EP2367615A1 - Formulations de siloxane aqueuses pour la production de mousses souples à froid de polyuréthanne à haute élasticité - Google Patents

Formulations de siloxane aqueuses pour la production de mousses souples à froid de polyuréthanne à haute élasticité

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Publication number
EP2367615A1
EP2367615A1 EP09756493A EP09756493A EP2367615A1 EP 2367615 A1 EP2367615 A1 EP 2367615A1 EP 09756493 A EP09756493 A EP 09756493A EP 09756493 A EP09756493 A EP 09756493A EP 2367615 A1 EP2367615 A1 EP 2367615A1
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EP
European Patent Office
Prior art keywords
water
foam
cold
particulate
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09756493A
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German (de)
English (en)
Inventor
Martin Glos
Matthias NAUMANN
Mladen Vidakovic
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
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Evonik Goldschmidt GmbH
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Publication date
Application filed by Evonik Goldschmidt GmbH filed Critical Evonik Goldschmidt GmbH
Publication of EP2367615A1 publication Critical patent/EP2367615A1/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use 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; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/10—Silicon-containing compounds

Definitions

  • Aqueous siloxane formulations for the production of highly elastic polyurethane foams are provided.
  • the present invention relates to aqueous cold-cure flexible foam siloxane formulations for use in the production of highly elastic polyurethane flexible foams or for use in the preparation of cold foam activator solutions for highly elastic polyurethane cold foams and their use.
  • the present invention further provides cold low foam activator solutions based on the aqueous cold flexible foam siloxane formulations and highly elastic polyurethane cold foams using the aqueous cold flexible foam siloxane formulations and / or cold soft foam activator solutions.
  • Cold-dry foam siloxane formulations in the context of this application include aqueous compositions
  • Siloxanes which are suitable for the production of cold foams to understand. Accordingly be under
  • Polyurethane cold foams are also referred to as “cold foams” or “high-resilience foams (HR-foams)”.
  • Car seats They are prepared by reacting isocyanates with polyols.
  • Polyurethane, crosslinking agents and polyisocyanates and customary auxiliaries, such as catalysts, stabilizers, blowing agents and the like, are usually used to prepare the polyurethane flexible foams. All these processes have in common that the system has a high intrinsic stability due to the early crosslinking of the polyurethane foam. Therefore, in many cases, the use of a polysiloxane-polyether copolymer, as an anti-reversion stabilizer additive, may or may not be dispensed with.
  • siloxanes described herein as stabilizers can perform various tasks in the foam, such as e.g. also cell regulation or cell opening, stabilization, marginal zone regulation, prevention of collapse phenomena, support of the flowability of the foaming mixture etc.
  • the siloxanes used are usually not used as pure substances, but incorporated as a component in a corresponding formulation in order to improve the meterability or incorporation into the reaction matrix.
  • various organic substances are used as a kind of solvent for such formulations.
  • Laid-open specification DE 2 356 443 describes a large number of organic solvents for the preparation of aralkyl-modified formulations containing siloxane oils. Often these are surface-active substances.
  • WO 2008/071497 describes water-based formulations of water-insoluble siloxanes for producing polyurethane cold foams, the formulations containing conventional molecular surfactants.
  • organic solvents bring a number of disadvantages, such as a problematic toxicological classification, too high flammability of the formulation and / or unwanted emission of organic solvent residues of the resulting foam with it. Further, the organic solvents may adversely affect the properties of the polyurethane foamed soft foam such as pore structure, elasticity and the like.
  • the use of water over organic solvents has the advantage that water is nearly unlimited available, non-toxic and non-flammable. Furthermore, water can be easily cleaned and disposed of without any technical effort. Another advantage is that the safety regulations for the storage of water are negligible.
  • the cold mild foam siloxane formulation can be made using other auxiliaries and additives, with the exception of the polyol and isocyanate components used to make Cold-cure polyurethane foams are required to be converted into a cold foam activator solutions.
  • the cold flexible foam siloxane formulation should have the highest possible proportion of water and water-insoluble polysiloxane compound.
  • the sum of water-insoluble polysiloxane compound and water should be greater than 50 wt .-% based on the total composition.
  • ⁇ -active substances can be used.
  • Advantages compared to the classic emulsion are the expected lower emissions of volatile organic components, corresponding to VOC (fogging) from the finished foam, which may result from blending components or surface-active substances.
  • solid state stabilized emulsions are known for their good stability to droplet coalescence, only creaming or sedimentation of the inner phase droplets depending on the droplet size, density difference between the outer and inner phases and the viscosity of the outer phase can be observed.
  • a stirred-up / sedimented solid-state-stabilized emulsion can be homogenized again simply by stirring; therefore, a good one
  • siloxanes in the form of a solid-state-stabilized emulsion are just as effective in foaming as siloxanes in a conventional one
  • Emulsion or a solution Surprisingly, in spite of the occupation of the interfaces from the solid-state-stabilized emulsion, the siloxane can be released already at the beginning of foaming. Since the interfaces between inner and outer phase in solid-stabilized emulsions with Particles are "occupied", their stability is significantly higher than when using surface-active molecules as emulsifiers. For this reason, surprisingly, the addition of emulsifiers can be largely or completely omitted.
  • the siloxanes in the inner phase must lower the surface tension of the overall system in order to ensure good nucleation, so that a corresponding fine-celled and regular foam can be formed.
  • Solid state stabilized aqueous emulsions were described in 1907 by S.U. Pickering ("Emulsions", Spencer Umfreville Pickering, Journal of the Chemical Society, Transactions
  • emulsion stabilization are nanoscale, predominantly inorganic particles, eg.
  • silica particles which are commercially available as "LUDOX®” in the form of aqueous sols or dispersions from Grace Davison
  • the mechanism of the stabilizing effect in the literature is the agglomeration of the particles and the agglomeration of the agglomerates the water / oil interface
  • the mechanism of emulsion stabilization by small silica (LUDOX®) particles Helen Hassander, Beatrice Johansson, Bertil Törnell, Colloids and Surfaces, 40, (1989), 93-105).
  • the inventive method also has the advantage that in the production of siloxane emulsions using particulate emulsifiers no or only small amounts of conventional emulsifiers are needed, which could interfere later in applications.
  • particulate preferably in at least one dimension nanoscale particles and / or nanostructured particles or nanoobjects which are particularly preferably selected from the group of semimetal oxides, metal oxides (for example Al, Si, Ti, Fe, Cu, Zr, B etc .), Mixed oxides, nitrides, carbides, hydroxides, carbonates, silicates, silicone resins, silicones and / or silica, and / or organic polymers wherein said classes of particles may all be optionally hydrophobed or partially hydrophobized, for.
  • semimetal oxides for example Al, Si, Ti, Fe, Cu, Zr, B etc .
  • Mixed oxides for example Al, Si, Ti, Fe, Cu, Zr, B etc .
  • nitrides for example Al, Si, Ti, Fe, Cu, Zr, B etc .
  • carbides for example Al, Si, Ti, Fe, Cu, Zr, B etc .
  • silicates for example Al, Si, Ti, Fe, Cu, Zr, B etc
  • nano-objects are understood as meaning materials which are nanoscale in one, two or three outer dimensions, preferably at least one dimension having a size of 1 to 100 nm, such as, for example, As nanoplates, nanorods and nanoparticles.
  • Nanostructured particles in the present invention are materials or particles which have an internal nanoscale structure. Typical representatives are z. B. aggregates and agglomerates of nano-objects.
  • Particularly preferred particulate emulsifiers have an average primary particle size in at least one dimension of less than 1000 nm, preferably less than 500 nm and particularly preferably from 1 to 100 nm.
  • the primary particle size can be determined in a manner known to the person skilled in the art, for example by means of SEM, TEM, DLS or static light scattering etc.
  • the primary particle size is determined by the optical evaluation of a
  • Coemulsifiers which can be used in the process according to the invention are, in particular, those compounds which interact with the solid-state emulsifier particles, preferably those which are absorbed by solid-state emulsifier particles to be hydrophobicized.
  • Coemulsifiers which can be used in the process according to the invention generally include cationic, nonionic or anionic, but also amphoteric surface-active substances, which are applied to the solid-state emulsifier particles.
  • VARISOFT 470P Commercially available under the trade names VARISOFT 470P, VARISOFT TC-90, VARISOFT 110, VARISOFT PATC, AROSURF TA-100, ADOGEN 442-100P, ADOGEN 432, ADOGEN 470, ADOGEN 471, ADOGEN 464, VARIQUAT K 300, VARIQUAT B 343, VARIQUAT 80 ME, REWOQUAT 3690, REWOQUAT WE 15, REWOQUAT WE 18, REWOQUAT WE 28 or REWOQUAT CR 3099 of Evonik Goldschmidt GmbH (the above-mentioned in capital letters written products are registered trademarks of Evonik Goldschmidt GmbH).
  • Cetyltrimethylammonium bromide or chloride (VARISOFT 300) or VARISOFT PATC are preferably used as cationic coemulsifiers in the process according to the invention.
  • coemulsifiers which may be used are, in particular, compounds selected from the group of anionic surfactants such as sodium lauryl sulfate, sodium lauryl ether sulfate, sulfosuccinates such as REWOPOL SB DO 75, alkyl ether phosphates, fatty acid anions, N-acylamino acids, olefinsulfonates or alkylbenzenesulfonates.
  • amphoteric or nonionic surfactants or surfactants can be used for this purpose. These compounds can exert a hydrophobicizing effect, but are alone - without particulate emulsifier - unable to develop the effect of the invention. However, the coemulsifiers may favor or optimize the action of the particulate emulsifier.
  • the modifi ⁇ z istsstoff having a functional group is at least capable of undergoing hydrogen bonds with the surface to be modified a covalent, ionic or coordinative bond or water.
  • These functional groups may be, for example, carboxylic acid groups, acid chloride groups, ester groups, nitrile and isonitrile groups, OH groups, SH groups, epoxide groups, anhydride groups, acid amide groups, primary, secondary and tertiary amino groups, Si-OH groups, hydrolyzable radicals of Silanes (Si-OR) or CH-acid groups such.
  • ⁇ -dicarbonyl compounds for example acetylacetone, 2,4-hexanedione, 3,5-heptanedione, diacetyl or acetoacetic acid.
  • modifying agent such as e.g. In betaines, amino acids, for example glycine, alanine, ß-alanine, valine, leucine, isoleucine, arginine and aminocaproic acid, as well as in EDTA.
  • Carboxylic acids for surface modification are, for example, fatty acids, formic acid, acetic acid, propionic acid, butyric acid, pentanoic acids, hexanoic acid, acrylic acid, adipic acid, succinic acid, fumaric acid, itaconic acid, stearic acid, hydroxystearic acid, ricinoleic acid and polyethercarboxylic acids and their corresponding anhydrides, chlorides, esters and amides, for example Methoxyacetic acid, 3, 6-dioxaheptanoic acid and 3, 6, 9-Trioxadecanklad and the corresponding acid chlorides, esters and amides.
  • fatty acids formic acid, acetic acid, propionic acid, butyric acid, pentanoic acids, hexanoic acid, acrylic acid, adipic acid, succinic acid, fumaric acid, itaconic acid, stearic acid, hydroxystearic acid, ricinole
  • the modifying agent may additionally have further radicals which modify the properties of the particle.
  • radicals, or parts thereof may for example be hydrophobic or hydrophilic or carry one or more functional groups, in order to render the silicone particles compatible with the surrounding medium, to render them inert or to render them reactive, which also binds to the surrounding Includes matrix.
  • These functional groups may, for example, be selected from the group of the alkyl, aryl, alkaryl, aralkyl, fluoroalkyl, hydroxy, alkoxy, polyalkoxy, epoxy, acryloyloxy, methacryloxy, acrylate, methacrylate, Carboxy-amino, sulfonyl, sulfate, phosphate, polyphosphate, phosphonate, amide, sulfide, hydrogen sulfide, haloalkyl, haloaryl and acyl groups.
  • the emulsions according to the invention are preferably prepared largely free of further co-emulsifiers. If, in addition, coemulsifiers are used, 0 to 10% by weight, based on the particulate emulsifier, are preferred 0.05 to 8 wt .-% and particularly preferably 0.2 to 5 wt .-% used.
  • compositions which are free of non-particulate emulsifiers are compositions which are free of non-particulate emulsifiers. If, for reasons of application technology, it is not possible to dispense with a nonparticulate emulsifier, it is contained in contents of> 0 to less than 10% by weight.
  • Oxidic particles e.g. pyrogenic, precipitated or Stöber process silica particles, but this does not exclude the use of other particulate materials.
  • silanes which additionally have at least one nonhydrolyzable radical.
  • silanes are represented by the general formula (IV)
  • R identical or different nonhydrolyzable groups
  • X identical or different hydrolyzable groups or hydroxyl groups
  • N 1, 2, 3 or 4.
  • Groups X for example H, halogen (F, Cl, Br, I), alkoxy
  • nonhydrolyzable radicals R may be both radicals with or without functional groups.
  • R in the general formula (IV) without functional groups may be, for example, an alkyl, alkenyl, alkynyl, aryl, alkylaryl or aralkyl radical.
  • radicals R and X may optionally have one or more customary substituents, such as, for example, halogen or alkoxy.
  • the functional group can be selected, for example, from the range of epoxide
  • These functional groups may be bonded to the silicon atom via alkylene, alkenylene or arylene bridging groups which may be interrupted by oxygen or NH groups.
  • These divalent bridging groups and optional substituents, as with alkylamino groups can be derived from the corresponding monovalent alkyl, alkenyl, aryl, aralkyl and alkaryl radicals.
  • the radical R may also have more than one functional group.
  • Nonhydrolyzable radicals R according to the general formula
  • (IV) with functional groups can be selected from the range of glycidyl or glycidyloxyalkylene radicals, such as, for example, ⁇ -glycidyloxyethyl, ⁇ -glycidyloxypropyl, ⁇ -glycidyloxypropyl, ⁇ -glycidyloxypentyl, ⁇ -glycidyloxyhexyl or 2- (3,4-epoxycyclohexyl ) ethyl, the methacryloxyalkylene and acryloxyalkylene radicals, such as, for example, methacryloxymethyl, acryloxymethyl, methacryloxyethyl, acryloxyethyl, methacryloxypropyl, acryloxypropyl, methacryloxybutyl or acryloxybutyl, and the 3-isocyanatopropyl radical.
  • glycidyl or glycidyloxyalkylene radicals such as, for example, ⁇ -
  • silanes with at least partially fluorinated alkyl radicals is also possible, for example 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8-tridecafluorooctyl or 3,3,3- Trifluoropropyl groups.
  • oxidic particles such. B., colloidal silica, as z. B. Grace Davison as LUDOX® is available to perform a surface modification with siloxanes and organopolysiloxanes. This can be done by using trimethylsiloxy-endcapped dimethylpolysiloxanes, cyclic dimethylpolysiloxanes, .alpha.,.
  • a suitable catalyst for example ammonium carbamate or alkylhydroxides
  • the surface modification with polysiloxanes or organopolysiloxanes can also be covalent or adsorptive, examples of such substance classes are organopolysiloxanes which are end- and / or comb-modified with polyether or polyester chains. Likewise, monofunctional polysiloxanes for surface modification of the
  • Particles are used, for example, with trimethylsilyl end-capped ⁇ -halo, ⁇ -alkoxy and ⁇ -Hydroxydimethylpolysiloxane.
  • Such a surface modification can be effected by the use of trimethylsiloxy-endcapped dimethylpolysiloxanes, cyclic dimethylpolysiloxanes, .alpha.,. Omega.-dihydroxypolydimethylsiloxanes, cyclic methylphenylsiloxanes, methylphenylpolysiloxanes end-capped with trimethylsiloxy groups and / or trimethylsiloxy- Groups of end-capped dimethylsiloxane-methylphenylsiloxane copolymers, optionally in the presence of a suitable cata- ⁇ sators (for example A ⁇ unoniumcarbamat or alkali metal hydroxides) and possibly also elevated temperatures.
  • a suitable cata- ⁇ sators for example A ⁇ unoniumcarbamat or alkali metal hydroxides
  • organopolysiloxanes can be covalent or adsorptive, examples of such substance classes are organopolysiloxanes end- and / or comb-modified with polyether or polyester chains.
  • monofunctional polysiloxanes can be used for surface modification of the particles, for example with ⁇ -halo, ⁇ -alkoxy and ⁇ -hydroxydimethylpolysiloxanes end-capped with trimethylsilyl groups.
  • an emulsion is produced whose average droplet size is adjusted from 0.01 to 1000 ⁇ m, preferably 0.1 to 500 ⁇ m and particularly preferably from 1 to 100 ⁇ m.
  • the droplet size can be estimated with the aid of light microscopy (up to about 1 ⁇ m as the lower limit) by measuring the smallest and largest droplet diameter in the field of view, it should be at least 10x10 drops in the field of view. Furthermore, it is possible to determine the droplet size distributions by the methods of static and dynamic light scattering familiar to the person skilled in the art.
  • pillate emulsion is understood to mean the novel aqueous siloxane composition stabilized using particulate additives or particulate emulsifiers.
  • Another object of the invention is a process for the preparation of a particulate emulsion, with droplet sizes in the preferred range, in which, in the simplest case, the particulate emulsifier is processed with the application of shear forces together with the liquid components to form a composition according to the invention.
  • Another object of the invention is a method in which coemulsifiers are used in addition to particles. It may be advantageous to add the coemulsifier or the coemulsifiers only after a preemulsion has been prepared in a substep al).
  • This pre-emulsion can be obtained by using a mixture of siloxanes of the general formula (I), water and emulsifier, preferably particulate emulsifier and particularly preferably nanoparticulate SiO 2 and very particularly preferably LUDOX® SM-AS from Grace Davison, with application of strong Shear forces, as z. B. is possible with a rotor-rotor system is emulsified.
  • a suitable rotor-rotor system is z. B. offered as a co-twister homogenizer from Symex.
  • This preemulsion is added in a further step a2) or the coemulsifiers.
  • the co-emulsifiers can be used as pure substance or in the form of a solution, for. B. an aqueous solution can be added.
  • the coemulsifier By adding the coemulsifier to the preemulsion, the droplet size of the droplets contained in the preemulsion can be quasi frozen.
  • the emulsifier particles are partially hydrophobized and occupy the interface between the inner and outer phases of the pre-emulsion.
  • the weight ratio of particulate emulsifier to coemulsifiers is up to 200 to 1, preferably up to 50 to 1.
  • emulsifier and coemulsifier can roughly preset the droplet size distribution of the emulsion.
  • Anionic surface-active compounds may be aliphatic of salts of carboxylic acids, alkyl benzene sulfonates, Alkylnaphthylsulfonaten, alkyl sulfonates, dialkyl sulfosuccinates, ⁇ -olefinsulfonates, salts example ⁇ example selected ⁇ - sulfonated aliphatic carboxylic acids, N-acyl-N-methyltaurates, Alkysulfaten, sulfated oils, ethoxylated poly- Alkyl ether sulfates, polyethoxylated alkyl phenyl ether sulfates, alkyl phosphates, polyethoxylated alkyl ether sulfates, polyethoxylated alkylphenyl ether sulfates and condensates of formaldehyde and naphthyl sulfonates.
  • Amphoteric surface-active compounds can be selected, for example, from N, N-dimethyl-N-alkyl-N-carboxymethylammonium betaines, N, N-dialkylaminoalkylenecarboxylates, N, N, N-trialkyl-N-sulphoalkyleneammammonium betaines, N, N-dialkyl-N, N-bispolyoxyethylene ammonium sulfate ester betaines, 2-alkyl-1-carboxymethyl-1-hydroxyethyl imidazolinium betaines.
  • Nonionic surface-active compounds can be selected, for example, from polyethoxylated alkyl ethers, polyethoxylated alkenyl ethers, polyethoxylated alkylphenyl ethers, polyethoxylated polystyrene phenyl ethers, polyoxyethylene-polyoxypropylene glycols, polyoxyethylene-polyoxypropylene alkyl ethers, partial esters of aliphatic carboxylic acids with polyfunctional alcohols, for example sorbitan esters, aliphatic glycerol esters, aliphatic polyglycerol esters, aliphatic decaglycerol esters, (mixed) aliphatic esters of ethylene glycol / pentaerythritol, (mixed) aliphatic esters of propylene glycol / pentaerythritol, polyethoxylated aliphatic partial esters of polyfunctional alcohols, for example polyeth
  • Such dispersing additives can be selected, for example, from the product portfolio of Evonik Goldschmidt GmbH, which are available there, for example, under the names "Tego® Dispers” or "Tegopren®”.
  • the content of such surface-active substances may be between 0.1 and 50% by weight, preferably between 1 and 30% by weight, based on the dispersion.
  • the emulsions can be aftertreated in a subsequent step a3), if appropriate by means of slit, jet or slot homogenizers, or else, for example, a so-called Microfluidizer from Microfluidics.
  • the particulate emulsion is aftertreated by means of the microfluidizer.
  • the particulate emulsion is dispersed in a homogenizer with interaction chamber.
  • the dispersion takes place in at least one interaction chamber containing microchannels, preferably with a capillary thickness (inner diameter) of 50 to 500 microns, and preferably at a pressure of 50 to 1000 bar, preferably 100 to 800 bar, more preferably 200 to 600 bar and subsequent Relaxation of the mixture to ambient pressure, z. B. in an outlet reservoir.
  • preferably one of the above-mentioned preferred droplet sizes is set. It can be advantageous if two or more in-line interaction chambers are used. In this way, the desired droplet size can be adjusted more easily.
  • interaction chambers are preferably used which have at least one microchannel with a capillary thickness of 100 to 300 ⁇ m.
  • Interaction chambers are particularly preferably used which have at least one, preferably exclusively, microchannels which have at least one deflection bend.
  • solid-state emulsifier is understood to mean a nanoscale particle, if appropriate with a corresponding co-emulsifier, at least in one dimension.
  • aqueous cold-cure flexible foam siloxane formulation for use in the preparation of flexible polyurethane foams or for use in the preparation of cold foam activator solutions for polyurethane cold foams, wherein the aqueous cold-cure flexible foam siloxane formulation is the following
  • Components includes:
  • % Water from 0.05% to 40% by weight, preferably from 0.3 to 30% by weight, more preferably from 0.5 to 20% by weight, and most preferably from 1 to 10% by weight % Solid emulsifier, d)> 0% by weight to 25% by weight, preferably 5 to 20% by weight, particularly preferably 10 to 20% by weight of functional substances, and e) optionally> 0% by weight.
  • % to 80 wt .-% preferably> 0 wt .-% to 20 wt .-%, particularly preferably 10 to 20 wt .-% of water-soluble siloxane / e, wherein the weight fraction of the aforementioned components is selected such that the total weight fraction of Components maximum 100 wt .-%, based on the aqueous Kaltweichschaum- siloxane formulation constitutes.
  • the novel cold flexible foam siloxane formulation may contain> 0.2% by weight to ⁇ 70% by weight, preferably> 0.5% by weight to ⁇ 60% by weight, more preferably> 1% by weight to ⁇ 50% by weight. -%, more preferably> 2 wt .-% to ⁇ 40 wt .-% and more preferably contain> 3 wt .-% to ⁇ 30 wt .-% of at least one water-insoluble polysiloxane compound.
  • the sum of water and water-insoluble polysiloxane compound is more than 50% by weight, preferably more than 60% by weight, more preferably more than 70% by weight and most preferably more than 80% Wt .-%, based on the total composition.
  • Another preferred cold-cure flexible siloxane composition according to the invention comprises the following components, which are also described in WO 2008/071497, which is hereby incorporated in its entirety as part of this disclosure:
  • R identical or different from one another, a linear, branched, unsaturated or saturated hydrocarbon radical having 1 to 50 C atoms,
  • aqueous cold-cure flexible foam siloxane formulation containing at least one water-insoluble polysiloxane compound according to the general formula (I) is preferred,
  • an aqueous cold-cure flexible foam siloxane formulation is preferred which contains at least one water-insoluble polysiloxane compound according to the general formula (I) in which at least one R 1 is a side chain, according to the formula (II):
  • R 3 identical or different from each other H, methyl, ethyl, propyl or phenyl,
  • the water-insoluble polysiloxane compound usable in the present invention has the following formula (III):
  • R identical or different from each other methyl or ethyl
  • water-insoluble polysiloxane compounds which can be used according to the invention are present in the form of a mixture whose distribution is determined essentially by statistical laws.
  • the various structural units in the above formulas (I), (II) and (III) may be arranged randomly or in blocks.
  • the values for a, g, n, m, k, p, r, and / or s therefore correspond to mean values.
  • the usable water-insoluble polysiloxane compounds in the composition according to the invention are suitable for the production of flexible polyurethane foams.
  • 0.1 to 5 parts by mass of the composition according to the invention are used per hundred parts by mass of polyol.
  • the proportion of water-insoluble polysiloxane compounds usable in the present invention is determined to be 0.005 to 5.0 parts by mass, preferably 0.01 to 2 parts by mass of water-insoluble polysiloxane compounds per hundred parts by mass of polyol.
  • water-insoluble polysiloxane polysiloxane understood that up to a maximum of 5 g in 100 ml of double-distilled water at 23 0 C in a 250 ml beaker by means of a Teflon-coated stirrer bar (3 cm length) at a stirrer speed of 200 U Stir homogeneously over a period of 1 hour without forming a phase separation after the mixture has stood for a period of at least 100 days.
  • water-soluble polysiloxane polysiloxane compounds understood that with> 5 g in 100 ml of double-distilled water at 23 0 C in a 250 ml beaker by means of a Teflon-coated stirrer (3 cm length) at a stirrer speed of 200 U Stir homogeneously over a period of 1 hour without forming a phase separation after the mixture has stood for a period of at least 100 days.
  • miscible solvents or soluble polymers such as xanthan gum, guar gum, carboxymethylcellulose, Polyvinylakohol, polyvinylpyrrolidone, carboxyvinyl, polyacrylates, hydroxyethylcellulose, Polythylenimine, polyethoxylated glycol stearate and clays, phyllosilicates, pyrogenic oxides such as AEROSIL® (Evonik Degussa), precipitated silicas, such as SIPERNAT® (Evonik Degussa), diatomaceous earth (diatomaceous earth), fumed silica, quartz powder, titanium dioxide, zinc oxide, cerium oxide, iron oxide, carbon black, graphite, carbon nanotubes or fibers, aluminosilicates, alkaline earth carbonates, aluminum trihydroxide, magnesium dihydroxide or Other known and customary solids from the prior art and any of the substances mentioned after surface modification with organosilicon compounds
  • Antifreezes include, for example, salts, such as
  • biocides for example chlorophen, benzisothiazolinone, hexahydro-1,3,5-tris (hydroxyethyl-s-triazine), chloro-methylisothiazolinone, methylisothiazolinone or 1,6-dihydroxy-2 , 5-dioxohexane, which are known under the trade names BIT 10, Nipacide BCP, Acticide MBS, Nipacide BK, Nipacide CI, Nipacide FC.
  • the cell openers which can be used are the substances known to the person skilled in the art, for example polyethers with a high proportion of polyethylene glycol (high EO content) as described in US Pat. No. 4,863,976, US Pat. No. 4,347,330.
  • Commercially available are, for example, Voranol CP 1421 from Dow Chemicals or polyethylene glycol 8000, polyethylene glycol 12000, polyethylene glycol 20000 or polyethylene glycol 35000 from Clariant.
  • These cell openers can be used particularly advantageously in the composition according to the invention, since phase separation occurs in the emulsions known hitherto, without the use of particles as surfactant, when these substances having a high EO content are added.
  • cold foams Because of the raw materials used, cold foams have very typical physical properties that distinguish them from hot foams.
  • the cold foams have:
  • rebound resilience Another important feature of the cold foams is the rebound resilience "ball rebound.”
  • a method of determining rebound resilience is described, for example, in ISO 8307, where a steel ball of specified mass is dropped from a certain height onto the specimen and then the height of the rebound Typical values for a cold soft foam are in the range of over 55%, whereas hot foams or polyurethane ester foams, also referred to below as ester foams, have only rebound values of a maximum of 30% to 48%.
  • the necessary Aufdrückkraft is a measure of the open cell. It is desirable to have foams with a high degree of open-cell character, which only require low printing forces. In the mold foaming polyurethane cold-cure flexible foams are in contrast to polyurethane hot ⁇ foams at a temperature of, for example ⁇ 9O 0 C was prepared.
  • the cold-water foam siloxane formulation containing water-insoluble polysiloxanes according to the invention as stabilizers and / or cold-low foam activator solution has advantageous properties for controlling cell size and cell size distribution as well as edge zone regulation.
  • the siloxanes used thus not only take over stabilizing function, but can also influence the cell opening, the cell size distribution or the flowability of the foam.
  • the necessary cell opening at the right time and to the right extent is the actual problem. If the cell opening is too early or too late, the foam may collapse or shrink. If a foam is not sufficiently open-celled, mechanical pressing can cause problems.
  • novel cold flexible foam siloxane formulation and / or cold soft foam activator solution have the following advantages:
  • water-insoluble polysiloxane compounds used have, per polysiloxane molecule, a maximum of 70 Si atoms, preferably not more than 50 Si atoms, particularly preferably 5 to 25 Si atoms, with polydimethylsiloxanes having 5 to 25 Si atoms in the molecule being most preferred.
  • the suitable polydimethylsiloxanes have a low viscosity. It has been found that polydimethylsiloxanes having a viscosity of> 200 mPas adversely affect the formation of the most regular cell structure possible. In particular viscosities of> 500 mPas or more lead to an undesired irregular spongy cell structure or even collapse of the foam.
  • polydimethylsiloxanes of the general formula (III) in which all radicals R, R 1 are methyl radicals and m is 0, are preferred, a viscosity of> 0 mPa-s to ⁇ 100 mPa-s, preferably a viscosity of> 0.5 mPa-s to ⁇ 80 mPa-s, preferably a viscosity of> 1 mPa-s to ⁇ 70 mPa-s and particularly preferably have a viscosity of> 1.5 mPa-s to ⁇ 50 mPa-s.
  • Viscosity unless otherwise indicated in the description of the present invention was measured according to DIN 53015 at 2O 0 C with a falling ball viscometer Höppler.
  • the viscosity of the cold mild foam siloxane formulation is in the range of 20 mPa-s to 10000 mPa-s, measured at 20 0 C according to Hoppler.
  • the size distribution of the present oil droplets is such that over 90% by volume of the oil droplets are smaller than 2 ⁇ m, smaller than 1 ⁇ m or smaller than 0.5 ⁇ m.
  • the size distribution was measured using a particle size analyzer from the company Beckman Coulter model "LS 230" according to the principle of laser diffraction, or the method of dynamic light scattering (DLS) is used for particularly finely divided emulsions and a micrograph can be evaluated by counting at least 10x10 drops.
  • the aqueous cold foam siloxane formulation is characterized by a very good stability.
  • the cold mild foam siloxane invention is storage stable at room temperature and forms, for example over a period of at least 10 days, preferably of at least 50 days and preferably of at least 100 days no droplet coalescence and consequent phase separation from. In the event that a creaming or sedimentation occurs, this can usually by easy stirring can be eliminated again without using high shear forces.
  • a particular advantage of the novel aqueous cold-cure flexible foam siloxane formulation is that it can be incorporated into an activator solution, giving a storage-stable, homogeneous activator solution.
  • known stabilizers based on water-insoluble siloxanes such as e.g.
  • TEGOSTAB® B 4113 LF available from Evonik Goldschmidt, does not produce homogeneous activator solutions.
  • the activator solution contains u.a. the siloxanes (stabilizers), the catalysts, such as amines, metal catalysts and the blowing agent, for example water, and possibly other additives, such as flame retardant, paint, biocides, etc., depending on the formulation of the foam.
  • the siloxanes stabilizers
  • the catalysts such as amines, metal catalysts and the blowing agent, for example water
  • the blowing agent for example water
  • additives such as flame retardant, paint, biocides, etc.
  • a homogeneous activator solution can be easily prepared without additional effort when mixing the cold foam siloxane invention having a composition comprising: - catalysts, preferably amines, metal catalysts, optionally physical blowing agents, preferably acetone, methylene chloride, additional water as a chemical Propellants, optionally flame retardants, UV stabilizers, dyes, biocides, pigments, cell openers, crosslinkers, other foam stabilizing substances and conventional additives that are needed for the production and use of the foam.
  • - catalysts preferably amines, metal catalysts, optionally physical blowing agents, preferably acetone, methylene chloride, additional water as a chemical Propellants, optionally flame retardants, UV stabilizers, dyes, biocides, pigments, cell openers, crosslinkers, other foam stabilizing substances and conventional additives that are needed for the production and use of the foam.
  • a preferred homogeneous cold soft foam activator solution according to the invention which is suitable for use in the production of highly elastic polyurethane flexible foams, comprises an aqueous cold spray foam siloxane formulation according to the invention and additives selected from the group comprising:
  • Catalysts preferably amines, metal catalysts, optionally physical blowing agents, preferably acetone, methylene chloride, - additional water as a chemical blowing agent, and optionally additives selected from the group comprising flame retardants, UV stabilizers, dyes, biocides, pigments, cell openers, crosslinking agents, other foam stabilizing Substances and common processing aids.
  • the cold mild foam activator solution may additionally contain all of the usual additives known in the art for activator solutions.
  • polyols it is possible to use all polyols which are suitable for the preparation of the cold soft foams in a manner familiar to the person skilled in the art.
  • suitable polyols are given in US 4477601, EP 0499200 and the publications cited therein.
  • highly reactive polyols are used. These are preferably trifunctional polyols which, in addition to a high molecular weight of usually between about 4800 and 6500 g / mol, have at least 70% up to 95% primary hydroxyl groups, such that their OH number is between 36 and 26 mg KOH / g ,
  • These polyols are up to 90% of propylene oxide, but contain almost exclusively from the addition of ethylene oxide resulting primary OH end groups.
  • the primary OH groups are far more reactive towards the isocyanate groups than the secondary OH groups of the polyols used for the production of polyurethane hot-flexible foam whose OH numbers are usually between 56 and 42 mg KOH / g at molecular weights between 3000 and 4500 g / mol.
  • SAN polyols These are highly reactive polyols containing a copolymer based on styrene / acrylonitrile (SAN) dispersed.
  • PHD polyols These are highly reactive polyols which also contain polyurea in dispersed form.
  • PIPA Polyols These are highly reactive polyols which contain a polyurethane in dispersed form, for example by in situ reaction of an isocyanate with an alkanolamine in a conventional polyol.
  • the formulations containing solids-containing polyols can be significantly less intrinsically stable and therefore, in addition to chemical stabilization by the crosslinking reaction, rather require physical stabilization as well.
  • solids content of the polyols they are used alone or in admixture with the above-mentioned unfilled polyols.
  • isocyanates organic isocyanate compounds containing at least two isocyanate groups can be used.
  • the known per se aliphatic, cycloaliphatic, araliphatic and preferably aromatic polyfunctional isocyanates come into question.
  • Isocyanates are particularly preferably used in a range from 60 to 140 mol% relative to the sum of the isocyanate-consuming components. Both TDI (2,4- and 2,6-toluene diisocyanate isomer mixture) and MDI (4,4'-diphenylmethane diisocyanate) are used.
  • Propellants include water whose reaction with the
  • Foam can be controlled by the added amount of water or blowing agent, with the preferred amounts of water used between 1.5 and 5.0 parts by mass, based on
  • Propellants such as carbon dioxide, acetone, hydrocarbons, such as n-, iso- or cyclopentane, cyclohexane, halogenated hydrocarbons, such as methylene chloride, tetrafluoroethane, Pentafluoropropane, heptafluoropropane, pentafluorobutane, hexafluorobutane and / or dichloromonofluoroethane.
  • the amount of the physical blowing agent is preferably in the range from 1 to 15 parts by weight, in particular from 1 to 10 parts by weight, the amount of water preferably in the range from 0.5 to 10 parts by weight, in particular from 1 to 5 Parts by weight.
  • Carbon dioxide is preferred by the physical blowing agent, which is preferably used in combination with water as a chemical blowing agent.
  • Another object of the invention are highly elastic polyurethane foams produced using compositions containing the particulate emulsifiers according to the invention.
  • Another object of the present invention relates to a product containing a highly elastic polyurethane cold foam, which is prepared using the aqueous cold-cure foam siloxane formulation and / or the Kaltweichschaum2011atoryour.
  • Another object of the invention is, for example, a car seat containing a highly elastic polyurethane cold foam which is prepared using the aqueous KaIt- soft foam siloxane formulation and / or the cold soft foam activator solution.
  • compositions according to the invention and the corresponding processes for their preparation are described below by way of example, without the invention being considered to be limited to these exemplary embodiments.
  • the water-insoluble siloxane used was a polydimethylsiloxane, as described in DE 25 33 074 A1, Example 4 as mixture 1.
  • Pre-emulsion was 7.5 g of a 5% aqueous CTAB solution
  • the mixture was treated with 200 g of water containing 0.4 g of TEGO® Carbomer 141 (available from Evonik Goldschmidt).
  • Comparative Example 1 anhydrous siloxane composition 30 g of siloxane were mixed with 270 g of dioctyl phthalate to form a homogeneous solution.
  • Example 5 and Comparative Example 2 show that activator solutions can be prepared only with the siloxane formulations according to the invention.
  • Example 6 shows that activator solutions can be prepared only with the siloxane formulations according to the invention.
  • Formulation B 60 parts of polyol having an OH number of 35 mg
  • KOH / g and a molecular weight of 5000 g / mol 40 parts of the PHD polyol with 20% solids and an OH number of 29 mg KOH / g and a molar mass of 6000 g / mol, 4 parts water, 1.5 parts diethanolamine, 0.5 parts TEGOAMIN ® 33, and 0.07 parts TEGOAMIN ® BDE and 48 parts of isocyanate (T80).
  • the foams were prepared in the known manner by mixing all components except the isocyanate in a beaker, then adding the isocyanate and stirring rapidly at high stirrer speed. Then the reaction mixture was placed in a paper-lined container with a footprint of 28x28 cm. One determined the rise height and the relapse. The blowing off of the foam was rated at 0-3, with 0 being given for bad or unrecognizable and 3 for very strong blowing, with values of 1-2 being targeted.
  • Relapse is the decrease of the height of rise in cm 1 minute after reaching the maximum rise height.
  • Blowing is the release of the Teibgase from the open cells of the foam.
  • Example 8 (using the activator solution from Example 5)
  • a foam was prepared using 6.5 parts of the activator solution prepared in Example 5 per 100 parts of polyol and 40 parts of isocyanate. The resulting foam had good stability. At a height of rise of 21.5 cm, the relapse was 0, 8 cm. The blow-off behavior was rated 1. The cell number was 10-11 cells / cm.
  • Example 9
  • the stabilizer used was the aqueous cold-cure flexible foam siloxane formulation from Example 1, taking into account the amount of water contained in the foam formulation.
  • the aqueous cold-cure flexible foam siloxane formulation was used in an amount such that 0.1 part of water-insoluble polysiloxane came to 100 parts of polyol.
  • the resulting foam had good stability. At a height of 21.8 cm, the relapse was 0.5 cm.
  • the blow-off behavior was rated 1.
  • the cell number was 10-11 cells / cm.
  • the stabilizer used was the aqueous cold-cure flexible foam siloxane formulation from Example 2, taking into account the amount of water in the foam formulation contained therein.
  • Cold foam siloxane formulation was used in an amount such that 0.1 part of water-insoluble polysiloxane came to 100 parts of polyol.
  • the resulting foam had good stability. At a height of 21.4 cm, the relapse was 1.1 cm.
  • the blow-off behavior was rated 1.
  • the cell number was 10-11 cells / cm.
  • the stabilizer used was the aqueous cold-cure flexible foam siloxane formulation from Example 3, taking into account the amount of water contained in the foam formulation.
  • the aqueous cold-cure flexible foam siloxane formulation was used in an amount such that 0.1 parts of water-insoluble polysiloxane 100 parts of polyol came.
  • the resulting foam had good stability. At a climbing height of 22.5 cm, the relapse was 0.4 cm.
  • the blow-off behavior was rated 1.
  • the cell count was 11 cells / cm.
  • the non-aqueous cold-cure flexible foam siloxane formulation of Comparative Example 1 was used as the stabilizer.
  • the cold mild foam siloxane formulation was used in an amount such that 0.1 part of water-insoluble polysiloxane came to 100 parts of polyol.
  • the resulting foam had good stability.
  • At a climbing height of 21 cm the relapse was 1.0 cm.
  • the blow-off behavior was rated 1.
  • the cell count was 11 cells / cm.
  • the foams were prepared in the known manner by mixing all components except the isocyanate in a beaker, then adding the isocyanate and stirring rapidly at high stirrer speed. The reaction mixture was then poured into a cuboid mold heated to 60 ° C. and allowed to cure for 6 minutes. Subsequently, the pressing forces were measured. Here, the foams were compressed 10 times to 50% of their height. Then (manual) was fully pressed in order to be able to determine the hardness of the pressed-on foam at the 11th measured value. After that, the Foams cut open to assess the skin and marginal zone and to determine the number of cells.
  • Example 7 shows that with the stabilizer formulations according to the invention also mold foams without Quality losses can be made.
  • the pressing force can be reduced.

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Abstract

L'invention concerne des formulations aqueuses de siloxane en mousse souple à froid, destinées à être utilisées pour la production de mousses souples à froid de polyuréthanne à haute élasticité, ou pour la production de solutions d'activateurs de mousses souples à froid pour des mousses à froid de polyuréthanne à haute élasticité.
EP09756493A 2008-12-23 2009-11-23 Formulations de siloxane aqueuses pour la production de mousses souples à froid de polyuréthanne à haute élasticité Withdrawn EP2367615A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008055115A DE102008055115A1 (de) 2008-12-23 2008-12-23 Wässrige Siloxanformulierungen für die Herstellung von hochelastischen Polyurethankaltweichschäumen
PCT/EP2009/065601 WO2010072488A1 (fr) 2008-12-23 2009-11-23 Formulations de siloxane aqueuses pour la production de mousses souples à froid de polyuréthanne à haute élasticité

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EP2367615A1 true EP2367615A1 (fr) 2011-09-28

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CN (1) CN102264461A (fr)
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CA (1) CA2748292A1 (fr)
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DE102011007479A1 (de) 2011-04-15 2012-10-18 Evonik Goldschmidt Gmbh Zusammensetzung, enthaltend spezielle Amide und organomodifizierte Siloxane, geeignet zur Herstellung von Polyurethanschäumen
DE102011083017A1 (de) 2011-09-20 2013-03-21 Evonik Industries Ag Verbundwerkstoffe umfassend eine offenzellige Polymermatrix und darin eingebettete Granulate
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EP2716673B1 (fr) * 2012-10-04 2016-04-06 Evonik Degussa GmbH Pièces de formage à base de produits de réaction composés de polyols et d'isocyanates
DE102013223444B4 (de) 2013-11-18 2015-06-03 Evonik Industries Ag Verwendung von Guanidinumsetzungsprodukten bei der Herstellung von Polyurethansystemen
DE102013226575B4 (de) 2013-12-19 2021-06-24 Evonik Operations Gmbh Zusammensetzung, geeignet zur Herstellung von Polyurethanschäumen, enthaltend mindestens einen ungesättigten Fluorkohlenwasserstoff oder ungesättigten Fluorkohlenwasserstoff als Treibmittel, Polyurethanschäume, Verfahren zu deren Herstellung und deren Verwendung
DE102014215388A1 (de) 2014-08-05 2016-02-11 Evonik Degussa Gmbh Stickstoffhaltige Verbindungen, geeignet zur Verwendung bei der Herstellung von Polyurethanen
DE102014215384A1 (de) 2014-08-05 2016-02-11 Evonik Degussa Gmbh Stickstoffhaltige Verbindungen, geeignet zur Verwendung bei der Herstellung von Polyurethanen
DE102014215382A1 (de) 2014-08-05 2016-02-11 Evonik Degussa Gmbh Stickstoffhaltige Verbindungen, geeignet zur Verwendung bei der Herstellung von Polyurethanen
EP3078696A1 (fr) 2015-04-08 2016-10-12 Evonik Degussa GmbH Fabrication de polyuréthane à faible émission
EP3115389B1 (fr) 2015-07-07 2020-04-01 Evonik Operations GmbH Fabrication de mousse de polyurethane
US11851583B2 (en) 2016-07-19 2023-12-26 Evonik Operations Gmbh Process for producing porous polyurethane coatings using polyol ester additives
JP7241487B2 (ja) 2017-09-25 2023-03-17 エボニック オペレーションズ ゲーエムベーハー ポリウレタン系の製造
US11390199B2 (en) * 2018-04-10 2022-07-19 Adient Us Llc Seating module for a seat
EP3940012A1 (fr) 2020-07-16 2022-01-19 Evonik Operations GmbH Additifs réticulés sans nitrogène et pauvre en nitrogène pour mousse souple de blocage à froid présentant des propriétés de compression et de vieillissement améliorées
CN112625297B (zh) * 2020-12-11 2021-09-03 四川大学 一种基于Pickering泡沫模板法制备WPU合成革发泡层的方法
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WO2010072488A1 (fr) 2010-07-01
CN102264461A (zh) 2011-11-30
BRPI0923686A2 (pt) 2016-01-19
US20110257280A1 (en) 2011-10-20
CA2748292A1 (fr) 2010-07-01
MX2011005961A (es) 2011-06-30
RU2011130598A (ru) 2013-01-27

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