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    • 专利摘要:
    Polyurethane foam, its use and its method of manufacture Method for the manufacture of polyurethane foams using compositions containing at least one halogen-containing olefin (fluorine) blowing agent and at least one siloxane of formula (i) )
    公开号:BR112012002073B1
    申请号:R112012002073-0
    申请日:2010-06-29
    公开日:2019-05-07
    发明作者:Martin Glos；Carsten Schiller；Christian Eilbracht
    申请人:Evonik Degussa Gmbh；
    IPC主号:
    专利说明:

    Descriptive Report of the Invention Patent for POLYURETHANE FOAM, ITS USE AND ITS MANUFACTURING METHOD. [001] The present invention relates to a method for making polyurethane foam using compounds, which support olefinic double bonds as a blowing agent and polyether siloxane copolymers, polyurethane foams, which contain this blowing agent and copolymers siloxane as well as the use of these polyurethane foams.
    STATE OF THE TECHNIQUE [002] Halogenated hydrocarbons, especially fluoride-containing hydrocarbons, have a wide application as an expansion agent for the manufacture of foams. However, these compounds have disadvantages in relation to their potential to damage the ozone layer, Ozon Depletion Potential (ODP), and to contribute to the warming of the Earth's atmosphere, Global Warming Potential (GWP). For this reason, alternative expansion agents have been developed with at least ODP and GWP. A current trend is the use of compounds containing halogen with an olefinic double bond in the molecule. It is also hydrohalo-olefin (HHO). Especially hydrofluorolefins (HFO) and hydrochlorofluorolefins (HCFO) are described as new blowing agents.
    [003] Patent documents US 2008/125505 and US 2008/125506 describe the use of fluorine-containing olefins as a blowing agent for foams. These expansion agents have minimal GWP and ODP.
    [004] The patent document WO 2008/121790 describes mixtures of hydrofluorolefins (HFO) and hydrochlorofluorolefins (HCFO) as a blowing agent for the manufacture of foams.
    [005] Patent document WO 2008/121779 describes a blowing agent composition, which contains at least one hydrochloro-olefin.
    Petition 870190016792, of 02/19/2019, p. 4/31
    2/20 [006] The patent document WO 2007/053670 describes blowing agent for the manufacture of foams containing unsaturated fluorocarbons. Bromofluorolefins are also mentioned.
    [007] Patent applications WO 2009/073487 and WO 2009/089400 describe cis-1,1,1,4,4,4-hexafluoro-2-butene and 2chloro-3,3,3-trifluoropropene as expansion in the manufacture of polyurethane and polyisocyanurate foams.
    [008] Patent document EP 2 004 773 describes a composition for use in air conditioning equipment, refrigeration installations, thermal pumps, containing a fluoro-olefin and at least one other component. Also described, among other things, is its use as a foam blowing agent.
    [009] The patent document US 5,900,185 describes olefins containing bromine, which have a short shelf life in the atmosphere and its use as a blowing agent for foams.
    [0010] Patent documents WO 2007/002703 and US 2008/207788 and WO 2009/067720 describe HFO-1234ze and HCFO1233zd or mixtures, which contain these substances together with ethers containing fluorine, in various applications including use as a blowing agent for foams PU.
    [0011] The patent document WO 2009/003165 describes mixtures of hydrofluorolefins (HFO) and / or hydrochlorofluorolefins (HCFO) with stabilizers, which prevent decomposition during storage, handling and use but allow in the atmosphere. As stabilizers, they are used as radical, oxygen and acid scavengers as well as polymerization inhibitors.
    [0012] In this case, a damaging action of the disintegrating products of the blowing agents on the siloxanes employed is described.
    [0013] No special siloxane structures are described, including silicone surfactants.
    Petition 870190016792, of 02/19/2019, p. 5/31
    3/20 [0014] US patent document 2009/0099272 describes the use of acid / amine adducts as catalysts in systems with fluorine-containing blowing agents, since free amines react with the blowing agents and these products then break down surfactants of silicone. In this way, the possibilities in the manufacture of a foam formulation become quite limited, since the amines in this case are weakened in their catalytic action, which results in a longer reaction time of the PU foam formulation.
    [0015] US patent document 2009/0099273 describes the use of Si-free surfactants to avoid the problem with reaction products, made from amine and fluorine-containing blowing agents. Therefore, only a limited amount of surfactants is available.
    [0016] Both alternatives represent a major restriction in the case of the manufacture of PU foam. For this reason, there is a demand for siloxanes, which do not have the disadvantages described above and are indicated as silicone surfactants in the manufacture of PU foam.
    [0017] It is the task of the present invention to prepare siloxanes, which do not have the disadvantages mentioned above in the use of halogenated olefins as a blowing agent and consequently enable improved results.
    [0018] Surprisingly it was found that siloxanes solve this task according to Formula (I).
    [0019] The selected siloxanes of Formula (I) actually show the typical structural elements already in the state of the siloxane technique described, differ mainly in the area of selection of the quantity of structural characteristics. Thus, it is totally surprising and unpredictable to the person skilled in the art the fact that special siloxanes have been discovered, which are in conditions for example without additional radical scavengers or properly in
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    4/20 presence of amines not blocked by acid, in meeting the typical tasks of siloxane in foam molding.
    [0020] An object of the present invention is, therefore, a method for the manufacture of polyurethane foams using a blowing agent composed of halogenated olefins and siloxanes of Formula (I). In this case, the siloxanes of Formula (I) can also be presented as a mixture in a suitable support medium. These mixtures can be present under certain conditions through the manufacturing process or even be manufactured later, in order to facilitate, for example, the dosage control of siloxanes or also to improve and incorporation of siloxanes in the mixture to be foamed.
    [0021] Other objects of the present invention are polyurethane foams and a method for the manufacture of polyurethane foams in which the compositions according to the invention are employed comprising the blowing agents and siloxanes. Furthermore, it is an object of the present invention to use polyurethane foams according to the invention or manufactured according to the invention.
    [0022] The method according to the invention has the advantage of optionally pre-formulated mixtures made of polyols and / or catalysts, of the foam stabilizer and possible other additives, which are marketed as ready-to-use polyurethane foam systems, to overcome the common storage periods on the market without worsening foam properties. Issi also applies especially to single-component systems, in which the isocyanate of the mixture according to the invention is also added.
    [0023] The polyurethane foam according to the invention has the advantage that it has a consistently high quality, that is, a fine cell structure with especially few foam defects (gaps, cracks, compactings).
    [0024] Siloxanes, according to the invention, present the
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    5/20
    following structure:
    R
    R
    R 2 --- Si-O
    R 3 = - O
    RRR 3 R 4 7 -O OSi OSi OSi R R 1 R 3R 3 The B ç R 7 - R R 3R 4 O OSi OSi OSi RR 1R 3R 3 The B ç- 1
    R
    R
    R
    R
    S d
    S d
    R 2 R 2
    Formula (I) in which the independently of each other is 0 to 500, preferably 1 to 300 and especially 2 to 150, b independently of each other is 0 to 60, preferably 1 to 50 and especially 1 to 30, and independently of each other is 0 to 10, preferably 0 or> 0 to 5, d independently from each other is 0 to 10, preferably 0 or> 0 to 5, with the proviso that per molecule of Formula (I) the average amount £ d of the T units and the average quantity £ c of Q units per molecule is not greater than 50 respectively, average quantity £ a of D units per molecule is not greater than 2000 and average quantity £ b of siloxy units carrying R 1 per molecule is not more than 100 , [0025] R independently of each other at least one radical from the group of linear, cyclic or branched, aliphatic or aromatic hydrocarbon radicals, saturated or unsaturated with 1 to 20 carbon atoms, preferably however a methyl radical,
    Petition 870190016792, of 02/19/2019, p. 8/31
    6/20 [0026] R 2 independently from each other is R 1 or R, [0027] R 1 is not equal to R and independently from each other is an organic radical and / or a radical selected from the group
    -ch 2 -ch 2 -ch 2 -o- (ch 2 -ch 2 0-) x - (CH 2 -CH (R ') O-) y -R''-ch 2 -ch 2 -o- ( ch 2 -ch 2 o-) x - (CH 2 -CH (R ') o-) y -R -ch 2 -r iv
    -ch 2 -ch 2 - (0) x --r iv
    -CH 2 -CH 2 -CH 2 -O-CH 2 -CH (OH) -ch 2 oh
    -CH2-CH2-CH2-O-CH2-C (CH 2 OH) 2-CH2-CH3, where x 0 to 100, preferably> 0, especially 1 to 50, x 0 or 1, y 0 to 100, preferably > 0, especially 1 to 50, z 0 to 100, preferably> 0, especially 1 to 10, [0028] R independently from each other is an alkyl or aryl group optionally substituted, for example with alkyl radicals, aryl radicals or halogenated alkyl radicals or halogenated aryl having 1 to 12 carbon atoms, and within a radical R 1 and / or a molecule of Formula (I) different R 'substituents may be present, and [0029] R independently from each other, means a hydrogen radical or an alkyl radical with 1 to 4 carbon atoms, a C (O) -R 'group with R' = alkyl radical, a -CH2-O-R 'group, an alkylaryl group, such as a benzyl group , The group -C (O) NH-R ', [0030] R IV a linear, cyclic or branched hydrocarbon radical,
    Petition 870190016792, of 02/19/2019, p. 9/31
    7/20 including later substituted, substituted for example with halogen, with 1 to 50, preferably 9 to 45, preferably 13 to 37 carbon atoms, [0031] R 4 can be independently R, R 1 and / or a radical substituted with heteroatoms, functionalized, organic, saturated or unsaturated, selected from the group of radicals alkyl, aryl, chloroalkyl, chloroaryl, fluoroalkyl, cyanoalkyl, acryloxyaryl, acryloxyalkyl, methacryloxyalkyl, methacryloxypropyl or vinyl, with the proviso that at least one made a substitute. R 1 , R 2 and R 4 do not equal R.
    [0032] The different monomer units of the components indicated in the Formulas (siloxane chains or polyoxyalkylene chains) can be structured together in blocks with a random number of blocks and be subject to a random sequence or a statistical distribution. The indices used in the Formulas must be considered as average statistical values.
    [0033] Mixtures containing siloxane according to the invention may contain other substances. In particular, the compositions according to the invention can have other additives / auxiliary means, such as they are used in the manufacture of polyurethane foam. Preferred additives / auxiliaries, which may have the compositions according to the invention, are preferably selected from conventional SiOC and SiC stabilizers, organic stabilizers, surfactants, nucleating agents, cell refining additives, cell openers, crosslinkers, emulsifiers, flame retardants, antioxidants, antistats, biocides, colored pastes, solid fillers, amine catalysts, metal catalysts, polyols and / or buffer substances.
    [0034] Furthermore, it can be advantageous if the composition according to the invention contains a solvent, especially an organic solvent, preferably a solvent selected from glycols, alkoxylates and oils of synthetic and / or natural origin.
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    8/20 [0035] The manufacture of siloxanes according to Formula (I) is carried out according to known methods such as the hydrosilylation reaction catalyzed by precious metal compounds, which contains double bond, with corresponding hydrogen siloxanes as described in patent document EP 1 520 870. EP 1 520 870 is hereby inserted as a reference and is considered to be part of the publication content of the present invention.
    [0036] As compounds, which have at least one double bond per molecule, eg α-Olefins, vinyl polyoxyalkylenes and / or allyl polyoxyalkylenes can be used. Preferably, vinyl polyoxyalkylenes and / or allyl polyoxyalkylenes are used. Especially preferred vinyl polyoxyalkylenes are, for example, vinyl polyoxyalkylenes with a molecular weight in the range of 100 g / Mol to 5,000 g / Mol, which can have a block structure or statistically distributed from the monomers of propylene oxide, ethylene oxide, butylene oxide and / or styrene oxide and which can be capped at the ends both with hydroxy functionality and also through a methyleter or acetoxy function. Especially preferred allyl polyoxyalkylenes are, for example, allyl polyoxyalkylenes with a molecular weight in the range of 100 g / Mol to 5,000 g / Mol, which can have a block structure or statistically distributed from monomers of propylene oxide, ethylene oxide, butylene oxide and butylene oxide and / or styrene oxide and which can be capped at the ends with hydroxy functionality or through a methyleter or acetoxy function. The α-Olefins mentioned in the examples, allylalcohol, 1-hexenol, vinylpolyoxyalkylenes and / or allyloxyalkylalkylenes, as well as allylglycidyleter and vinylcyclohexene, can be especially preferably used as compounds, which have at least one double bond per molecule.
    [0037] Preferably siloxanes of Formula (I) are used in the method according to the invention wherein the independently of each other is 1 to 300, b independently of each other is 1 to 50, and independent
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    9/20 between themselves is 0 to 4, d independently from each other is> 0 to 4, with the proviso that per molecule of Formula (I) the average quantity £ d of the T units and the average quantity £ c of the Q units per molecule respectively is not greater than 20, the average quantity £ a of the D units per molecule is not greater than 1500 and the average quantity £ b of the siloxy units carrying R 1 per molecule is not greater than 50, [0038] In one especially preferred embodiment of the method according to the invention, siloxanes of Formula (I) are used, where R 1 independently of one another is an organic radical
    -CH 2 -CH 2 -CH 2 -O- (CH 2 -CH 2 O-) x - (CH 2 -CH (R ') O-) y -R''-ch 2 -ch 2 -o- ( CH 2 -CH 2 O-) x - (CH 2 -CH (R ') O-) y -R ”-ch 2 -r iv where x is 0 to 100, preferably> 0, especially 1 to 50 and y is 0 to 100, preferably> 0, especially 1 to 50, R 'independently of each other may be different and represent methyl, ethyl and / or phenyl radicals. R independently of each other means a hydrogen radical or an alkyl group with 1 to 4 carbon atoms, a C (O) -R 'group with R' = alkyl radical, a -CH2-O-R 'group, an alkylaryl group, as for example a benzyl group, which means group C (O) NH-R ', R lv is a linear, cyclic or branched hydrocarbon radical, optionally substituted, eg with halogen with 1 to 50, preferably 9 to 45, preferably 13 to 37 carbon atoms.
    [0039] In another preferred embodiment of the method siloxanes of Formula (I) are used, where R 1 independently of each other is an organic radical selected from the group comprising -CH2-CH2-CH2-O- (CH2-CH2O-) x- (CH2-CH (R ') O-) yR and / or -CH 2 -CH2-O- (CH2-CH2O-) x- (CH2-CH (R') O-) yR and / or
    -CH 2 -R iv , where x is 0 to 100, preferably> 0, especially 1 to 50, y is 0 to
    Petition 870190016792, of 02/19/2019, p. 12/31
    10/20
    100, preferably> 0, especially 1 to 50, R 'means methyl and R' 'independently of one another a hydrogen radical or an alkyl group with 1 to 4 atoms, a group -C (O) -R' '' with R ' '' = alkyl radical, a -CH2-O-R 'group, an alkylaryl group, as e.g. A benzyl group, which means -C (O) NH-R 'group, with the molar percentage of oxyethylene units decreasing to 70% of the oxyalkylene units, also x / (x + y) is> 0.7. In addition, it may be advantageous if the polyoxyalkylene chain carries at the end a hydrogen and at the same time the molar percentage of oxyethylene units makes up 70% of the oxyalkylene units, also x / (x + y) is <0.7 and R '' means a hydrogen radical.
    [0040] In another preferred embodiment of the method according to the invention, siloxanes of Formula (I) are used in which, in hydrosilylation, they are used among other olefins in which R 1 is composed of at least 10 moles per center, preferably at least 20 mole percent, especially preferably at least 40 mole percent -CH2-R IV , where R IV is a linear or branched hydrocarbon with 9 to 17 carbon atoms.
    [0041] In another preferred embodiment of the method according to the invention, siloxanes of Formula (I) are employed in which the final positions, or also referred to alpha and omega in the siloxane, are at least partially functionalized with R 1 radicals. In this case, at least 10 mole percent, preferably at least 30 mole percent, especially preferably at least 50 mole percent of the end positions with R 1 radicals are functionalized.
    [0042] In an especially preferred embodiment of the method according to the invention, siloxanes of Formula (I) are employed, in which, on average, a maximum of 50%, preferably a maximum of 45%, especially preferably a maximum of 40% by weight total molecular weight of siloxane fall on the mass
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    11/20 molar sum of all optionally different radicals R 1 in the siloxane.
    [0043] In another preferred embodiment of the method according to the invention, siloxanes of Formula (I) are used in which the radical R represents methyl and the amount of structural elements with the index a are present in amounts greater than those of the structural elements with index b, so that the quotient a / b is at least equal to seven, preferably greater than 10, especially preferably greater than 12.
    [0044] In another embodiment of the method according to the invention, siloxanes of Formula (I) are used in which the oxalkylene units present in the radical R 1 are exclusively the oxyethylene units, and in this case, the radical R '' is not hydrogen. [0045] In another preferred embodiment of the method according to the invention, siloxanes of Formula (I) are employed, which have no branching or at least in the statistical average less than one branching in the siloxane skeleton and for which, therefore, , it applies that Zc + Zd is <1.
    [0046] In another preferred embodiment of the method according to the invention, siloxanes of Formula (I) are employed, which in the statistical average have one or more branches in the siloxane skeleton and for which Zc + is applied. Zd is> 1.
    [0047] The siloxanes according to the invention can also be used as part of compositions with different carrier agents. As carrier agents, for example, glycols, alkoxylates or oils of synthetic and / or natural origin can be used. Preferably, as much as the mass percentage of compounds of Formula (I) in the ready polyurethane foam is added to the composition from 0.01 to 10% by weight, preferably from 0.1 to 3% by weight.
    [0048] The compositions according to the invention can be used as foam stabilizers in common formulations for
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    12/20 the manufacture of cellular polyurethane materials, composed of one or more organic isocyanates with two or more isocyanate functionalities, of one or more polyols with two or more isocyanate reactive groups, catalysts for the isocyanate-polyol reactions and / or isocyanate-water and / or isocyanate-trimerization, water, optionally physical blowing agents, optionally flame retardants and optionally other additives.
    [0049] Iosicanates suitable for the purposes of this invention are all multifunctional organic isocyanates such as 4,4'diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI) and isophorone diisocyanate (IPDI). Especially suitable is the mixture known as „polymeric MDIO („ crude MDI) made of high-grade condensed MDI and analogs with an average functionality of 2 to 4, as well as the different isomers of TDI in pure form or as an isomeric mixture.
    [0050] Suitable polyols in the sense of this invention are all substances with various groups reactive to isocyanates, as well as their preparations. Preferred polyols are all polyether polyols and polyester polyols commonly used for the manufacture of cellular materials based on polyurethane. Polyether polyols are obtained by reacting polyvalent alcohols or amines with alkylene oxides. Polyester polyols are based on esters of polyvalent carboxylic acids (which can be aliphatic, for example adipinic acid, or aromatics, for example phthalic acid or terephthalic acid) with polyvalent alcohols (mostly glycols).
    [0051] An adequate ratio of isocyanate and polyol, expressed as an index of the formulation, that is, as a stoichiometric ratio of isocyanate groups forming groups reactive to isocyanat (eg OH groups, NH groups) multiplied by 100, if in the range of 10 to 1000, preferably 80 to 350.
    [0052] Catalysts suitable for the purpose of this invention are
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    13/20 substances, which catalyze the reaction in gel (isocyanate-polyol), the expansion reaction (isocyanate-water) or the di- or trimerization of the isocyanate. Typical examples are the amines triethylamine, dimethylcyclohexylamine, tetramethylethylenediamine, tetramethylhexanediamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, triethylenediamine, dimethylpiperazine, 1,2-dimethylimethylamino-dimethylmethyl, dimethylamine, dimethylamine (dimethylaminoethyl) ether, as well as metal-containing compounds such as tin compounds such as tin dibutyl dilaurate or tin-II-2-ethylhexanoate and potassium salts such as potassium acetate and potassium 2-ethylhexanoate. [0053] Suitable amounts of application are governed by the catalyst type and are normally in the range of 0.05 to 5 pphp (= parts by weight with respect to 100 parts by weight of polyol) or 0.1 to 10 pphp for salts of potassium.
    [0054] Adequate water content in the sense of this invention depends on whether water will be added in addition to halogenated olefin or not. Amounts of water from 0.1 to 5 pphp are normally used.
    [0055] In addition to the halogenated olefins mentioned above, other suitable physical blowing agents can also be used. These are for example liquefied CO2, and easily fluidizable liquids, for example hydrocarbons with 4 or 5 carbon atoms, preferably cyclo-, iso- and n-pentane, fluorohydrocarbons, preferably HFC 245fa, HFC 134a and HFC 365mfc, fluorochlorohydrocarbons, preferably HCFC 141b, oxygen-containing compounds such as methylformate and dimethoxymethane, or chlorohydrocarbons, preferably dichloromethane and 1,2-dichloroethane.
    [0056] In addition to water and physical blowing agents, other chemical blowing agents can also be used, which react with isocyanates under the formation of gases such as acid
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    14/20 formic.
    [0057] Suitable flame retardants for the purposes of this invention are preferably liquid organic phosphorus compounds such as organic phosphates, eg triethylphosphate (TEP), halogenated phosphates, eg tris (1-chloro-2-propyl) ) phosphate (TCPP) and tris (2-chlorethyl) phosphate (TCEP) and organic phosphonates, eg dimethylethane phosphonate (DMMP), dimethylpropane phosphonate (DMPP), or solids such as ammonium polyphosphate (APP) and red phosphorus. In addition, halogenated compounds, for example halogenated polyols, are suitable as flame retardants, as well as solid materials such as expandable graphite and melamine.
    [0058] The processing of the formulations according to the invention forming cellular materials can also be done according to all the methods known to the person skilled in the art, for example in the manual mixing method or preferably with the aid of high foam molding machines pressure. In this case, discontinuous methods can be used, for example for the production of molded foams, refrigerators and panels, or continuous methods, for example in insulation boards, metal composite elements, blocks or in spray methods.
    [0059] Shaving foams 1- and 1.5-components represent a special case, in which a polyurethane prepolymer is used. Also in this application, compositions containing siloxane according to the invention can be used as foam stabilizers.
    [0060] The polyurethane foams according to the invention are notable for the fact that they present or contain a composition containing siloxane according to the invention. Preferably, the mass percentage of compounds of Formula (I) in the ready polyurethane foam is 0.01 to 10% by weight, preferably 0.1 to 3% by weight.
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    15/20 [0061] The polyurethane foams according to the invention can be, for example, a hard polyurethane foam, a flexible polyurethane foam, a viscoelastic foam, an HR foam, a semi-hard polyurethane foam, a thermosetting polyurethane foam or integral foam. The designation polyurethane in this case should be understood as a generic term for a polymer made of di- or polyisocyanates and polyols or other species reactive to isocyanate, such as amines, and the urethane bond need not be of the exclusive bond type or predominant. Polyisocyanurates and polyureas are also expressly included.
    [0062] In a preferred embodiment, these are foams manufactured in accordance with the invention and closed cell foams.
    [0063] The polyurethane foams according to the invention can be used as components of or in and / or, for example, refrigerator insulation, insulation plates, sandwich element, pipe insulation, spray foam, shaving foam of 1 - and 1.5-components, artificial wood, shaping foam, packaging foam, mattresses, upholstered furniture, car seat upholstery, head restraints, instrument panel, interior car cladding, car roof cladding, matewrial sound absorption, steering wheel, shoe sole, back side foam of carpet, filter foam, sealing foam and adhesives.
    [0064] Other objects and embodiments of the invention are included in the claims, whose content of disclosure is in all its scope part of the description.
    [0065] The method, according to the invention for the manufacture of polyurethane foams, the polyurethane foams themselves as well as their applications are described below by way of example, without the invention being restricted to these concrete forms
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    16/20 tization presented as an example. If margins, general formulas or classes of compounds are presented then these should cover not only the corresponding areas or corresponding groups of compounds, but also all the partial areas and partial groups of compacts, which can be obtained by extracting individual values (areas) or compounds. If documents are cited within the scope of this description, then their content will be integral to the description of the present invention.
    [0066] In the examples listed below the present invention is described by way of example without the invention, the scope of which is contained in the full description and the claims, being limited to the embodiments mentioned in the examples.
    Examples
    Manufacture of siloxanes according to the invention [0067] Siloxanes according to the invention of Formula (I) can be manufactured according to the methods known in the art by reaction with corresponding hydrogen siloxanes by hydrosilylation.
    [0068] Alylpolieter and olefins are reacted to form compounds according to formula (I). The manufacture was made analogously to the method in relation to example 7 from the patent document DE 1020070554852 and consequently in accordance with the state of the art for the manufacture of polyether siloxanes in SiC bond, as it for example is described even in the patent document EP 1520870.
    [0069] Table 1 shows the polyethers used.
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    Table 1: For the manufacture of allyl polyether compounds used in table 2 (x = ethylene oxide units, y = propylene oxide units, R '' = end groups)
    Polieter Initiators R '' x = y = PE 1 Alylalcool - H 11 0 PE 2 Alylalcool - H 9 3 PE 3 Alylalcool - H 13 4 PE 4 Alylalcool - H 12 9 PE 5 Hydroethylvinyl ether - H 15 7 PE 6 Alylalcool - H 13 14 PE 7 Alylalcool - CH3 10 0 PE 9 Alylalcool - H 36 38
    [0070] The structure of the compound obtained from Formula (I) can be found in Table 2. The parameters listed in Table 2 refer to Formula (I) above.
    Table 2: Siloxanes of examples 1 to 10, containing compounds of Formula (I)
    Ex. R Za R 1 R 4 Zb Zc Zd R 2 1 CH3 44 PE 2 CH3 5 0 << 1 R 2 CH3 65 PE 4 CH3 4 0 << 1 R 3 CH3 50 PE 1) 1 CH3 8 0 << 1 R 1 4 CH3 20 PE 1 CH3 2 0 << 1 R 5 CH3 40 PE 7 CH3 5 0 << 1 R 6 CH3 65 PE 6 / PE 8) 2 CH3 5 0 << 1 R 1 7 CH3 40 PE 4 / PE 1) 3 CH3 3 0.5 2 R 1
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    8 CH3 40 PE 3 CH3 3 0 1 R 9 CH3 40 PE 3 C8H17 3 0.5 2 R 1 10 CH3 40 PE 5 CH3 4 0 << 1 R 1
    ) 1 Mixture composed of 80 Aq .-% PE 1 + 20 Aq.% Ci6-Olefin) 2 Mixture composed of 60 Aq .-% PE 6 + 40 Aq.% PE 8) 3 Mixture composed of 50 Aq .-% PE 4 + 50 Aq.% PE 1
    Foam molding examples [0071] The following foam formulation was used to check the technique for applying the formulations according to the invention:
    Table 3: Formulations of rigid foam applications (rigid foam panel / insulation board) in mass percentages
    Formulation A: PUR flowable formulation B: PIR insulation board Polyol Mixture of poloeterpoliol 100 parts Stepanpol® PS2352 * 100 pieces Tris (1-chloro-2propyl) phosphate 15 pieces N, N, N ', N' ', N' '-pentamethyldiethylenetriamine 0.2 parts 0.2 Parts N, N-dimethylcyclohexylamine 2.0 Parts - Potassium octoate (75% by weight in diethylene glycol)4.0 Parts Water 2.0 Parts 0.8 Parts 1,3,3,3-tetrafluoropropene (E-isomer) 3.0 Parts 4.0 Parts 1-chloro-3,3,3trifluoropropene (isomer 12.0 Parts 18.0 Parts
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    19/20
    AND) 1,2,3,3,3-pentafluoropropene 3.0 Parts 4.0 Parts Siloxane 2.0 Parts 2.0 Parts Desmodur 44V20L ** 140 Parts 200 Pieces
    * Polyesterpoliol by Firma Stepan ** Polymeric MDI by Firma Bayer, 200 mPa * s, 31.5% NCO, Functionality
    2.7 [0072] The foam molding was performed using the manual mixing method. For that, formulations A and B described in table 3 were made with different siloxanes and weighed in a glass. Then MDI was added, the reaction mixture stirred with a 6 cm diameter plate shaker for 5 seconds under 3000 Upm transferred immediately to a 50 cm x 25 cm x 5 cm thermostatized aluminum mold, which was coated with polyethylene film. The amount of application of foam formulation was mentioned in this case so that it was 10% above the amount needed for the minimum filling of the mold.
    [0073] A day later, the honeycomb materials were analyzed. On the upper side and the lower side, the surfaces were evaluated and after the opening by cutting the foams, the internal irregularities in a subjective way with the aid of a scale from 1 to 10, with 10 representing a foam without any irregularity and 1 representing an extremely foam problematic. The porous structure (average number of cells per 1 cm) was evaluated visually on a cutting surface by comparison with reference foams.
    [0074] The results are shown in Table 4. The siloxanes used, the foam formulations, the
    Petition 870190016792, of 02/19/2019, p. 22/31
    20/20 rather as the visual assessment and the porous structure of the foams.
    Table 4: Results of foam moldings
    Example Ex siloxane. Formul.defoam Top / bottom / can in rating Cells/ cm 11 1 THE 9/7/8 46-50 12 2 B) 4 8/8/7 46-50 13 3 B) 4 9/7/8 46-50 14 4 B 6/8/9 46-50 15 5 B 7/7/9 46-50 16 6 B) 4 6/7/8 41-45 17 7 B 8/8/7 41-45 18 8 B 8/9/8 46-50 19 9 B 9/7/8 46-50 20 10 THE 9/7/8 46-50
    ) 4 foam formulation was stored together with siloxane for 3 days at 50 ° C before molding epsuma [0075] The data in table 4 shows that with siloxanes according to the invention in formulations, which contains halogenated olefins as expansion, good quality honeycomb materials are obtained. Also, after the aging of the polyol components readily formulated with stabilizer, fault-free foams are obtained. Such a result could not be obtained according to US patent document 2009/0099272 - and example 2.
    Petition 870190016792, of 02/19/2019, p. 23/31
    权利要求:
    Claims (12)
    [1]
    claims
    1. Method for making polyurethane foams, characterized by the fact that it uses compositions containing one or more than one blowing agent consisting of halogenated olefins and one or more than a siloxane of Formula (I)
    R
    R
    R 2 --- SUO - Si - O
    Si — O R 1
    R
    R
    R
    R 3 = - O - Si — O
    Si --- O
    Si — O R 3 R 3
    Si — O - S c
    R 3
    Si --- O R 3 R 3
    Si --- O - S c
    R 4 R 2
    R 2
    Formula (I) in which a in each occurrence is independently from 1 to 500, b in each occurrence is independently from 1 to 30, c in each occurrence is independently from 0 to 5, d in each occurrence is, independently, from 0 to 5, with the proviso that, per molecule of Formula (I), the average quantity £ d of the T units and the average quantity £ c of the Q units, per molecule, are not respectively greater than 50, the average quantity £ a of the D units, per molecule, is not greater than 2000, and the average quantity £ b of the siloxy units carrying R 1 , per molecule, is not greater than 100,
    R is a methyl radical,
    R 2 , in each occurrence, is, independently, R 1 or R,
    R 4 , in each occurrence, is, independently, a saturated hydrocarbon radical having from 1 to 20 carbon atoms,
    Petition 870190016792, of 02/19/2019, p. 24/31
    [2]
    2/4 with the proviso that at least one substituent of R 1 , R 2 and / or R 4 is different from R, and siloxanes of Formula (I) are used, where R 1 , in each occurrence, is, independently , an organic radical selected from the group comprising
    R 1 is not equal to R and independently of each other is an organic radical and / or a radical selected from the group
    -CH2-CH2-CH2-O- (CH2-CH2O-) x- (CH2-CH (R ') O-) y-R and / or
    -CH2-CH2-O- (CH2-CH2O-) x- (CH2-CH (R ') O-) y-R in which x is 0 to 100, x' is 0 or 100,
    R 'is methyl, and
    R '', in each occurrence, is independently a hydrogen or an alkyl group with 1 to 4 carbon atoms, a C (O) -R '' 'group with R' '' = alkyl, a -CH2- group O-R ', an alkylaryl group, a -C (O) NH-R' group, the molar fraction of the oxyethylene units comprising at least 70% of the oxyalkylene units, that is, x / (x + y) is> 0.7, or the molar fraction of the oxyethylene unit comprises at most 70% of the oxyalkylene units, that is, that is, x / (x + y) is <0.7, and R ”is hydrogen.
    2. Method for the manufacture of polyurethane foams, according to claim 1, characterized by the fact that it uses blowing agents consisting of fluorinated olefins, as a blowing agent, and siloxanes of Formula (I), in which:
    a in each occurrence, is independently from 1 to 150, b in each occurrence, is, independently, from 1 to 30, c in each occurrence, is, independently,> 0 to 4, d in each occurrence, is, independently ,> 0 to 4, with the condition that, per molecule of Formula (I), the amount
    Petition 870190016792, of 02/19/2019, p. 25/31
    [3]
    3/4 average Zd quantity of T units and the average Zc quantity of Q units, per molecule, are not respectively greater than 20, the average Za quantity of D units, per molecule, is not greater than 1500, and the average quantity Zb of siloxide units carrying R 1 , per molecule, does not exceed 50.
    3. Method according to claim 1 or 2, characterized by the fact that at least 10% of the radicals R 2 are equal to R 1 .
    [4]
    Method according to any one of claims 1 to 3, characterized by the fact that it uses siloxanes of Formula (I), in which, in the statistical average, a maximum of 50%, preferably a maximum of 45%, especially preferred, at most 40% of the total average molar weight of the siloxane falls on the added molar mass of all optionally different R 1 radicals in the siloxane.
    [5]
    Method according to any one of claims 1 to 4, characterized by the fact that R is methyl, and the quotient a / b is not less than 7.
    [6]
    6. Method according to any one of claims 1 to 5, characterized by the fact that, at R 1 , y = 0 and R '' is not hydrogen.
    [7]
    Method according to any one of claims 1 to 6, characterized by the fact that Zc + Zd is <1.
    [8]
    Method according to any one of claims 1 to 7, wherein Zc + Zd is> 1.
    [9]
    9. Polyurethane foam, characterized by the fact that it is obtained according to a method, as defined in any one of claims 1 to 8.
    [10]
    10. Polyurethane foam, according to claim 9, characterized in that it is closed cell.
    [11]
    11. Polyurethane foam according to claim 9 or 10, characterized in that it is a rigid polyurethane foam, a flexible polyurethane foam, a viscoelastic foam,
    Petition 870190016792, of 02/19/2019, p. 26/31
    4/4 an HR foam, a semi-rigid polyurethane foam, a thermosetting polyurethane foam or an integral foam.
    [12]
    12. Use of polyurethane foams, as defined in any of claims 9 to 11, characterized by the fact that it is in and / or as refrigerator insulation, insulation plates, interleaved elements, pipe insulation, spray foam, foam 1- and / or 1.5-component shaving, artificial wood, shaping foam, packaging foam, mattresses, upholstered furniture, car seat upholstery, head restraints, instrument panel, car interior trim, seat cover automobile roof, sound-absorbing matewrial, steering wheel, shoe sole, back side foam of carpet, filter foam, sealing foam and adhesives or for manufacturing corresponding products.
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    同族专利:
    公开号 | 公开日
    KR20120052250A|2012-05-23|
    CN102471446B|2014-08-06|
    DE102009028061A1|2011-02-10|
    KR101752933B1|2017-07-03|
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    JP2013500362A|2013-01-07|
    US20120088856A1|2012-04-12|
    WO2011012390A1|2011-02-03|
    JP2014210934A|2014-11-13|
    JP6139475B2|2017-05-31|
    BR112012002073A2|2016-05-31|
    PL2459612T3|2019-09-30|
    MX2012001179A|2012-03-07|
    CN102471446A|2012-05-23|
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    法律状态:
    2017-08-15| B25A| Requested transfer of rights approved|Owner name: EVONIK DEGUSSA GMBH (DE) |
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-01-29| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-04-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-05-07| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/06/2010, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/06/2010, OBSERVADAS AS CONDICOES LEGAIS |
    2020-05-12| B25D| Requested change of name of applicant approved|Owner name: EVONIK OPERATIONS GMBH (DE) |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102009028061.8|2009-07-29|
    DE102009028061A|DE102009028061A1|2009-07-29|2009-07-29|Process for the production of polyurethane foam|
    PCT/EP2010/059190|WO2011012390A1|2009-07-29|2010-06-29|Method for producing polyurethane foam|
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