WO2015028295A1 - Utilisation de mélanges de polysiloxanes à modification organofonctionnelle et d'amides dans la fabrication de mousses de polyuréthane souples - Google Patents

Utilisation de mélanges de polysiloxanes à modification organofonctionnelle et d'amides dans la fabrication de mousses de polyuréthane souples Download PDF

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WO2015028295A1
WO2015028295A1 PCT/EP2014/067142 EP2014067142W WO2015028295A1 WO 2015028295 A1 WO2015028295 A1 WO 2015028295A1 EP 2014067142 W EP2014067142 W EP 2014067142W WO 2015028295 A1 WO2015028295 A1 WO 2015028295A1
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carbon atoms
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Sarah Schmitz
Roland Hubel
Martin Glos
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Evonik Industries Ag
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    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
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    • C08G2110/00—Foam properties
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    • C08G2110/005—< 50kg/m3
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond

Definitions

  • the invention is in the field of polyurethanes, in particular polyurethane flexible foams. It relates in particular to the use of mixtures of organofunctionally modified polysiloxanes with amides and organic solvent in the production of flexible polyurethane foams and to a process for the production of flexible polyurethane foams.
  • Polysiloxane-polyoxyalkylene block copolymers referred to below as polyethersiloxanes, are used in the production of polyurethane foams. They allow the formation of a uniform, fine pore structure and stabilize the foam during the manufacturing process. Depending on the manufacturing process and depending on which other raw materials are used, however, one obtains in some cases only an insufficient cell fineness. For example, the use of highly polypropylene oxide-containing polyols often leads to a more coarse cell structure. Even machine conditions can lead to an irregular or coarse cell structure, for example, when using low-pressure mixing heads or even with simple stirring of the raw materials at atmospheric pressure.
  • the normally slow (without C0 2 / methylene chloride) foaming process which lays the foundation for the morphological properties - cell number and cell size distribution of the resulting foam - shrinks to fractions of a second, the time frame required for the raw materials to dissipate pressurized mixing head of a foaming machine and the subsequent application device to reach the ambient pressures of one atmosphere.
  • CO 2 foaming similar to a shaving foam from a spray can, spontaneously a foam forms by evaporating liquid CO 2 .
  • the occurring defect in such foams are uneven, partially coarsened cells within the foam structure, the use of suitable foam stabilizers quite helpful for Minimization of these errors can be.
  • EP-A-0 900 811 describes the use of cyclic carbonates in flexible foam formulations as cell refining agents.
  • the cyclic carbonates are effective only in amounts of the order of the polyethersiloxane and also have the disadvantage of thinning volatile components from the finished foam.
  • EP-A-0 976 781 describes the combined use of polyether siloxanes with salts of organic acids. Cell refinement occurs at low concentrations, but the solubility of the salts is relatively limited, requiring the use of water as a cosolvent. The application is therefore limited only to hydrolysis-stable polyether siloxanes. Furthermore, water contributes to the blowing reaction with isocyanate and must be taken into account, depending on the use concentration, if appropriate, in the formulation calculation.
  • EP-A-1 029 878 relates to the use of improved polysiloxane-polyoxyalkylene block copolymers as additives in the preparation of polyurethane foams, the improvement being that, through the use of both Si-C and Si-OC linked silicone polyethers Block copolymers are allowed in a mixture special property combinations of activity and cell fineness.
  • US-A-4 520 160 describes a process for the preparation of polyethersiloxanes in the presence of fatty alcohols. The latter prevent gelation during manufacture. The resulting products are preferably used as emulsifiers in cosmetic applications or as stabilizers in the production of elastomers, but not for the production of x-mas foam.
  • US-A-1 132 867 involves the use of fatty alcohols as a blending component of the polyethersiloxane.
  • fatty alcohols which are selected from Guerbet and Ziegler alcohols, in particular branched oxo and Isotridecylalkohole.
  • amide-containing compounds is not mentioned there.
  • the object of the present invention was to allow an effective influence name on the cell refining in the production of flexible polyurethane foam.
  • mixtures of certain polyether siloxanes with certain amide group-containing compounds and organic solvent in the production of flexible polyurethane foams have a significantly more effective effect on cell refining than the corresponding polyether siloxanes alone or with conventional blending components.
  • the mixtures according to the invention enable the production of flexible polyurethane foams having a particularly regular cell structure and increased cell fineness.
  • R 1 independently of one another, are alkyl radicals or aryl radicals,
  • R 2 independently of one another, are identical to R 1 and / or R 3 , with the proviso that at least one radical R 2 has the meaning R 3 ,
  • Y is a hydrocarbon radical which is optionally branched
  • Z is a hydrogen radical or a monovalent organic radical including an acyl radical
  • a is a number from 1 to 100, if b is a number from> 6 to 8,
  • a is a number from 1 to 200, when b is a number from> 3 to 6,
  • a is a number from 1 to 300, when b is a number from 0 to 3,
  • b 0 to 8, e.g. 1 to 8,
  • R ' is identical or different and is H or organic radical, preferably C 1 -C 2 -alkyl, aryl, alkylaryl radical, which may optionally contain oxygen or nitrogen atoms, in particular hydroxyl or amino groups, or a radical -XZ,
  • Suitable amides of the formula (III) may preferably be obtained by reacting a fatty acid or a fatty acid ester with an alkanolamine.
  • the mixtures according to the invention allow a particularly effective influence name on the cell refining. In particular, they allow a significantly more effective influence on the cell refinement than the corresponding polyether siloxanes alone or with the usual blending components.
  • propellants such as in particular liquid C0 2 or methylene chloride, which usually make particularly high demands on the polyether siloxane with regard to achieving a fine-pored cell structure.
  • the simultaneous use of the components (a) to (c) as a mixture is particularly advantageous, since this leads to a significantly better effect on cell refining than a separate addition, such as e.g. the addition of the amide compound (b) via the polyol component.
  • a mixture comprising constituents (a) to (c) should be used.
  • the mixtures according to the invention comprising components (a) to (c) consist of at least> 40% by weight, preferably> 50% by weight, of the abovementioned components (a) and (b).
  • they may contain other ingredients, such as preferably water and additional surfactants. They can also be free of water and additional surfactants.
  • Preferred mixtures according to the invention may optionally contain water in addition to the components (a) to (c).
  • Particularly preferred mixtures according to the invention comprise, in addition to components (a) and (b) as component (c), dipropylene glycol and / or propylene glycol, and optionally water and optionally at least one additional surfactant.
  • component (c) dipropylene glycol and / or propylene glycol are included, but no water and also no additional surfactant is included.
  • compositions according to the invention comprise, in addition to components (a) and (b) as component (c), dipropylene glycol and / or propylene glycol, as well as water and at least one additional surfactant.
  • non-reactive polyethers preferably of higher molecular weight, phthalates, animal and vegetable oils and / or antifreeze in liquid form, as additional mixing component in the mixture.
  • a preferred mixture according to the invention which can be used, in particular, as a flexible polyurethane foam stabilizer solution comprises:
  • organic surfactant such as, preferably Alkylbenzenesulfonate, especially when using
  • a mixture according to the invention may also be free of water and additional organic surfactant.
  • the mixture according to the invention which is in particular a Polyurethanh exertweichschaumstabilisatoryour, as additional components have further additives.
  • the proportion of the components used is in each case selected so that the total content of the components does not exceed 100% by weight.
  • a preferred mixture according to the invention comprises:
  • Another mixture particularly preferred according to the invention comprises:
  • organic solvents preferably propylene and / or dipropylene glycol, especially dipropylene glycol.
  • This preferred mixture is preferably free of water and additional organic surfactant.
  • organic surfactants are described in more detail. These may in particular be selected from the group comprising anionic surfactants, cationic surfactants, nonionic surfactants and / or amphoteric surfactants, wherein the organic surfactant is preferably an anionic surfactant.
  • the mixtures according to the invention may preferably contain one or more surfactants selected from anionic, nonionic, cationic, ampholytic (amphoteric, zwitterionic) surfactants and mixtures thereof.
  • compositions of the invention preferably comprise an anionic surfactant.
  • anionic surfactant may include salts including, for example, sodium, potassium, ammonium and substituted ammonium salts, such as mono-, di- and triethanolamine salts of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants.
  • Anionic sulfate and sulfonate surfactants are preferred.
  • surfactant systems comprising a sulfonate or a sulfate surfactant, preferably a linear or branched alkyl benzene sulfonate and alkyl ethoxy sulfates as described herein, optionally also combined with cationic surfactants as described herein.
  • anionic surfactants include the isethionates, such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, Monoester of sulfosuccinate (especially saturated and unsaturated Ci2-Ci 8 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C 6 -C 4 diesters), N-acyl sarcosinates.
  • Resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil are also suitable.
  • Anionic sulfate surfactant include the linear and branched, primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C 5 -C 7 acyl-N- (C 1 -C 4 alkyl) and -N- (C 1 -C 2 -hydroxyalkyl) glucamine sulfates, and sulfates of the alkyl polysaccharides such as the sulfates of alkyl polyglucoside (wherein the nonionic unsulfated compounds are described herein).
  • Alkyl sulfate surfactants are preferably selected from the linear and branched primary do-C-is-alkyl sulfates, more preferably the branched chain Cii-C 5 straight chain alkyl sulfates and the C 2 -C 4 alkyl sulfates.
  • Alkylethoxysulfate surfactants are preferably selected from the group consisting of the Ci 0 -Ci 8 alkyl sulfates, which are ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a Cn-Ci 8 -, most preferably Cn-Ci 5 - alkyl sulfate ethoxylated with from 0.5 to 7, preferably 1 to 5 moles of ethylene oxide per molecule.
  • Anionic sulfonate surfactant include the salts of linear C 5 -C 2 o alkyl benzene sulfonates, alkyl ester sulfonates, primary or secondary C 6 - C 2 2-alkane sulfonates, C 6 -C 24 olefin sulfonates, aryl sulfonates (especially unsubstituted and alkyl-substituted benzene and naphthalene sulfonate), sulfonated polycarboxylic acids, alkyl glycerol, fatty acyl glycerol sulfonates, monoester of sulfosuccinate (especially saturated and unsaturated C 2 -C 8 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C 6 -C 4 diesters), fatty oleyl glycerol
  • Anionic carboxylate surfactant include the alkyl ethoxy carboxylates, the alkyl polyethoxypolycarboxylate surfactants and the soaps ("alkyl carboxyls"), especially certain secondary soaps as described herein.
  • Suitable alkyl ethoxy carboxylates include those with the formula RO (CH 2 CH 2 0) x CH2 COO-M ® wherein R is a C 6 - to Cie alkyl group, x ranges from 0 to 10 and that the amount of material the ethoxylate distribution is such where x is 0, less than 20 wt%, and M is a cation.
  • Suitable alkyl polyethoxypolycarboxylate surfactants include those having the formula RO (CHR 1 -CHR 2 -O) -R 3 , wherein R is a C 6 to C 18 alkyl group, x is from 1 to 25, R 1 and R 2 are selected from the group consisting of hydrogen, methyl acid residue, succinic acid residue, hydroxysuccinic acid residue and mixtures thereof, and R 3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having from 1 to 8 carbon atoms, and mixtures thereof.
  • Suitable soap surfactants include the secondary soap surfactants containing a carboxyl moiety bonded to a secondary carbon.
  • Preferred secondary soap surfactants are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1 - octanoic acid and 2-pentyl-1-heptanoic acid.
  • Sarcosinate surfactant Other suitable anionic surfactants are the sarcosinates of the formula R-CON (R 1 ) CH 2 COOM, where R is a linear or branched C 5 -C 17 alkyl-; or alkenyl group, R 1 is a CC 4 alkyl group and M is an alkali metal ion.
  • R is a linear or branched C 5 -C 17 alkyl-; or alkenyl group, R 1 is a CC 4 alkyl group and M is an alkali metal ion.
  • Preferred examples are the myristyl and Oleoylmethylsarcosinate in the form of their Sodium salts.
  • the anionic surfactant may particularly preferably be selected from the group comprising alkyl sulfates, aryl sulfonates, fatty alcohol sulfates, secondary alkyl sulfates, paraffin sulfonates, alkyl ether sulfates, alkyl polyglycol ether sulfates, fatty alcohol ethersulfates, alkylbenzenesulfonates, alkylphenol ether sulfates, alkyl phosphates, phosphoric mono, di-, tri-esters, alkyl ether phosphates , Ethoxylated fatty alcohol phosphoric esters, phosphonic acid esters, sulfosuccinic acid esters, sulfosuccinic acid monoesters, sulfosuccinamides, sulfoxylates, ⁇ -olefinsulfonates, alkylcarboxylates, alkylethercarboxylates, al
  • Suitable cationic surfactants which may be used as the surfactant component include quaternary ammonium surfactants.
  • the quaternary ammonium is a mono C 6 -C 6 -, preferably C 6 -C 0 N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxy-ethyl or hydroxypropyl groups.
  • the monoalkoxylated and bisalkoxylated amine surfactants are also preferred.
  • cationic surfactants that can be used are cationic ester surfactants.
  • the cationic ester surfactant is a preferably water-dispersible compound having surfactant properties comprising at least one ester (i.e., -COO) bond and at least one cationically charged group.
  • ester bond and the cationically charged group in the surfactant molecule are separated by a spacer group consisting of a chain comprising at least three atoms (ie chain length of three atoms), preferably three to eight atoms, more preferably three to five atoms, most preferably three atoms.
  • the atoms forming the spacer group chain are selected from the group consisting of carbon, nitrogen and oxygen atoms and any mixtures thereof, with the proviso that any nitrogen or oxygen atom in the chain is attached only to carbon atoms in the chain.
  • spacer groups having, for example, -O-O- (ie peroxide) -NN- and -NO- are excluded bonds, whereas spacer groups having, for example - 2 bonds are included, and -CH2-NH-CH - CH 2 -0-CH. 2
  • the spacer group chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain.
  • Cationic monoalkoxylated amine surfactants Preferably usable cationic monoalkoxylated amine surfactants have the general formula V:
  • Particularly preferred Z n R 4 groups are -CH 2 CH 2 OH, -CH 2 CH 2 CH 2 OH, -CH 2 CH (CH 3 ) OH and CH (CH 3 ) CH 2 OH, wherein --CH 2 CH 2 OH is particularly preferred.
  • Preferred R 1 groups are linear alkyl groups. Linear R 1 groups of 8 to 14 carbon atoms are preferred.
  • the ethoxy (CH 2 CH 2 O) units (EO) of the formula II can also be prepared by butoxy, isopropoxy [CH (CH 3 ) CH 2 O] and [CH 2 CH (CH 3 ) O] units (US Pat. i-Pr) or n-propoxy units (Pr) or mixtures of EO and / or Pr and / or i-Pr units.
  • Cationic bisalkoxylated amine surfactant preferably has the general formula VII:
  • R 1 is an alkyl or alkenyl moiety having 8 to 18 carbon atoms, preferably 10 to 16 carbon atoms, most preferably 10 to 14 carbon atoms
  • R 2 is an alkyl group having one to three carbon atoms, preferably methyl
  • R 3 and R 4 may vary independently and are selected from hydrogen (preferred), methyl and ethyl
  • X- is an anion such as chloride, bromide, methylsulfate, sulfate or the like sufficient to provide electrical neutrality.
  • Z may vary independently and are each selected from C 1 -C 4 alkoxy, especially ethoxy (ie, -CH 2 CH 2 O-), propoxy, butoxy, and mixtures thereof; n is the same or different from each other 1 to 30, preferably 1 to 4, and most preferably 1.
  • Preferred cationic bisalkoxylated amine surfactants have the formula VIII:
  • R 1 is C 0 -C 8 hydrocarbyl and mixtures thereof, preferably Ci 0 -, C 12 -, C 4 alkyl, and mixtures thereof.
  • X is any suitable anion to provide charge balance, preferably chloride.
  • R 1 is derived from (coconut) C 12 -C 14 alkyl fatty acids.
  • suitable cationic bisalkoxylated amine surfactants include compounds of the formula IX:
  • R 1 do-C-is-hydrocarbyl, preferably C 0 -C 4 alkyl, p is 1 to 3 and q is 1 to 3 independently, R 2 is -C 3 - alkyl, preferably methyl, and X is a Anion, preferably chloride or bromide.
  • the cationic surfactant may more preferably be selected from the group comprising esterquats, preferably di (tallow fatty acid amidoethyl) methylpolyethoxyammonium methosulfate, diamidoamine quats, alkyloxyalkyl quats, preferably cocopentaethoxymethylammonium methosulfate and / or trialkyl quats, preferably cetyltrimethylammonium chloride.
  • esterquats preferably di (tallow fatty acid amidoethyl) methylpolyethoxyammonium methosulfate, diamidoamine quats, alkyloxyalkyl quats, preferably cocopentaethoxymethylammonium methosulfate and / or trialkyl quats, preferably cetyltrimethylammonium chloride.
  • Nonionic Surfactant Substantially all nonionic surfactants are suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred.
  • Preferred alkoxylated surfactants may be selected from the classes of nonionic condensates of alkylphenols, nonionic ethoxylated alcohols, nonionic ethoxylated / propoxylated fatty alcohols, nonionic ethoxylate / propoxylate condensates with propylene glycol and the nonionic ethoxylate condensation products with propylene oxide
  • Nonionic surfactant of alkoxylated alcohol The condensation products of aliphatic alcohols with 1 to 25 moles of alkylene oxide, especially ethylene oxide, propylene oxide, butylene oxide, dodecene oxide or styrene oxide are also usable according to the invention.
  • the alkyl chain of the aliphatic alcohol may be either straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
  • Particularly preferred are the condensation products of alcohols having an alkyl group of 8 to 20 carbon atoms with 2 to 10 moles of ethylene oxide per mole of alcohol.
  • Nonionic polyhydroxy fatty acid amide surfactant Polyhydroxy fatty acid amides which are suitable are those having the structural formula R 2 CONR 1 Z wherein: R 1 is H, C 1 -C 4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl ethoxy, propoxy or a mixture thereof, preferably CrC 4 Alkyl, more preferably Ci or C 2 alkyl, most preferably d-alkyl (ie methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C 5 -C 9 alkyl or alkenyl, more preferably straight chain C 9 -C 7 alkyl or alkenyl, most preferably straight chain Cn-Ci 7 - Alkyl or alkenyl, or a mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain in which at least 3 hydroxyl groups are attached directly to the chain or an alkoxylated derivative (preferably ethoxylated or propoxy
  • Nonionic fatty acid amide surfactant include those having the formula: R 6 CON (R 7 ) 2 wherein R 6 is an alkyl group of 7 to 21, preferably 9 to 17 carbon atoms and each R 7 is selected from the group consisting of Hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and - (C 2 H 4 0) X H is selected, where x is in the range 1 to 3
  • Nonionic Alkyl Polysaccharide Surfactant Suitable alkyl polysaccharides for use herein are disclosed in U.S. Patent 4,565,647, having a hydrophobic group containing from 6 to 30 carbon atoms and a hydrophilic polysaccharide, e.g. B. a polyglycoside group containing 1 to 3 to 10 saccharide units.
  • Preferred alkylpolyglycosides have the formula: R 2 O (CnH 2 nO) t (glycosyl) x wherein R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof in which the alkyl groups have from 10 to 18 carbon atoms contain; n is 2 or 3; t is from 0 to 10 and x is from 1, 3 to 8.
  • the glycosyl is preferably derived from glucose.
  • the nonionic surfactant may particularly preferably be selected from the group comprising alcohol ethoxylates, fatty alcohol polyglycol ethers, fatty acid ethoxylates, fatty acid polyglycol esters, glyceride monoalkoxylates, alkanolamides, fatty acid alkylolamides, ethoxylated alkanolamides, fatty acid alkylolamidoethoxylates, imidazolines, ethylene oxide-propylene oxide block copolymers, alkylphenol ethoxylates, alkylglucosides, ethoxylated sorbitan esters and / or amine alkoxylates.
  • Amphoteric surfactant Suitable useful amphoteric surfactants include the amine oxide surfactants and the alkyl amphocarboxylic acids.
  • Suitable amine oxides include those compounds of the formula R 3 (OR 4 ) x NO (R 5 ) 2 wherein R 3 is selected from alkyl, hydroxyalkyl, acylamidopropyl; and alkylphenyl group or mixtures thereof having from 8 to 26 carbon atoms; R 4 is an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms or mixtures it is; x is from 0 to 5, preferably from 0 to 3; and each R 5 is an alkyl or hydroxyalkyl group of 1 to 3 or a polyethylene oxide group of 1 to 3 ethylene oxide groups.
  • C 8 - - alkyldimethylamine oxide and C1 0 - Ci 8 -Acylamidoalkyldimethylaminoxid C1 0 are preferred.
  • amphoteric surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are preferred amphoteric surfactants.
  • Suitable betaines are those compounds of the formula R (R ') 2 N + R 2 COO- wherein R is a C 6 -C 8 hydrocarbyl group, each R 1 is typically CrC 3 alkyl and R 2 is CrC 5 - Hydrocarbyl group is.
  • Preferred betaines are C 2 -C 8 - Dimethylammoniohexanoat and the C 0 -C 8 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable according to the invention.
  • amphoteric surfactant may more preferably be selected from the group comprising amphoacetates, amphodiacetates, glycinates, amphopropionates, sultaines, amine oxides and / or betaines.
  • the mixtures according to the invention can be used for the production of flexible polyurethane foams, which include in particular (conventional) polyether soft foams, as well as polyester flexible foams, viscoelastic foams and high resilience (cold) foams, but in particular (conventional) polyether soft foams, and thereby allow a particular effective influence name on the cell refinement.
  • foams include in particular (conventional) polyether soft foams, as well as polyester flexible foams, viscoelastic foams and high resilience (cold) foams, but in particular (conventional) polyether soft foams, and thereby allow a particular effective influence name on the cell refinement.
  • blowing agents such as in particular liquid C0 2 or methylene chloride, which are usually particularly high Requirements for the polyether siloxane with regard to reaching a fine-pored cell structure.
  • polyether siloxanes of the general formula (I) on which this invention is based are, in particular, polysiloxane-polyoxyalkylene copolymers which contain modified polyoxyalkylene building blocks.
  • the polysiloxane can be varied almost arbitrarily with respect to the number of siloxane units and the number of possible connections with the polyoxyalkylene.
  • DE-A-15 70 647 describes the so-called SiOC-linked polyethersiloxanes.
  • the preparation of this polyethersiloxane class is described i.a. in DE-A-10 12 602, DE-A-10 40 251, DE-A-11 20 147 and in US Pat. No. 3,115,512.
  • Polysiloxane-polyoxyalkylene block copolymers are described, for example, in US Pat. No. 2,846,431 458 and in the Auslegeschriften DE-A-12 20 615 and DE-A-11 53 166 described.
  • the amides of the general formula III are used in an amount of from 0.1 to 200 parts by weight, in particular from 10 to 150 parts by weight, based on 100 parts by weight of the polysiloxanes of the general formula I. become.
  • Suitable amides of the formula (III) may, for. Example by reacting alkanolamines with carboxylic acids, preferably of fatty acids or fatty acid esters are prepared.
  • monocarboxylic acids dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids are used for example based on aliphatic or aromatic hydrocarbons or derivatives thereof.
  • Preferred acids are straight-chain saturated or unsaturated fatty acids having up to 40 carbon atoms, such as.
  • Butyric acid (butanoic acid), caproic acid (hexanoic acid), caprylic acid (octanoic acid), capric acid (decanoic acid), lauric acid (dodecanoic acid), Myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid), arachic acid (eicosanoic acid), behenic acid (docosanoic acid), lignoceric acid (tetracosanic acid), palmitoleic acid ((Z) -9-hexadecenoic acid), oleic acid ((Z) -9-hexadecenoic acid ), Elaidic acid ((E) -9-octadecenoic acid), cis-vaccenic acid ((Z) -11-octadecenoic acid), linoleic acid ((9Z, 12Z) -9,12
  • dimer and oligomer fatty acids such as those resulting from the oligomerization of unsaturated fatty acids, can be used.
  • Suitable amines for the preparation of amides of the formula (III) are those having at least one primary or secondary amine function for amidation, which may optionally have one or more hydroxyl groups.
  • Suitable amines are, for example: ethylenediamine, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylenehexamine, hexapropylenepheptamine, and higher homologs based on ethylenediamine or propylenediamine, 1,2-propylenediamine, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4-methylenediphenylenediamine, isophoronediamine, trimethylhexamethylenediamine, neopentanediamine, octamethylenediamine, polyetheramines such as polyetheramine D 2000 (BASF), Polyetheramine D 230 (BASF), polyetheramine T 403 (
  • Suitable hydroxylamines having at least one OH function are, for example: ethanolamine, propanolamine, alkylethanolamines, arylethanolamine, alkylpropanolamine, for example: diethanolamine, monoethanolamine, diisopropanolamine, isopropanolamine, methylisopropanolami, digylcolamine (2- (2-aminoethoxy) ethanol), dimethylethanolamine , N- (2-hydroxyethyl) aniline, 1- (2-hydroxyethyl) piperazine, 2- (2-aminoethoxy) ethanol, 3-amino-1-propanol, 5-amino-1-pentanol, butylethanolamine, ethylethanolamine, N- Methylethanolamine, aminopropylmonomethylethanolamine, 2-amino-2-methylpropanol, trishydroxymethylaminomethane (THMAM or TRIS), N- (2-aminoethyl) ethanolamine (
  • alkoxylates in particular ethoxylates and / or propoxylates of amines, for example alkylamines having a hydroxyethyl or hydroxypropyl unit or, for example, N-hydroxyethylcyclohexyldiamine, N-hydroxethylisophoronediamine, N-hydroxyethylpiperazine, bis (hydroxyethyl) toluenediamine.
  • Amides of the formula (III) according to the invention may also be commercially available amides having OH or NH functions, e.g. from Evonik Industries: Rewomid® DC 212 S, Rewomid® DO 280 SE, Rewocid® DU 185 SE, Rewolub® KSM, REWOMID® C 212, REWOMID® IPP 240, REWOMID® SPA, Rewopon® IM AO, Rewopon® IM AN or Rewopon® IM R 40 and DREWPLAST® 154, NINOL® 1301, NINOL® 40-CO, NINOL® 1281, NINOL® COMF, NI NOL® M-10 and ethoxylated diethanolamine such as NINOL® C-4 I, NINOL® C-5 , NINOL® 1301 from Stepan or DACAMID® MAL and DACAMID® DC from Sasol.
  • Evonik Industries Rewomid® DC 212 S, Rewomid® DO
  • the mixtures according to the invention comprising (a) polysiloxane of the general formula I and (b) amide group-containing compounds according to the general formula III, and (c) at least one organic solvent, in particular dipropylene glycol, in a total amount of 0.01 to 13% by weight, preferably 0.1 to 13% by weight, based on the total polyurethane foam formulation used.
  • the proportion of erfindunswashen mixture comprising (a) polysiloxane of the general formula I and (b) amide group-containing compounds according to the general formula III, and (c) at least one organic solvent, in particular dipropylene glycol, based on 100 parts by mass of polyol preferably from greater than 0.05 to 20 parts by mass, preferably from 0.2 to 10 parts by mass, and more preferably from 0.5 to 5 parts by mass.
  • the amides of the formula (III) are already used as solvent in the production process of the Si compounds to be used in the mixture, usually a hydrosilylation process. In this way, an additional separation step and / or the entry of undesired solvents in the compositions according to the invention are avoided.
  • the amide of the formula (III) is at least one compound of the formula (IIIa)
  • the mixture according to the invention as amide of the formula (III) preferably comprises at least one compound of the formula (IV) with R defined above for formula (III), wherein the amide of the formula (IV) is preferably obtained by reacting a fatty acid with diethanolamine.
  • Another object of the present invention is a process for the preparation of flexible polyurethane foams using organofunctionally modified polysiloxanes of the general formula I.
  • R 1 are independently of each other, alkyl radicals or aryl radicals
  • R 2 are independently of one another, equal to R 1 and / or R 3 , with the proviso that at least one radical R 2 has the meaning R 3 ,
  • R 3 independently of one another, a polyether radical of the formula II
  • Y is a hydrocarbon radical which is optionally branched
  • Hydrocarbon radicals of C1 to C18 is,
  • Z is a hydrogen radical or a monovalent organic radical, optionally an acetyl radical,
  • m + p 1 to 200, where p and m blocks can be arranged in any order, a is a number from 1 to 100, if b is a number from> 6 to 8,
  • a is a number from 1 to 200, when b is a number from> 3 to 6,
  • a is a number from 1 to 300, when b is a number from 0 to 3,
  • b 0 to 8, e.g. 1 to 8,
  • R ' is identical or different and is H or organic radical, preferably C 1 -C 2 -alkyl, aryl, alkylaryl radical, which may optionally contain oxygen or nitrogen atoms, in particular hydroxyl or amino groups, or a radical -XZ,
  • the mixtures according to the invention can be used.
  • the simultaneous application of the Ingredients (a) to (c) as a mixture very particularly advantageous, since this leads to a significantly better effect on cell refining than a separate addition, such as the addition of the amide compound (b) via the polyol component.
  • a mixture comprising constituents (a) to (c) should be used.
  • the preparation of the flexible polyurethane foams can otherwise be carried out in the usual way and as described in the prior art. It is well known to those skilled in the art and includes in particular the reaction of at least one polyol component with at least one isocyanate component in the presence of one or more catalysts which catalyze the isocyanate-polyol and / or isocyanate-water and / or isocyanate trimerization reactions preferably also water, physical blowing agents, flame retardants and / or other additives can be added, and wherein the method, as stated above, according to the invention using organofunctionally modified polysiloxanes of the general formula I is carried out, wherein the polysiloxanes of general formula I in admixture with organic solvent and at least one compound of formula III.
  • the amides of the general formula III in an amount of 0.1 to 200 parts by wt., In particular 10 to 150 parts by wt., Based on 100 parts by weight of the polysiloxanes of the general formula I use.
  • Particularly preferred are the mixtures of polysiloxane (a) and amide compound (b) and at least one organic solvent in an amount of 0.01 to 13 wt .-%, preferably 0.1 to 13 wt .-% based on the total polyurethane foam Formulation used.
  • the polyol component which can be used in the context of the process according to the invention is preferably different from the amide compounds of the formula (III) and the siloxane compounds (I) present in the mixture.
  • Suitable polyols which can advantageously be used in the context of this invention are all organic substances having a plurality of isocyanate-reactive groups and also their preparations.
  • Preferred polyols are all for the production of polyurethane foams, in particular polyurethane or polyisocyanurate flexible foams, commonly used polyether polyols and polyester polyols.
  • Polyether polyols are obtained by reacting polyhydric alcohols or amines with alkylene oxides.
  • Polyester polyols are based on esters of polybasic carboxylic acids (usually phthalic acid or terephthalic acid) with polyhydric alcohols (usually glycols).
  • corresponding polyols are used, for example as described in: US 2007/0072951 A1, WO 2007/11 1828 A2, US 2007/0238800, US 6359022 B1 or WO 96 12759 A2.
  • preferably usable vegetable oil-based polyols are described in various patents, such as in WO 2006/094227, WO 2004/096882, US 2002/0103091, WO 2006/116456 and EP 1 678 232 and polymer polyols, as for example in the documents US Re-28,715 and US-A-3,346,557, US-A-3,823,201, US-A-3,850,861, US-A-4,454,255, US-A-4,458,038, US-A- 4,550,194, US-A-4,390,645 and US-A-4,431,754.
  • Isocyanatkomponente for the production of polyurethane foams, in particular polyurethane or polyisocyanurate flexible foams, suitable Isocyanate compounds are used.
  • one or more organic isocyanates having two or more isocyanate functions can be used.
  • Suitable isocyanates in the context of this invention are, for. B. all polyfunctional organic isocyanates, such as 4,4'-diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI) and isophorone diisocyanate (IPDI).
  • MDI 4,4'-diphenylmethane diisocyanate
  • TDI toluene diisocyanate
  • HMDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • polymeric MDI ("crudeMDI) of MDI and higher condensed analogues having an average functionality of 2 to 4.
  • suitable isocyanates are described in EP 1 712 578 A1, EP 1 161 474, WO 058383 A1, US 2007/0072951 A1, EP 1 678 232 A2 and WO 2005/085310.
  • Preferred amines which can be used for catalysing the isocyanate-water reaction are selected from triethylamine, dimethylcyclohexylamine, tetramethylethylenediamine, tetramethylhexanediamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, triethylenediamine, dimethylpiperazine, 1,2-dimethylimidazole, ⁇ , ⁇ -dimethylhexadecylamine, silamorpholine, N -Ethylmorpholin,
  • Evonik Industries AG such amines or amine catalysts z. B. under the name Tegoamin ® SMP, Tegoamin ® 33 or Tegoamin ® ZE 4, are obtained.
  • tin (II) salts Preferably used as the metal salt of a carboxylic acid are preferably potassium, tin, zinc or bismuth salts, preferably tin (II) salts.
  • at least one tin (II) salt of 2-ethylhexanoic acid, ricinoleic acid or 3,5,5-trimethylhexanoic acid can be used.
  • a tin-Il salt of 2-ethylhexanoic acid exhibiting catalyst under the name KOSMOS ® 29 can be obtained.
  • organic tin compounds such as dibutyltin dilaurate, in particular, when it comes to HR foam production.
  • Another object of the invention is a composition suitable for the production of flexible polyurethane foams, the at least one polyol component, a catalyst which catalyzes the formation of a urethane or isocyanurate bond, optionally a blowing agent, optionally further additives and an isocyanate component, wherein
  • a mixture according to the invention, as described above, is included.
  • Another object of the invention is a flexible polyurethane foam, obtainable by a method as previously described.
  • polyurethane foams or the polyurethane foams resulting from the process according to the invention can be used especially in furniture (eg as furniture molded foam) and mattress industry, vehicle (eg for headrests for automobile seats, automobile seat upholstery, sheet material made of flexible PU foam for vehicle interior decoration) -, shoe and textile industry, but also in the household and in the technical sector (eg as packaging material) are used.
  • Another object of the invention is the use of the mixtures according to the invention for the production of flexible polyurethane foams, in particular for increasing the cell fineness in the production of flexible polyurethane foams.
  • a flexible polyurethane foam was made in a 27 x 27 cm open crate with a wall height of 27 cm by foaming various formulations with the following ingredients.
  • a formulation with a very small amount of stabilizer (formulation I: 0.6 parts)
  • a formulation with an extremely high amount of stabilizer (formulation II: 10 parts) and methylene chloride was chosen to create extreme conditions and to compare the cell structure under these conditions:
  • TEGOSTAB ® silicone stabilizers available from Evonik Industries
  • TDI 80 tolylene diisocyanate 80% 2,4-isomers and 20% 2,6-isomer
  • a foam-stabilizing agent a by hydrosilylation of Si-H group-containing siloxanes with allyl started polyethers available silicone polyether copolymer having the trade designation TEGOSTAB ® BF 2470 according to a SiC-polyether siloxane according to the formula (I), used for stabilization of the resulting foams ,
  • this stabilizer was mixed with small amounts of an amide-containing fatty alcohol of the formula IV, while in the comparative experiments I and VI no amide group-containing fatty alcohol was used.
  • the amide group-containing alcohol was not blended with the stabilizer but added separately to the formulation with the polyol.
  • the ratio of polyether siloxane to blending component / amide mixture was 1 to 1.
  • the foam body obtained was cut horizontally and the cell structure found at a height of 15 cm above the foam bottom at the cut surface was evaluated. Assessment criteria were both the number of cells / cm and the regularity of the cell structure obtained.
  • a ranking was introduced which compares the cell structure with a standard foam. A ranking of 1 means a very rough, a ranking of 5 a maximum fine cell structure.
  • the back pressure was measured, which, when flowing through the foam sample with 8 liters per Minute at a circular feed line with 2 cm diameter results.
  • Blending component 75% water, 12.5% sodium alkylbenzenesulfonate, 12.5%
  • Amide amide group-containing fatty alcohol of formula IV It is clear that the use of amide group-containing fatty alcohols as a component of a flexible foam stabilizer has a surprisingly positive effect on the fineness of the resulting polyurethane foams. It can be seen that as the proportion of amide-group-containing fatty alcohol increases, an increased fine-celledness results. In this case, two to three cells / cm can be obtained, which corresponds to a considerable improvement. The ranking value also shows an increase of up to 1, 5 points, which corresponds to a very clear refinement of the cell structure.
  • the experiment XVI shows that the addition of the component into the polyol also leads to a positive effect with regard to cell refining.
  • the cell refining effect could also be demonstrated in machine trials with liquid, pressurized C0 2 as propellant (according to the CarDio®, Novaflex TM or Beamech TM method).

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Abstract

L'invention concerne des mélanges comprenant (a) du polysiloxane à modification organofonctionnelle, (b) des composés amidiques, et (c) un solvant organique, facultativement en combinaison avec d'autres partenaires de mélangeage, ainsi que leur utilisation dans la fabrication de mousses de polyuréthane souples et un procédé de fabrication de mousses de polyuréthane souples.
PCT/EP2014/067142 2013-09-02 2014-08-11 Utilisation de mélanges de polysiloxanes à modification organofonctionnelle et d'amides dans la fabrication de mousses de polyuréthane souples WO2015028295A1 (fr)

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CN115505127A (zh) * 2022-09-29 2022-12-23 苏州思德新材料科技有限公司 一种改善硬质泡沫表面缺陷的泡沫稳定剂及其制备方法
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