealants, adhesives, coatings, or for use in the manufacture of corresponding products, or more preferably automotive seat cushioning, instrument panels, sound-absorbing materials, headrests, armrests, automotive headlinings, steering wheels, or even more preferably automotive seat cushioning.

[0107] 26. A method for preparing a siloxane-functional compound as described in any of Clauses 1 to 17, comprising the step of reacting a polyether containing at least two carbon-carbon double bonds reactive to Si-H bonds with a hydrogen siloxane in the presence of a catalyst suitable for hydrosilylation, wherein the hydrogen siloxane is a hydrogen trisiloxane, a hydrogen tetrasiloxane, or a mixture thereof.

[0108] 27. The method according to Clause 26, wherein the hydrogen siloxane is 1,1,1,3,5,5,5-heptamethyltrisiloxane or 1,1,1,3,5,7,7,7-octamethyltrisiloxane or a mixture thereof.

[0109] 28. A polyether having at least two reactive carbon-carbon double bonds in a Si-H bond is as defined in any one of clauses 7, 8, 10, 12, or 13 to 17, according to the method of clause 26 or 27.

[0110] 29. The method according to any one of the claims 26 to 28, wherein a polyether having at least two carbon-carbon double bonds reactive to the Si-H bond is prepared by reacting an alcohol having two carbon-carbon double bonds, preferably trimethylolpropanediallyl ether, with one or more epoxides preferably selected from ethylene oxide, propylene oxide, and butylene oxide, in the presence of one or more catalytic amounts of catalysts, if applicable.

[0111] 30. A polyether containing at least two carbon-carbon double bonds reactive to the Si-H bond is prepared by reacting an alcohol containing one carbon-carbon double bond, preferably an allyl alcohol, with one or more epoxides preferably selected from ethylene oxide, propylene oxide, and butylene oxide, and then reacting it with a compound containing a carbon-carbon double bond reactive to the Si-H bond and one epoxy group, preferably an allyl glycidyl ether, in the presence of one or more catalysts, each in which the reaction is preferably complete.

[0112] 31. Use of a siloxane-functional compound as described in any of Clauses 1 to 17 or a siloxane composition as described in either Clause 18 or 19 as an additive in the manufacture of polyurethane foam.

[0113] In the embodiments described below, the present invention is explained by example, but the scope of application of the present invention is determined by the entire specification and claims, and is not intended to limit the present invention to the embodiments described in the examples.

[0114] Examples All quantities mentioned throughout the examples are in parts by weight unless otherwise specified.

[0115] 1. Synthesis of polyether precursors for preparing siloxane-functional compounds 1.1 Synthesis of Polyether 1 (PE1) To prepare polyether PE1, 561.6 g of trimethylolpropanediallyl ether (obtained from Perstorp GmbH in Malmö, Sweden, as Trimethylolpropane Diallylether 90, purity 90% or higher) and 9.8 g of sodium methylate were placed under nitrogen in a 3-liter autoclave. The reaction mixture was then heated to 115°C with stirring, and the system was evacuated to an internal pressure of 100 mbar to remove volatile components by distillation. 60.0 g of propylene oxide was added under constant stirring and cooling to maintain the temperature of the reaction mixture at 115°C. After a noticeable pressure drop, a further 676.0 g of propylene oxide was continuously added over 2 hours with stirring and cooling to maintain the temperature of the reaction mixture at 115°C and a maximum (absolute) internal reactor pressure of 3.0 bar. After complete addition and a further reaction time of 2.5 hours, the reactor was degassed again, the reaction mixture was cooled to 95°C, the reaction mixture was neutralized with H3PO4 (i.e., 30% by weight of H3PO4 in water based on the total mass of the solution), and 500 ppm of Anox 20 AM® was added based on the total mass of the composition. Water was removed by vacuum distillation, and the precipitated salt was filtered off. In this way, 1273.5 g of a clear yellow polyether was obtained. The structure PE1 of the polyether, which is reproduced below, 1 The values ​​were determined by 1H NMR, hydroxyl value, and iodine value determination. PE1 is the average formula, where the number of repeating units represents the average value averaged over all representative examples of the compound. [ka]

[0116] 1.2 Synthesis of polyether 2 (PE2) To prepare polyether PE2, 281.3 g of trimethylolpropanediallyl ether (obtained from Perstorp GmbH in Malmö, Sweden as Trimethylolpropane Diallylether 90, purity 90% or higher) and 4.9 g of sodium methylate were placed under nitrogen in a 3 liter autoclave. The reaction mixture was then heated to 115°C with stirring, and the system was evacuated to an internal pressure of 100 mbar to remove volatile components by distillation. 50.0 g of a mixture of ethylene oxide (EO) and 1,2-butylene oxide (BO), with a molar ratio of EO to BO equal to 3:2, was added with stirring and cooling to maintain the temperature of the reaction mixture at 115°C. After a noticeable pressure drop, 392.0 g of a mixture of ethylene oxide (EO) and 1,2-butylene oxide (BO), with a molar ratio of EO to BO equal to 3:2, was continuously added over 1 hour under stirring and cooling to maintain the temperature of the reaction mixture at 115°C and a maximum (absolute) internal reactor pressure of 3.0 bar. After a further reaction time of 1 hour, 116.0 g of 1,2-butylene oxide was continuously added under stirring and cooling to achieve a final molar ratio of EO to BO equal to 3:3, maintaining the temperature of the reaction mixture at 115°C and a maximum (absolute) internal reactor pressure of 3.0 bar over 3 minutes. After complete addition and a subsequent 4-hour reaction time, the reactor was degassed again, the reaction mixture was cooled to 95°C, the reaction mixture was neutralized with H3PO4 (i.e., 30% by weight of H3PO4 in water based on the total mass of the solution), and 500 ppm of Anox 20 AM® was added based on the total mass of the composition. Water was removed by vacuum distillation, and the precipitated salt was filtered off. In this way, 798.9 g of a clear yellow polyether was obtained. The structure PE2 of the polyether, which is reproduced below, 1 The values ​​were determined by 1H NMR, OH value, and iodine value determination. PE2 is the average formula, where the number of repeating units represents the average value averaged over all representative examples of the compound. Furthermore, although the repeating units are shown as blocks in PE2, the individual units are partially statistically distributed in the structure. Terminal BO units are attached during the final alkoxylation step. [ka]

[0117] 2. Preparation of siloxane-functional compounds from the obtained polyethers 2.1 Siloxane Solution 1 (according to the present invention) In a 500 mL three-necked flask equipped with a KPG stirrer, reflux condenser, and dropping funnel, 113.3 g of polyether PE1 was charged, and Pt in the form of a toluene solution of Karstedt catalyst (w(Pt)=2%) was added in an amount of 15 ppm based on the total weight of the polyether and heptamethyltrisiloxane. The mixture was heated to 80°C. Then, 86.7 g of 1,1,1,3,5,5,5-heptamethyltrisiloxane (purity >99 wt%) was slowly added via a dropping funnel over 30 minutes. The exothermic reaction was initiated. During the addition, the temperature rose to a maximum of 102°C. After the addition was complete, stirring was continued at 90°C for 2 hours. The conversion rate of the SiH functional group was then determined by volumetric measurement. For this purpose, a small sample of the reaction mixture was reacted with a sodium butanoxide solution (w(NaOBu)=5%), and the volume of hydrogen formed was measured. The SiH conversion rate was 100%. A clear solution containing a siloxane-functional compound (siloxane 1) having the following general structure was obtained: [ka]

[0118] The obtained solution was blended as a 5% by weight solution in a monofunctional polyether alcohol (Dow's Synalox 100-15B) with a hydroxyl value of 84 mg KOH / g, and the resulting solution (siloxane solution 1) was used in the foaming experiment.

[0119] 2.2 Siloxane Solution 2 (according to the present invention) In a 500 mL three-necked flask equipped with a KPG stirrer, reflux condenser, and dropping funnel, 117.8 g of polyether PE2 was charged, and Pt in the form of a toluene solution of Karstedt catalyst (w(Pt)=2%) was added at a concentration of 15 ppm based on the total weight of the polyether and heptamethyltrisiloxane. The mixture was heated to 80°C. Then, 60.0 g of 1,1,1,3,5,5,5-heptamethyltrisiloxane (purity >99%) was slowly added via a dropping funnel over 30 minutes. The exothermic reaction was initiated. During the addition, the temperature rose to a maximum of 100°C. After the addition was complete, stirring was continued at 90°C for 4 hours. Next, the conversion rate of the SiH functional group was determined by volumetric measurement. For this purpose, a sample of the reaction mixture was reacted with a sodium butanoxide solution (w(NaOBu)=5%), and the volume of hydrogen formed was measured. The SiH conversion rate was 99%. Subsequently, the reaction product was decontaminated to remove slightly volatile components under a vacuum at 130°C (<1 mbar). A clear solution containing a siloxane-functional compound (siloxane 2) having the following general structure was obtained: [ka]

[0120] The obtained solution was blended as a 7% by weight solution in a monofunctional polyether alcohol (Dow's Synalox 100-15B) with a hydroxyl value of 84 mg KOH / g, and the resulting solution (siloxane solution 2) was used in the foaming experiment. 2.3 Siloxane solution 3 (not according to the present invention)

[0121] 80.6 g of polyether PE3 was charged into a 500 mL three-necked flask equipped with a KPG stirrer, reflux condenser, and dropping funnel. Pt in the form of a toluene solution of Karstedt catalyst (w(Pt)=2%) was added at a concentration of 15 ppm based on the total weight of the polyether and heptamethyltrisiloxane. The mixture was heated to 80°C. Then, 80.1 g of 1,1,1,3,5,5,5-heptamethyltrisiloxane (purity >99) was slowly added via a dropping funnel over 30 minutes. The exothermic reaction was initiated. During the addition, the temperature rose to a maximum of 98°C. After the addition was complete, stirring was continued at 90°C for 90 minutes. The conversion rate of the SiH functional group was then determined by volumetric measurement. For this purpose, a sample of the reaction mixture was reacted with a sodium butanoxide solution (w(NaOBu)=5%) and the volume of hydrogen formed was measured. The SiH conversion rate was 100%. A clear solution containing a siloxane-functional compound (siloxane 3) having the following general structure was obtained: [ka]

[0122] The obtained solution was blended as a 1% by weight solution in a monofunctional polyether alcohol (Dow's Synalox 100-15B) with a hydroxyl value of 84 mg KOH / g, and the resulting solution (siloxane solution 3) was used in the foaming experiment.

[0123] 3. Polyurethane foam (Formulation 1) for testing physical foam properties Polyurethane foam was prepared in the laboratory as a so-called hand-mixed molded foam according to Formulation 1, detailed below. The foam was prepared at 22±1°C and a pneumatic pressure of 762 mmHg, according to the following specifications. A heat-resistant aluminum mold measuring 40 × 40 × 10 cm was used for foam preparation. The mold was treated with a solvent-based release agent before foam preparation.

[0124] Collapse properties were determined using the foam of formulation 1 (FTC analysis), and the skin and surrounding zones were analyzed.

[0125] The composition 1 is described in Table 1 below. The amounts of each stabilizer are described in Table 2 below. [Table 1] 1 : Polyether triol (5000 g / mol) from Covestro 2 : Triethanolamine 3 : Demineralized water 4 : Gel catalyst from Evonik (registered trademark) 5 : Amine catalyst of Evonik (registered trademark) 6 : Used in the form of the aforementioned siloxane solution, and the amount refers to the entire siloxane solution (including the siloxane compound and the carrier solvent). 7 : Foam stabilizer from Evonik (registered trademark) 8 : Mixture of 40% SUPRASEC (registered trademark) 2447 (methylene diphenyl diisocyanate from Huntsman) and 60% DESMODUR (registered trademark) T80 (Toluol diisocyanate T80 from Covestro), NCO = 41.3%, NCO index = 95 [Table 2]

[0126] For the preparation of the polyurethane foam, polyol DESMOPHEN® 10WF15 was used in the relative amounts specified in Table 1. The other components of the formulation were converted according to the proportions shown in Tables 1 and 2, where, for example, 1.0 part (1.0 pphp) of a component means 1 g of this substance per 100 g of polyol. For the preparation of the foam, the polyol, along with all other formulation components except the diisocyanate mixture, was brought into contact with the respective siloxane solutions and mixed with a paddle stirrer at 1000 rpm for 1 minute to form a premix. The diisocyanate mixture was then added to the premix within a few seconds, and the mixture was stirred at 2500 rpm for 7 seconds. The polymerization and foaming reaction mixture was transferred within a few seconds to an aluminum mold preheated to 40°C, and the mold was closed until demolding. After 10 minutes, the product was demolded as a finished foam cushion.

[0127] Next, the foam body was compressed by crushing force measurement and then manually crushed after the 10th measurement cycle, as described below. The foam body was then weighed and stored overnight. Skin quality was determined as described below. The foam cushion was cut to approximately 1 / 4 of its length, and the surrounding zone of each foam cushion was visually evaluated as a whole and classified as excellent, good, fair, or poor (severe defects). Air bubble counting was performed on the cut edge side of the foam.

[0128] Measurement methods for characterizing physical form properties a) Number of bubbles per 1 cm (bubble count): The number of bubbles is optically determined on the cross-section according to the method described in DIN EN15702:2009-04.

[0129] b) Measurement of crushing force The compressive force (FTC) was measured using a Tinius Olsen H10K-S universal testing machine (manufacturer number: 672) with a maximum measurement of 10kN. The measurement was performed for each polyurethane foam as follows: Immediately after demolding (less than 15 seconds thereafter), the foam pad was placed in the starting position of the FTC machine, the measuring leg / measuring plate / probe was placed 115mm away from the base plate, in contact with the foam, and moved at a speed of 500mm / min towards the base plate. The initial foam thickness was measured when the force reached 5N. Without stopping at 5N, the measuring leg continued to penetrate the foam at a speed of 500mm / min until the distance to the base plate reached 50mm. At this point, the force FTC1 was acquired. There was no interruption to the measurement. The measuring leg returned to the starting position, i.e., 115mm from the base plate, at a speed of 500mm / min, thus completing the first cycle. Without delay, nine additional cycles are performed following the same protocol as the first cycle (i.e., FTC2-FTC10). After 10 cycles, the measuring leg stops at the starting position. The foam pad is then manually pressed completely by hand and placed back into the measuring position of the FTC machine. Another cycle (11th) is performed under the same conditions as the first 10 cycles. Here, the foam thickness at the end is measured in the same way as the foam thickness at the start of the first cycle. The initial foam thickness is determined by FTC1. The remaining closed-cell content is described by the difference FTC10-FTC11, and the collapseability of the foam is read from the shape of the curve (how quickly the FTC drops). In particular, a rapid decrease in the FTC value during the first few cycles (FTC1-FTC2, FTC2-FTC3) indicates high (good) collapseability. The FTC11 value (i.e., the hardness of the new foam) can be used as a measure of foam hardening.

[0130] c) Skin quality The overall skin quality of each foam cushion was visually evaluated and classified into Excellent, Good, Fair, and Poor (severely defective).

[0131] d) Quality of the surrounding zone The foam cushions were cut to approximately one-quarter of their length, and the surrounding zones of each foam cushion were visually evaluated as a whole and classified as excellent, good, acceptable, or poor (severely defective).

[0132] result Polyurethane foam cushions were prepared with Formulation 1 (see above) and analyzed as described above to test the effects of siloxane on press-on hardness (FTC measurement), bubble count, foam weight, and the quality of the skin and surrounding zones. The results are shown in Table 3. [Table 3]

[0133] Example 1 corresponds to a foam without stabilizers and is a comparative example. It exhibits only low intrinsic stability at the boundary (FTC1=837N), and its peripheral zone shows subcutaneous defects. Furthermore, the foam of Comparative Example 2 was prepared by adding TEGOSTAB® B 8734 LF 2, a product commonly used as a stabilizer for molded foams, as another reference. The foam of Comparative Example 2 does not tend to shrink upon cooling, has sufficiently high stability (FTC1=1363N), and also has a very well-conditioned or defect-free peripheral zone. The foams of Examples 3-7, to which the siloxane functional compounds according to the present invention are applied in siloxane solutions 1 and 3, demonstrate that the use of siloxane functional compounds according to the present invention yields foams with good material properties similar to those of the foam in Comparative Example 2. For example, the initially measured crush hardness FTC1 value was in the range of 1100-1350N in all examples, FTC10 was always less than 200N, and the final crush hardness FTC11 after manual crushing was slightly lower than that of Comparative Example 2. The FTC data of the foams of Examples 3-9 show similarly good crushability compared to the foam of Comparative Example 2. The peripheral zone is significantly improved compared to the foam of Comparative Example 1 and, in most cases, is adjusted to be equivalent to or as good as the foam of Comparative Example 2, which represents an ideal state, by the use of TEGOSTAB® B 8734 LF 2. Furthermore, the foams of Examples 8 and 9 demonstrate, through examples of siloxane solution 2 according to the present invention, that the combination of the siloxane functional compound according to the present invention and a very small amount of the established stabilizer TEGOSTAB® B 8734 LF 2 results in superior foam. These foams are characterized by high intrinsic stability (FTC1 = 1117N and 1308N) and good or excellent peripheral properties. A further advantage of this combination compared to conventional stabilizer-containing foams is demonstrated below by the effluent profile of a foam containing the siloxane-functionalized compound according to the present invention, which contains a small amount of conventional stabilizer.

[0134] 4. Polyurethane foam (Formulation 2) for testing stabilizer-related foam discharge. The polyurethane foam was prepared in the laboratory as a so-called hand-mixed molded foam according to Formulation 2, which will be described in detail below. The preparation of the foam was carried out at an air pressure of 22 ± 1 °C and 762 mmHg according to the following specifications. For the preparation of the foam, a heatable aluminum mold with dimensions of 40 × 40 × 10 cm was used. Before the preparation of the foam, the mold was treated with a solvent-based release agent.

[0135] Using the foam of Formulation 2, the emission characteristics were determined by thermal desorption analysis.

[0136] Formulation 2 is described in Table 4 below. The amounts of each stabilizer are described in Table 4 below.

Table 4

Table 5

[0137] For the preparation of the polyurethane foam, polyol Arcol® 1374 was used in the relative amounts specified in Table 4. The other components of the formulation were converted according to the proportions shown in Tables 4 and 5, where, for example, 1.0 part (1.0 pphp) of a component means 1 g of this substance per 100 g of polyol. For the preparation of the corresponding foam, the polyol, along with all other formulation components except the diisocyanate, was brought into contact with the respective siloxane solutions and mixed with a paddle stirrer at 1000 rpm for 1 minute to form a premix. The diisocyanate was then added to the premix within a few seconds, and the mixture was stirred at 2500 rpm for 7 seconds. The polymerization and foaming reaction mixture was transferred within a few seconds to an aluminum mold preheated to 55°C, and the mold was closed until demolding. After 4 minutes, the product was demolded as a finished foam cushion.

[0138] The foam samples obtained in this manner were subjected to thermal desorption analysis according to the following procedure to characterize the foam extrusions. Thermal desorption analysis to characterize foam extrusions

[0139] Polyurethane pads were characterized in terms of the type and amount of organic substances that may be released from them. This was done by thermal desorption analysis using the VDA278 standard (05 / 2016) of the German Association of the Automotive Industry ("Verband der Automobilindustrie eV", VDA). This analysis determines two semi-quantitative sum values ​​that allow for the estimation of the emissions of slightly volatile organic compounds, i.e., VOC values, and the proportion of condensable substances, i.e., FOG values. Furthermore, the individual substances of the emissions are determined.

[0140] Thermal desorption analysis was performed using a TDS-3 type GC-MS instrument equipped with a KAS-4 injection system from Gerstel GmbH, a manufacturer in Mülheim an der Ruhr, Germany. Tenax® desorption tubes were used. In addition, a 7890A gas chromatograph and an Agilent Technologies 5975C mass spectrometer were utilized. An Agilent Technologies HP Ultra 2 column with dimensions of 50 m (length), 0.32 mm (inner diameter), and 0.52 μm (film thickness) was used. Helium was the carrier gas.

[0141] Sample preparation and thermal desorption analysis were performed as follows: After demolding the foam, they were stored at 21°C and approximately 50% relative humidity for 24 hours. Subsequently, test specimens were collected uniformly at appropriate and representative points across the width of the (cooled) molded parts. The samples were then wrapped in aluminum foil and sealed in polyethylene bags.

[0142] From each form sample, 10–15 mg, weighed to the nearest 0.1 mg, was placed in the center of the desorption tube. A helium stream was flowed over the sample, and the sample was heated to 90°C for 30 minutes to cast volatile organic compounds (VOCs). The volatile substances (VOCs) emitted during this process were guided by an inert gas stream to a cold trap in a temperature-programmable evaporator cooled by liquid nitrogen, where they were captured in the cooling trap. After the bake-out stage was complete, the cold trap was rapidly heated to 280°C. During this process, the focusing material was evaporated, separated by a gas chromatography separation column, and then detected by mass spectrometry. Subsequently, a helium stream was flowed over the sample again, and the sample was heated to 120°C for 60 minutes to cast even some semi-volatile compounds called FOGs. The FOG substances were also captured in the cooling trap and further analyzed for VOCs by GC according to the method described above. Calibration using a reference material allowed for semi-quantitative estimation of emissions expressed in "μg / g". Toluene (VOC value) was used as a reference substance for VOC analysis, and n-hexadecane was used as a reference substance for FOG values. Based on their mass spectra and retention indices, signal peaks can be assigned to the substances. The VOC values ​​of detected VOC substances identified as containing silicon are called silicon-containing VOCs (similar to silicon-containing FOGs).

[0143] result Stabilizer-related emissions were analyzed by thermal desorption analysis using VDA278 on the foam of Formulation 2 (see above), and by using each stabilizer listed in Table 5. Furthermore, a foam of Formulation 2 without stabilizers was prepared and used as a reference. The amount of stabilizer emissions used in each case was determined by the difference between the value measured for each foam and the blank value of the reference foam without stabilizers, for example, VOC(stabilizer of foam in Example 12) = VOC(foam in Example 12) - VOC(reference foam without stabilizers). The results are shown in Table 6. [Table 6]

[0144] The foam of Example 12 was prepared using a commonly applied stabilizer optimized for applications sensitive to emissions, but it has an emission rate of 50 ppm VOC, completely eliminated from the silicon-containing compound. However, the foams of Examples 13-14, to which the siloxane-functionalized compound of the present invention is applied, show no emissions within the measurement accuracy (VOC=0 ppm). The stabilizer-related fogging values ​​(FOG values) of the foams of Examples 13-14 are 10 and 70 ppm, respectively. However, no silicon-containing compound is detected; i.e., the VOC and FOG values ​​of the Si-containing compound are 0 ppm in all cases. Therefore, the siloxane-functionalized compound according to the present invention, i.e., siloxane solutions 1-2, show no silicon-containing emissions in thermal desorption analysis at the tested amounts. Thus, the foams containing the stabilizer according to the present invention are characterized not only by very good mechanical foam properties, including a very good peripheral zone, but also by excellent emission properties.

[0145] In the foam of Example 16, when the siloxane solution 2 according to the present invention was combined with a small amount of TEGOSTAB® B 8734 LF 2, only a very low silicon-containing VOC emission of 10 ppm was produced (an 80% reduction compared to the foam of Example 12). The Si-containing FOG emission was 0 ppm in the foam of Example 16 as well. As a result, the combination of the siloxane functional compound according to the present invention and the aforementioned conventional stabilizer TEGOSTAB® B 8734 LF 2 not only provides very good mechanical foam properties, including a very good peripheral zone, but also provides improved emission properties compared to the use of conventional stabilizers alone.

Claims

1. A siloxane-functional compound comprising at least two trisiloxane units bonded to a polyether-functional skeleton, wherein formula (1) 【Chemistry 1】 (In the formula, R ＰＯ = 【Chemistry 2】 R ＢＯ = 【Transformation 3】 h = 1 to 2, i = 0 to 20, preferably 0 to 10, more preferably 0 to 5, j = 0 to 20, preferably 0 to 10, more preferably 0 to 5, k = 0 to 20, preferably 0 to 10, more preferably 0 to 5, Preferably, h + i + j + k ≥ 1, The order of the units having indices h, i, j, and k in equation (1) is arbitrary, and the units may be in the form of blocks or statistically distributed in the structure of equation (1). R １２ = Each individually, H or CH ３ Selected from, R １３ = Each individually, H or CH ３ Selected from, R １４ = each individually, OH, hydrogen, CH ３ , C ２ H ５ , CH ２ OH or CH ２ -O-[CH ２ -CH ２ O] ｌ [CH ２ -CH(CH ３ )O] ｍ [CH ２ -CH(C ２ H ５ )O] ｎ -R １６ selected from, and the order of the units having indices l, m, and n in R １４ is arbitrary, and the units can be arranged in block units or distributed statistically, R １５ = Hydrogen, CH, each individually. ３ , C ２ H ５ or CH ２ Selected from OH, R １６ = Hydrogen, CH, each individually. ３ ,CH ２ -CH ２ -CH ２ -X ３ or CH ２ -C(CH ３ ) H-CH ２ -X ４ Selected from, l = 0 to 10, more preferably 1 to 5. m = 0 to 10, more preferably 0 to 5, n = 0 to 10, more preferably 1 to 5, X １ , X ２ , X ３ and X ４ Each of these corresponds individually to an alkyltrisiloxane unit, preferably a heptamethyltrisiloxane unit, and more preferably a 1,1,1,3,5,5,5-heptamethyltrisiloxane unit. A siloxane-functional compound characterized by being represented by [a specific symbol].

2. i = 0, j = 0, and k = 0 The siloxane-functional compound according to claim 1.

3. h=1, i = 0, j = 0, k = 0, R １２ =H、 R １３ =H、 R １４ = CH - O [CH ２ -CH ２ O] ｌ [television] ２ -CH(CH ３ )O] ｍ [television] ２ -CH(C) ２ H ５ )O] ｎ -R １６ , R １４ The order of the units having indices l, m, and n is arbitrary, and the units can be arranged in block units or in a statistically distributed manner. R １５ =C ２ H ５ 、 R １６ = Hydrogen, l = 0 to 10, more preferably 1 to 5. m = 0 to 10, more preferably 0 to 5, n = 0 to 10, more preferably 1 to 5, X １ and X ２ Each of these corresponds individually to an alkyltrisiloxane unit, preferably a heptamethyltrisiloxane unit, more preferably a 1,1,1,3,5,5,5-heptamethyltrisiloxane unit. A siloxane-functional compound according to claim 1 or 2.

4. R １４ = CH - O [CH ２ -CH ２ O] ｌ [television] ２ -CH(CH ３ )O] ｍ [television] ２ -CH(C) ２ H ５ )O] ｎ -R １６ , R １４ The order of the units having indices l, m, and n is arbitrary, and the units can be arranged in block units or in a statistically distributed manner. l = 0 to 10, m = 0 to 5, n = 0 to 10 The siloxane-functional compound according to any one of claims 1 to 3.

5. R １４ =CH−O[CH ２ −CH ２ O] ｌ [CH ２ −CH(CH ３ )O] ｍ [CH ２ −CH(C ２ H ５ )O] ｎ −R １６ 、R １４ The order of the units having indices l, m, and n in R, R is arbitrary, and the units can be arranged in block units or distributed statistically, l = 1 to 5, m = 0 to 5, n = 1 to 5 The siloxane-functional compound according to any one of claims 1 to 3.

6. A siloxane composition comprising one or more siloxane-functional compounds according to any one of claims 1 to 5, and optionally one or more further silicon-containing and / or silicon-free foam stabilizers.

7. The siloxane composition according to claim 6, further comprising one or more siloxane-functionalized compounds as defined in any one of claims 1 to 5, wherein one or more trisiloxane units are replaced by tetrasiloxane units, and at least one of the tetrasiloxane units optionally comprises an octamethyltetrasiloxane unit, preferably a 1,1,1,3,5,7,7,7-octamethyltetrasiloxane unit.

8. A composition for preparing polyurethane foam, a) At least one isocyanate-reactive compound having at least two reactive groups on average per molecule on the isocyanate group, b) At least one polyisocyanate having at least two isocyanate groups on average per molecule, c) at least one foaming agent, d) at least one catalyst, e) at least one siloxane-functional compound according to any one of claims 1 to 5 or a siloxane composition according to claim 6 or 7, f) Depending on the case, one or more additives selected from the group including dyes, pigments, fillers, antistatic additives, crosslinking agents, chain extenders, bubble openers, nucleating agents, thickeners, fragrances, bubble expanders, plasticizers, curing accelerators, additives to prevent low-temperature flow, aldehyde scavengers, additives to enhance the resistance of polyurethane foam to hydrolysis, compatibilizers (emulsifiers), adhesion promoters, and hydrophobic additives. A composition containing the following:

9. A method for preparing polyurethane foam, - A step of providing a composition comprising: at least one isocyanate-reactive compound having at least two reactive groups on average on an isocyanate group; at least one siloxane-functional compound according to any one of claims 1 to 5 or a siloxane composition according to claim 6 or 7; at least one blowing agent; at least one catalyst; and optionally one or more further additives. - The step of contacting the composition with a polyisocyanate or a mixture of polyisocyanates having at least two isocyanate groups on average per molecule, - A step of curing the composition under the formation of a polyurethane foam. Methods that include...

10. A polyurethane foam prepared preferably according to the method of claim 9 in the presence of at least one siloxane-functional compound described in any one of claims 1 to 5, wherein the polyurethane foam is preferably a flexible polyurethane foam, a rigid polyurethane foam, a semi-rigid polyurethane foam, a molded polyurethane foam, a high-rebound polyurethane foam, a viscoelastic foam, a hyper-soft polyurethane foam, or an integral foam, more preferably a molded polyurethane foam.

11. - The silicon-containing volatile organic compound (silicon-containing VOC) value is determined in accordance with VDA standard 278 to be 10 ppm or less, preferably 5 ppm or less. - The percentage of condensable silicon-containing material (Si content FOG value) is determined in accordance with VDA standard 278 to be 10 ppm or less, preferably 5 ppm or less. The polyurethane foam according to claim 10, relating to one or both of the above.

12. Articles comprising the polyurethane foam described in claim 10 or 11, preferably refrigerator insulation, insulation panels, sandwich elements, pipe insulation, spray foam, one-component or 1.5-component can foam, imitation wood, modeling foam, packaging foam, mattresses, furniture cushioning, automotive seat cushioning, airplane or train seat cushioning, headrests, armrests, instrument panels, automotive interior trim, automotive headlining, sound-absorbing materials, steering wheels, shoe soles, carpet backing foam, filter foam, sealing foam, sealants, adhesives, coatings, or for use in the manufacture of corresponding products, or more preferably automotive seat cushioning materials, instrument panels, sound-absorbing materials, headrests, armrests, automotive headlinings, steering wheels, or even more preferably automotive seat cushioning materials.

13. A method for preparing a siloxane-functional compound according to any one of claims 1 to 5, comprising the step of reacting a polyether containing at least two carbon-carbon double bonds reactive to Si-H bonds with a hydrogen siloxane in the presence of a catalyst suitable for hydrosilylation, wherein the hydrogen siloxane is a hydrogen trisiloxane, a hydrogen tetrasiloxane, or a mixture thereof.

14. - The hydrogen siloxane is 1,1,1,3,5,5,5-heptamethyltrisiloxane or 1,1,1,3,5,7,7,7-octamethyltrisiloxane, or a mixture thereof. The method according to claim 13.

15. Use of a siloxane-functional compound according to any one of claims 1 to 5 or a siloxane composition according to claim 6 or 7 as an additive in the manufacture of polyurethane foam.

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