WO2007090376A1 - Polyuréthannes à faible taux d'émission - Google Patents

Polyuréthannes à faible taux d'émission Download PDF

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Publication number
WO2007090376A1
WO2007090376A1 PCT/DE2007/000204 DE2007000204W WO2007090376A1 WO 2007090376 A1 WO2007090376 A1 WO 2007090376A1 DE 2007000204 W DE2007000204 W DE 2007000204W WO 2007090376 A1 WO2007090376 A1 WO 2007090376A1
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Prior art keywords
catalyst
polyurethane
scavenger
starting material
supported catalyst
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PCT/DE2007/000204
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German (de)
English (en)
Inventor
Martin Kreyenschmidt
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Fachhochschule Münster
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Publication of WO2007090376A1 publication Critical patent/WO2007090376A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/089—Reaction retarding agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2290/00—Compositions for creating anti-fogging

Definitions

  • the invention relates to polyurethanes, in particular low-emission polyurethanes, obtainable by reacting an isocyanate component with a polyol component, characterized in that the reaction is a polyurethane catalyst (i) and a supported catalyst scavenger in deactivated form (ii) is added, wherein the supported catalyst scavenger (ii) thermally is activatable.
  • the invention further relates to a process for the preparation of the polyurethane according to the invention and its use for the manufacture of the interior of motor vehicles, furniture, carpets or mattresses and shoe soles.
  • modified, incorporable catalysts are known.
  • WO 94/2525 describes modified amine catalysts obtained by reacting a reactive tertiary amine and polyols with isocyanate compounds. The aim of the modification is to increase the catalytic activity.
  • WO 02/40568 also describes modified amine catalysts which are obtained for improving the solubility properties by reacting a reactive tertiary amine and polyols with isocyanate compounds, using as isocyanate a polyisocyanate of the diphenylmethane series having a functionality of 2.5 to 4.0.
  • polyurethanes are subject to aging processes, which generally lead to a deterioration in service properties with increasing time. Significant aging effects are, for example, hydrolysis, photooxidation and thermal oxidation, which lead to bond breaks in the polymer chains. For polyurethanes, especially the action of moisture, especially in conjunction with elevated temperature, a hydrolytic cleavage of urethane and urea bonds result.
  • TDI-based flexible polyurethane foam which utilizes incorporable catalysts in their manufacture, has a dramatic decline in dynamic mechanical properties following aging simulation tests.
  • the invention is intended to solve this problem by helping to produce low-emission or emission-free polyurethanes which exhibit good dynamic mechanical properties even after hydrolytic aging. Furthermore, the release of aromatic amines from polyurethanes should be prevented.
  • the catalytically active center is usually the free electron pair of a tertiary amine, which is converted by this measure into an ammonium salt, which is no longer catalytically active.
  • Possible solutions that pursue this route are described, for example, in WO 00/011059. However, in this context, the authors primarily considered the aromatic amines released by the aging process and intended to develop a solution that led to the reduction of the aromatic amines.
  • the inhibitors are usually added to the polyol component or the isocyanate component before the reaction in pure form.
  • the disadvantage here is that they react before or during the preparation of the polyurethanes with the amine catalysts or amines used as chain extenders. This can lead to disturbances in the network structure of the polyurethanes and / or to a slowing down of the reaction. This leads to longer demolding times of the products and thus to a loss of efficiency.
  • WO 03/99895 describes the above-mentioned inhibitors, wherein the release of the inhibitors should take place only after extensive reaction of polyol component with polyisocyanate component. It has been shown that the release of the inhibitors, although largely carried out as desired after the end of the polyurethane reaction, but the unfolding of the efficacy is still capable of improvement.
  • the inhibitors still have a high mobility within the polymer network, especially under the high temperatures of the aging simulation tests and emissions test. Since the interaction between the inhibitor and the catalysts is chemical equilibrium, the equilibrium is shifted to the side of the free compounds, especially at higher temperatures. The released catalysts can subsequently support the aging and are detected in the emission test.
  • the object of the invention was therefore to provide polyurethanes which are advantageous on the one hand in terms of emissions, in particular with respect to emissions of volatile catalyst components such as tertiary amines. It was also an object to provide polyurethanes which, on the other hand, are advantageous in terms of dynamic and mechanical properties after hydrolytic or thermal aging and do not lead to discoloration even at relatively high temperatures. In addition, it was an object of the present invention to find a way to fix the aromatic amines formed during the hydrolysis in the foam. A further object of the present invention was to identify a route which ensures the reaction properties of the PUR systems in the processing process constantly and is not influenced by the storage conditions.
  • polyurethanes which have advantageous properties with respect to hydrolytic aging, advantageous dynamic properties, ie rebound resilience, compression set and / or tensile and tear strengths, with simultaneous low emission of catalyst components and liberated aromatic amines.
  • emission it was a particular object of the invention to provide polyurethanes, which high temperature are low emissions.
  • elevated temperature is meant a residence time of about 1 hour at about 80 ° C. or higher.
  • the objects could be achieved by reducing the polyurethane reaction, i. preferably the reaction of isocyanate and polyol, a supported catalyst scavenger (ii) is added in a deactivated form which is thermally activated.
  • a supported catalyst scavenger (ii) is added in a deactivated form which is thermally activated.
  • the invention therefore relates to a polyurethane obtainable by reacting a
  • Isocyanate component with a polyol component characterized in that the
  • the invention further provides a process for preparing the polyurethanes according to the invention by reacting an isocyanate component with a polyol component, characterized in that a catalyst (i) and a supported catalyst scavenger in deactivated form (ii) are added to the reaction, the supported catalyst scavenger being activatable ,
  • polyurethanes according to the invention for the production of the interior decoration of vehicles, for the production of furniture, for the production of carpets, for the production of mattresses or for the production of shoe soles.
  • the invention further provides a catalyst system comprising a polyurethane catalyst (i) and a supported catalyst scavenger in deactivated form (ii); and its use for the production of low-emission polyurethanes.
  • the invention further provides a catalyst starting material (ii-a) which is applied to a carrier (ii-b) and surrounded by a protective layer (ii-c); and its use for the production of low-emission polyurethanes.
  • the invention provides a process for the reduction of emission from polyurethanes, characterized in that already in the preparation of the polyurethane, a polyurethane catalyst (i) and a supported catalyst scavenger in deactivated form (ii) is added to the reaction of isocyanate component with polyol component, wherein the activated, supported catalyst scavenger (ii) is activated during the reaction, so that in the resulting polyurethane foam, a catalyst-catalyst complex (iii) is present.
  • the polyurethane according to the invention is obtainable by reacting an isocyanate component with a polyol component.
  • Isocyanate component and polyol component may contain the following components:
  • polyisocyanates b) compounds with isocyanate-reactive hydrogen atoms, preferably polyols, c) inventive catalyst system comprising a polyurethane catalyst (i) and a supported catalyst scavenger in deactivated form (ii) d) blowing agent, and e) additives.
  • the isocyanate component preferably contains polyisocyanates which are optionally present in the form of isocyanate prepolymers.
  • the polyol component contains compounds with isocyanate-reactive groups, preferably polyols.
  • the components c), d) and e) can both the isocyanate and the polyol before the Implementation be added. They are preferably added before the reaction of the polyol component.
  • the polyisocyanates (a) used for the polyurethanes of the invention are isocyanates customary in the polyurethane field. Aliphatic, cycloaliphatic, arylaliphatic and aromatic polyfunctional isocyanates are generally suitable.
  • aromatic polyisocyanates are preferably used. Examples of these are 2,4- and 2,6-toluene diisocyanate (TDI) and any desired mixtures of these isomers; and optionally in smaller quantities technically produced position isomers of toluene diisocyanates. Also 2,2'- and 2,4'- and 4,4'-diphenylmethane diisocyanate and mixtures of these isomers, mixtures of 2,2'- 2,4'-, 4,4 l-diphenylmethane diisocyanates and Polyphenyl polymethylene polyisocyanates (PMDI-MDI) are preferred. Furthermore, naphthylene diisocyanate (NDI) is preferred.
  • TDI 2,4- and 2,6-toluene diisocyanate
  • NDI naphthylene diisocyanate
  • TDI TDI
  • MDI / or PMDI
  • mixtures of toluene diisocyanates and crude MDI mixtures of toluene diisocyanates and isomers of diphenylmethane diisocyanates.
  • aliphatic polyisocyanates are also preferred.
  • these are hexamethylene diisocyanate (HDI) and hexamethylene diisocyanate trimers.
  • IPDI isophorone diisocyanate
  • polyisocyanates can be used.
  • examples of these are tetramethylene diisocyanate, tetramethylene diisocyanate trimers, 4,4'-methylenebis (cyclohexyl) diisocyanate, xylylene diisocyanate, dodecyl diisocyanate, 2-butyl-2-ethylpentamethylene diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, isocyanatomethyl-1-methylcyclohexyl isocyanate, 1,4-diisocyanato 4-methylpentane, 2,4'-methylenebis (cyclohexyl) diisocyanate and 4-methylcyclohexane-1,3-diisocyanate (H-TDI).
  • tetramethylene diisocyanate tetramethylene diisocyanate trimers
  • 4,4'-methylenebis (cyclohexyl) diisocyanate
  • the polyisocyanates (a) can also be used in the form of polyisocyanate prepolymers. These prepolymers are known in the art. The preparation is carried out in a manner known per se, for example by reacting the abovementioned polyisocyanates (a), for example at temperatures of about 80 ° C., with the polyols (b) described below to give the prepolymer.
  • the polyol-polyisocyanate ratio is generally chosen so that the NCO content of the prepolymer 8 to 30 wt .-%, preferably 10 to 28 wt .-%, particularly preferably 13 to 25 wt .-% is.
  • Suitable compounds with isocyanate-reactive hydrogen atoms (b) are compounds which contain reactive groups selected from OH groups, SH groups, NH groups, NH 2 groups and CH-acidic groups, such as, for example, ⁇ -diketo groups to carry in the molecule.
  • the term "polyurethanes" in the context of this invention comprises not only compounds which have urethane bonds in a strictly chemical sense, but the term “polyurethanes” generally encompasses polyisocyanate polyaddition products obtained by reacting the constituents (a ) and (b) are available. If component (b) has, for example, NH 2 groups, polyureas, for example, form as resulting polyisocyanate polyaddition products.
  • component (b) it is preferred to use compounds having a functionality of from 1.8 to 8, preferably from 2 to 6, and a molecular weight of from 100 to 10,000, preferably from 200 to 7,000.
  • Polyether polyamines and / or preferably polyols selected from the group of polyether polyols, polyester polyols, polythioether polyols and polyester amides; or mixtures thereof.
  • polyester polyols Preferably used polyester polyols and / or polyether polyols.
  • component (b) comprises one or more of the following parts: (b-1) Polyester polyols (b-1-PESOL) and / or polyether polyols (b-1-PEOL), (b-2) polymer polyols, and (b-3) chain extenders.
  • Suitable polyester polyols are usually obtained by condensation of polyfunctional alcohols, preferably diols, having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, for example hexanediol, with polyfunctional carboxylic acids having 2 to 12 carbon atoms, for example adipic acid and / or phthalic acid , produced.
  • the polyester alcohols used usually have a functionality between 2 and 6, preferably between 2 and 4.
  • the polyester polyols used usually have a molecular weight of 400 to 8000 g / mol, preferably greater than 600 to 5000 g / mol, and in particular 1200 to 3500 g / mol.
  • Suitable polyether polyols are generally prepared by known processes, for example by anionic polymerization of one or more alkylene oxides, preferably selected from propylene oxide (PO) and ethylene oxide (EO), but also butylene oxide.
  • the reaction is usually catalysed with alkali hydroxides, such as sodium or potassium hydroxide.
  • the reaction is usually added at least one starter molecule, which preferably contains 2 to 6 reactive hydrogen atoms bound.
  • low-unsaturated polyetherols are understood as meaning, in particular, polyether alcohols having a content of unsaturated compounds of less than 0.02 meq / g, preferably less than 0.01 meq / g.
  • polyether alcohols are usually by addition of alkylene oxides, in particular ethylene oxide, propylene oxide and mixtures thereof, at least difunctional alcohols prepared in the presence of so-called double metal cyanide catalysts.
  • the alkylene oxides can be used individually, alternately in succession or as mixtures.
  • the use of an EO / PO mixture leads to a polyether polyol with random PO / EO unit distribution. It is possible first to use a PO / EO mixture and then to use only PO or EO before termination of the polymerization, then one obtains a polyether polyol with PO or EO endcap.
  • Suitable starter molecules include, for example, water, organic dicarboxylic acids, diamines, e.g. optionally mono- and dialkyl-substituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1, 3-propylenediamine, and / or 1, 3 or 1, 4-butylenediamine. Also suitable as starter molecules are: alkanolamines, e.g. Ethanolamine, N-methyl and N-ethylethanolamine, dialkanolamines, e.g. Diethanolamine, N-methyl and N-ethyldiethanolamine and trialkanolamines such as e.g. Triethanolamine and ammonia.
  • alkanolamines e.g. Ethanolamine, N-methyl and N-ethylethanolamine
  • dialkanolamines e.g. Diethanolamine, N-methyl and N-ethyldiethanolamine and trialkanolamines such as e.g. Triethanolamine
  • starter molecules di-, trihydric or tetrahydric alcohols, such as ethanediol, propanediol-1, 2 and -1.3, diethylene glycol, dipropylene glycol, butanediol-1, 4, hexanediol-1, 6, glycerol, trimethylolpropane and / or pentaerythritol ,
  • the polyether polyols used usually have a molecular weight of 200 to 12,000 g / mol, preferably greater than 400 to 8,000 g / mol, and in particular 800 to 6600 g / mol.
  • the polyether polyols are present individually or in the form of a mixture of two or more of the aforementioned polyether polyols.
  • polymer polyols which are also often referred to as graft polyols used.
  • These polymer polyols are usually prepared by radical polymerization of suitable olefinic monomers, For example, styrene, acrylonitrile, acrylates and / or acrylamide, prepared in a serving as a graft carrier polyetherol.
  • Suitable carrier polyetherols are polyetherols described above.
  • the polymer polyols (b-2) are preferably used in admixture with polyether polyols (b-1-PEOL).
  • the polymer polyol (b-2) is in an amount of 5 to 40 wt .-%, preferably from 6 to 28 wt .-%, particularly preferably from 8 to 18 wt .-%, based on the total weight of Component (b), before.
  • chain extenders are further optionally used. Suitable chain extenders are known in the art. Preference is given to using 2-functional alcohols having molecular weights below 400 g / mol, in particular in the range from 60 to 150 g / mol. Examples are ethylene glycol, 1, 3-propanediol, diethylene glycol, butanediol-1, 4, pentanediol, hexanediol, glycerol or trimethylolpropane, and mixtures thereof. Preferably, ethylene glycol and butanediol and trimethylolpropane are used.
  • the chain extender is usually used in an amount of from 1 to 20% by weight, preferably from 3 to 15% by weight, more preferably from 4 to 10% by weight, based on the total weight of component (b).
  • the catalyst system (c) according to the invention is added to the reaction of isocyanate component and polyol component.
  • the invention Catalyst system contains a polyurethane catalyst (i) and a supported catalyst scavenger in deactivated form (ii).
  • the catalyst system (c) contains at least one polyurethane catalyst (i) which catalyzes a reaction of polyisocyanates (a) with compounds having at least two isocyanate-reactive hydrogen atoms (b).
  • crosslinking catalysts which catalyze a reaction of an isocyanate group with an OH-functional group to form a urethane bond
  • blowing catalysts catalysts which, in particular, support the reaction of water with isocyanate to give carbamic acid.
  • a mixture of crosslinking catalysts and blowing catalysts is preferred.
  • a preferred embodiment contains polyurethane catalysts based on organic amines, in particular based on tertiary amines.
  • the other preferred embodiment contains organometallic polyurethane catalysts.
  • the organic amines are usually monomolecular compounds having at least one amino group, preferably at least one tertiary amino group. Usually, the organic amines have not more than 4 amino groups. Preferably, they have a molecular weight of from 50 to 1400 g / mol, more preferably from 60 to 750 g / mol.
  • suitable compounds are triethylamine, triethylenediamine, tributylamine, dimethylbenzylamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylbutanediamine, N, N, N ', N'-tetramethylamine hexane-1,6-diamine, dimethylcyclohexylamine, pentamethyldipropylenetriamine, pentamethyldiethylenetriamine, 3-methyl-6-dimethylamino 3-azapentol, dimethylaminopropylamine, 1, 3-bisdimethylaminobutane, bis (2-dimethylaminoethyl) ether, N, N, N-trimethyl-N-hydroxyethyl-bis (aminoethyl ether), N, N, N'-trimethylaminoethylethanolamine, 2, (2- (n, N-dimethylamino) ethoxy
  • mixtures of said amines are possible. Mixtures containing aliphatic and / or cycloaliphatic amines are preferred.
  • organometallic compounds are used.
  • organic tin compounds such as tin (II) salts of organic carboxylic acids, e.g. Tin (II) acetate, stannous octoate, stannous (II) ethyl hexoate, and stannous laurate and the dialkyltin (IV) salts of organic carboxylic acids, e.g.
  • mixtures of the organometallic compounds containing are possible. Furthermore, mixtures of the organometallic compounds containing and of said amine catalysts are possible.
  • the polyurethane catalyst (i) is usually added in an amount of 0.001 wt% to 9.0 wt%, preferably 0.01 to 7.0 wt%, and more preferably 0.1 wt% to 4.0 wt .-%, based on the total weight of the polyurethane used.
  • the catalyst system according to the invention contains a supported catalyst scavenger in deactivated form (ii). This initially deactivated, supported catalyst catcher (ii) can be activated.
  • the deactivated, supported catalyst scavenger (ii) is preferably thermally activatable. With particular preference, the deactivated, supported catalyst scavenger (ii) can be activated by the resulting heat of reaction.
  • the "supported catalyst scavenger in deactivated form” (also referred to in this application as a “deactivated supported catalyst scavenger” and labeled “(ii)”) preferably contains an active ingredient (ii-a), a carrier component (ii-b) and a Protective Ingredient (ii-c)
  • the active ingredient is the active catalyst (referred to in this application as (ii-a)), ie the substance capable of binding the polyurethane catalyst (i)
  • the carrier component is a carrier, preferably an organic or inorganic macromolecular builder (referred to in this application as (ii-b))
  • the protective ingredient (referred to in this application as (ii-c)) is a substance which deactivates the catalyst starting material (ii-a), ie which is responsible for the fact that the active ingredient in the deactivated state is not capable of producing the polyurethane alysator (i) to bind.
  • the catalyst scavenger in deactivated form (ii) is a catalyst scavenger (ii-a) applied to a support (ii-b) and surrounded by a protective layer (ii-c).
  • Captures are well known in the art and are often referred to as “getters” or “getters”.
  • Fumigant means a substance, preferably a solid, which is capable of binding other substances.
  • a catalyst starting material (ii-a) is understood as meaning a substance capable of binding the polyurethane catalysts (i) to form a catalyst-starting catalyst complex (iii).
  • Catalyst-target polyurethane-catalyst complex (iii) preferably can not emit from the polyurethane of the present invention.
  • the catalyst starting material (ii-a) is usually able to bind amines.
  • the catalyst starting material (ii-a) is therefore preferably an amine scavenger.
  • complex is to be interpreted broadly and not in a strictly chemical sense, for example, complexation may be by adsorption or absorption or reaction.
  • the catalyst scavenger (ii-a) contains metals in a form which makes it possible to bind the polyurethane catalyst (i).
  • the bond can be covalent. Further, it may be a complex bond. Also, the bond can be done via van der Waals forces.
  • the metal-containing catalyst starting materials (ii-a) are preferably in the form of metal, metal salt or organometallic compound.
  • the metals used are preferably characterized in that these complexes can enter into with primary, secondary or tertiary amines.
  • suitable metals are Li + , Na + , K + , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Al 3+ , Ga 3+ , In 3+ , Cr 3+ , to Cr 5+ , Ce 3+ , Cu, Cu 1+ , Cu 2+ , Co, Co + , Co 2+ , Co 3+ , Co 4+ , Ni, Ni 1+ , Ni 2+ , Ni 3+ , Ni 4+ , Mn, Mn 1+ , Mn 2+ , Mn 3+ , Mn 4+ , Fe, Fe 2+ , Fe 3+ , Zr, Zr + , Zr 2+ Zn, Zn 2+ , Sn 0 to Sn 4+ , V 0 to V 5+ Ag, Ag + , Ag 2+ ,, In and / or Ti ° to Ti 4+ , Mo 0 to Mo 6+ , (La, Sc, Y, W, Ge, Hf, G)
  • the common anions can be used.
  • these are halides and pseudohalides such as chloride, bromide, iodide, fluoride, Chlorates, bromates, iodates; Phosphate and polyphosphates, sulfate and polysulfates, sulfite, nitrate, nitrite, oxide, peroxide, cyanides, thiocyanides, silicates, borates, polyborates, thiosulfates, polythionates, carbonates, and or carboxylates having 1 to 10 carbon atoms, preferably having 2 to 6 carbon atoms.
  • Preferred metal salts are copper (II) sulfate, copper (II) chloride, nickel (II) sulfate, cobalt (II) chloride, iron (II) chloride and / or iron (III) chloride, copper carbonates, iron carbonates, zirconium carbonates, manganese carbonates, vanadium carbonates , Copper borates, iron borates, vanadium borates, vanadium halides, copper nitrates, iron nitrates, vanadium and manganese nitrates, titanium carbonates, titanium borates, titanium carbonates, titanium halides, titanium oxides, iron oxides, vanadium oxides, manganese oxides, copper oxides as well as the carboxylates of all the above metals.
  • This first preferred embodiment of the catalyst starting materials (ii-a) finds particular application when the polyurethane catalyst (i) is amines. That is, metal compounds or metals are used as catalyst scavenger (ii-a) which have good complexing properties to amines, especially to tertiary amines.
  • the catalyst scavenger is preferably an amine scavenger.
  • the catalyst starting material (ii-a) contains compounds which have groups reactive with metal catalysts.
  • the catalyst starting material (ii-a) in this case are preferably compounds which have reactive groups which can complex (i) organometallic polyurethane catalysts.
  • the compounds of the second preferred embodiment of the catalyst starting material (ii-a) preferably have a molecular weight of 50 to 1400 g / mol, more preferably from 60 to 750 g / mol. They are preferably non-polymeric compounds (in particular monomolecular compounds) which can be applied to the carrier (ii-b).
  • Suitable reactive groups which can complex organometallic polyurethane catalysts (i) are amino groups or hydroxyl groups. Further, crown ethers or cyclodextrins are suitable. Also suitable are sulfur ligands such as thiols. Other suitable compounds are cyano groups, thiogyano groups, cyanuric acid groups. Also suitable are hydrazines, triazines or tetrazines, polysulfanes. Also suitable are ligands with phosphorus or sulfur, such as phosphanes, thiophosphoric acids.
  • Suitable groups are acid groups such as those of sulfuric acid, phosphoric acid, nitric acid, boric acid, or the organic carboxylic acid groups in their various combinations and other functional groups.
  • the catalyst starting material (ii-a) contains compounds which have reactive groups with respect to amine groups. These reactive groups are particularly preferably able to protonate the catalytically active center of the amine polyurethane catalyst or to react with aromatic amine groups. The reactive groups are either present in free form in the catcher or are e.g. converted by aging in the active form.
  • the compounds of the third preferred embodiment of the catalyst starting material (ii-a) preferably have a molecular weight of from 50 to 1400 g / mol, more preferably from 60 to 750 g / mol. They are preferably non-polymeric compounds (in particular monomolecular compounds) which can be applied to the carrier (ii-b). Examples of such reactive groups include carboxylic acid groups, sulfuric and phosphoric acid groups, nitric acid groups, halogen acids. Also suitable are organic and inorganic acid anhydrides and acid esters, such as carboxylic acid anhydrides, carboxylic acid esters or sulfuric acid esters, phosphoric acid esters and the corresponding anhydrides.
  • the catalyst starting material (ii-a) generally does not comprise any of the ingredients mentioned above as polyurethane catalysts (i).
  • the catalyst starting material (ii-a) is applied to a carrier (ii-b).
  • Carrier substances (ii-b) are basically all solid, preferred macromolecular substances which are capable of binding the catalyst starting material (ii-a). The binding can be via adsorption or absorption. The binding of the catalyst starting material (ii-a) to the support preferably takes place via adsorption.
  • the carriers (ii-b) are usually inorganic, organic or organically modified inorganic materials. These may be particulate, porous or compact.
  • the carrier substances (ii-b) are preferably particles having an average diameter of 1 nm to 2 mm, preferably 15 nm to 1000 nm, more preferably 40 nm to 800 nm and most preferably from 80 nm to 500 nm
  • the supports (ii-b) may be round or irregular depending on the manufacturing process.
  • Porous carriers (ii-b) to be used in the method of the invention include organic or inorganic materials.
  • the excipients which have suitable porosity are generally nanoporous, microporous, mesoporous and / or macroporous.
  • the term "porosity" refers hereafter to the entire arrangement of pores and channels and cages.These solids may be amorphous or have a periodically crystalline structure or combine both features.
  • the arrangement of pores and channels and cages may be irregular, ie not periodic Alternatively, they may be regular or periodic.
  • the pores or channels may be isolated or interconnected and may be one or two-dimensional.
  • a "nanopore” is defined as a pore having a radius of 100 pm to 10 nm
  • a “micropore” is defined as a pore in the range of 10 nm to 100 nm
  • a “mesopore” is to be defined as a pore from 1 OOnm to 10 nm and as "macropores", all pores larger than 10 nm should be defined.
  • the excipients (ii-b) can generally fix metals or metal ions by complexation or chemical bonding.
  • the carriers (ii-b) preferably have a sufficient amount of surface sites.
  • the porous carriers (ii-b) preferably have a surface area of greater than 1 square meter per gram and less than 20,000 square meters per gram, more preferably greater than 10 square meters per gram and less than 10,000 square meters per gram, more preferably greater than 100 square meters per gram and less than 8,000 Square meters per gram.
  • the inorganic carriers (ii-b) include amorphous (non-crystalline) metal oxide materials. Crystalline inorganic carriers (ii-b), such as molecular sieves, are also included as carriers. These molecular sieves are preferably ordered, porous, crystalline material having a defined crystalline structure. Within this structure, there are a large number of smaller cavities that can be connected by a series of even smaller channels or pores. The dimensions of these channels or pores are such as to allow adsorption of molecules of certain dimensions while avoiding those of larger dimensions.
  • Molecular sieves can be classified into different groups by their chemical composition and their structure.
  • One group of molecular sieves is commonly referred to as zeolites.
  • the carrier (ii-b) is a molecular sieve, in particular a zeolite.
  • Zeolites are composed of a lattice of silica and optionally alumina, preferably with exchangeable cations such.
  • B. alkali or alkaline earth metal ions is combined.
  • zeolites includes materials containing silica and optionally alumina, the silica and alumina portions may be wholly or preferably partially replaced by other oxides.
  • germanium oxide, titanium oxide, tin oxide, phosphorus oxide and mixtures thereof can replace the silica content.
  • Boron oxide, iron oxide, titanium oxide, gallium oxide, indium oxide and mixtures thereof can replace the alumina content.
  • zeolite zeolites
  • zeolite material as used herein are intended to mean crystalline and / or amorphous porous molecular sieves containing silicon and / or optionally aluminum and / or titanium atoms as well as oxygen in the crystal lattice structure thereof Structures in which a proportion of these atoms has been replaced by other elements of the periodic table.
  • carrier (ii-b) in the context of this application further refers to inorganic oxides and mixed oxides, such as silica, alumina, Magnesium oxide, titanium oxide, aluminum silicates, silicon carbide, minerals containing aluminum, magnesium, such as. Talc and kaolin, alumina or magnesia, bentonites or modified bentonites, montmoriolinites and modified monomoriolinites and like minerals.
  • inorganic oxides and mixed oxides such as silica, alumina, Magnesium oxide, titanium oxide, aluminum silicates, silicon carbide, minerals containing aluminum, magnesium, such as. Talc and kaolin, alumina or magnesia, bentonites or modified bentonites, montmoriolinites and modified monomoriolinites and like minerals.
  • carrier (ii-b) in the context of this application further refers to organic carriers (ii-b).
  • the organic carriers (ii-b) may be polymer structures.
  • the surface of the polymer structures may have been modified. It is preferably a natural or synthetic polymer which has been prepared from monomers which preferably contain functional groups or ligands.
  • the polymeric materials can be compact or porous.
  • a selection of possible carriers (ii-b) based on different polymers is presented below.
  • Synthetic polymers may be emulsion polymers and / or latices containing at least one monomer having functional groups.
  • Examples of natural polymers are polysaccharides, such as cellulose, starch or chittosan, which may be partially etherified with C1-C4-alkyl or esterified with C1-C8-acyl.
  • Synthetic polymers with functional groups are known and can be prepared by known methods.
  • the polymer for the carrier (ii-b) may also contain thermosetting resins such as epoxy resins, melamine-formaldehyde resins and phenol-formaldehyde resins.
  • the polymers described can be modified by complexing functional groups either on the surface of the carrier (ii-b) or as a polymer by functional groups.
  • the modification can be carried out either after the preparation of the carrier (ii-b) or already in the synthesis of the polymer.
  • the modification involves the introduction of functional groups, wherein these functional groups are capable are to bind or complex metals in neutral or charged form and thus to fix on the carrier.
  • Organic ion exchange resins can also be used as the carrier (ii-b).
  • the organic ion exchange resins useful as carriers (ii-b) are organic, porous materials having a surface charge and ion exchange capacity for anions or cations.
  • the organic ion exchangers are polymer based.
  • Polymer-based ion exchangers are commercially available or can be readily prepared from resins that are commercially available.
  • resins examples include resins offered by the Rohm and Haas Company under the registered trademark Amberlyst, and resins offered by the Dow Chemical Co. under the registered trademark "Dowex". These exchangers cover a wide range of different cation and anion exchangers with varying ion exchange capacity, porosity, pore size and particle size.
  • the number average weight average molecular weight of the polymers used as the carrier (ii-b) is usually in the range of 10 3 to 8xlO 6 , preferably from 10 4 to 2 ⁇ 10 6 , in particular from 2 ⁇ 10 4 to 10 6 g / mol, the determination preferably by Gel permeation chromatography using polystyrene standards for calibration.
  • organically modified inorganic carriers are materials typically used for separation in high performance liquid chromatography.
  • organic structures are preferably applied, wherein a connection via silanization takes place.
  • the organic functional groups can be separated from the silicate surface by nonpolar spacers. Typical functional groups are the amino, hydroxy, cyano-thiocyno, Nitro, sulfo, thio and other groups. These groups are able to fix metals.
  • porous materials are the known chromoliths.
  • the application of the catalyst starting materials (ii-a) to the carriers (ii-b) can be carried out by known methods.
  • suitable methods of application are e.g. in the case of metals as a catalyst starting material (ii-a) the application by precipitation from an aqueous solution of water-soluble salts of the metals, for. B. by adjusting the pH.
  • Another method of applying a metallic catalyst scavenger is to adsorb a catalyst scavenger precursor, such as a catalyst scavenger.
  • a catalyst scavenger precursor such as a catalyst scavenger.
  • the catalyst starting material (ii-a) can also be precipitated onto the carrier (ii-b) simultaneously with another material.
  • the catalyst starting material (ii-a) may be added to the carrier (ii-b) by deposition, e.g. the ion exchange can be applied.
  • the specific carriers which are exchanged with exchanger groups or complexing ligands in a column and a solution containing the catalyst to be applied catalyst (ii-a) in this case metals or metal ions, are continuously passed to the carrier (ii-b) wherein absorption of the desired metal or metal ion occurs on the carrier (ii-b). Subsequently, it is still possible by heating or reduction to optimize the properties of the catalyst material.
  • the application of the Fangstoffs (ii-a) can be further carried out by applying a metal salt to an organic ion exchanger. Then the Washed ion exchanger with distilled water, dried thereon and this dried loaded ion exchanger to give a mixture of which thereon by known methods a carrier (ii-b) such as a zeolite produces (eg Na 2 O, TPAOH, Al 2 O 3 , SiO 2 and H 2 O).
  • a carrier (ii-b) such as a zeolite produces (eg Na 2 O, TPAOH, Al 2 O 3 , SiO 2 and H 2 O).
  • the captures (ii-a) are functional groups capable of protonating the amine catalysts and thus fixing them to the surface, they can be applied as follows, for example.
  • the carrier By impregnating the carrier with organic compounds containing acid groups or can be converted into acid groups. After surface coverage has been achieved, it is preferred to remove the scrubber (ii-a) that has not been adsorbed on the surface by a washing process.
  • fixation on the support material (ii-b) can be carried out in an optional subsequent polymerization step. If the catcher (ii-a) itself possesses polymerisable functional groups, these can be linked to one another according to the various possibilities of polymerization.
  • the optional polymerization step can be carried out by adding a co-monomer. The addition of the co-monomer converts the originally monomeric capture agent into a polymeric network.
  • the capture agents (ii-a) can be provided with reactive groups so that they are able to react with the surface of the carrier (ii-b) and be fixed there (customary technique in the preparation of functionalized carrier materials for the HPLC).
  • the carrier (ii-b) may contain functional groups capable of reacting with functional groups of the entrapping agent (ii-a), for example, to undergo substitution reactions.
  • the catcher (ii-a) can be applied by impregnation to the surface of the carrier (ii-b) and subsequently - preferred by energization (heat, light, etc.) excited react with the carrier polymer (ii-b) and are thus fixed to the polymer.
  • organic polymer carrier substances (ii-b) can be modified or prepared in such a way that they can fix metals as capture agents (ii-a) via any ligands and functional groups for complexation or other form of bonding.
  • the application of the metals is carried out similarly to the method described above for inorganic carriers (ii-b).
  • the weight ratio of carrier (ii-b) to catalyst starting material (ii-a) is usually from 0.1 to 1000: 1, preferably from 0.5 to 100: 1, particularly preferably from 0.5 to 10: 1, and in particular from 1: 1 to 10: 1.
  • the supported catalyst scavengers i.e., the catalyst scavengers (ii-a) already applied to the carrier (ii-b) are usually present as particles.
  • these particles have an average particle diameter of 10 nm to 1 mm, more preferably from 1 .mu.m to 500 .mu.m, in particular from 5 .mu.m to 250 .mu.m.
  • the average particle diameter which is also referred to as the D 50 value of the integral mass distribution, is defined in the context of this invention as the particle diameter at which 50% by weight of the particles have a smaller diameter than the diameter which corresponds to the D 50 . Value corresponds. Likewise, then 50 wt .-% of the particles have a larger diameter than the D 50 value.
  • the determination of the particle diameter was carried out by the dynamic light scattering whereby ball-like particles are estimated to the equivalent spherical diameter.
  • Dynamic light scattering is one of the standard methods for determining the mean particle size in the submicron range.
  • the particle size distribution can be determined by various distribution functions such as length, area, volume or Mass distribution are presented. In dynamic light scattering in the context of this invention, the volume distribution is shown.
  • the characteristic size for the distribution function is often the diameter D.
  • the active ingredient of the supported catalyst scavenger i. the catalyst starting material (N-a) is initially deactivated by the protective component (ii-c) as described above. However, the protective ingredient can be removed so that the active ingredient can exhibit the desired effect. The at least partial removal of the protective component (ii-c) thus leads to the activation of the supported catalyst scavenger (ii).
  • the supported catalyst scavenger in deactivated form (ii) is preferably a supported catalyst scavenger (ii- a) surrounded by a protective layer (ii-c).
  • all substances are suitable which on the one hand can initially surround the catalyst starting material (ii-a) so that it can not react with the polyurethane catalyst (i) and on the other hand can be activated in the course of the reaction, i. are removable so that the catalyst starting material (ii-a) can react with the polyurethane catalyst (i).
  • the protective layer (ii-c) comprises a polymer, preferably a polymer having a melting temperature of between 40 and 200 ° C.
  • suitable polymers are polyesters, polyethylene oxides, polypropylene oxides, polybutylene oxides, polyacrylates, polyether esters, polyvinyl alcohols, polytetrahydrofuran, Polystyrenes and any copolymers containing styrene, polybutadienes and / or polyolefins.
  • the protective layer preferably completely surrounds the catalyst starting material (ii-a).
  • the catalyst scavenger is thus preferably encapsulated in a polymer.
  • the encapsulation of substances is well known and has also been used in the field of polyurethane chemistry for other uses.
  • GB-B-1, 035,903 describes a process for the production of polyurethane foams wherein a catalyst encapsulated in a protective sheath is used.
  • the protective sheath has a melting point of 30 to 40 0 C, serves to improve the storage stability of the system before the reaction and is preferably removed by shearing forces in mixing, dielectric heating or ultrasonic waves.
  • GB-B-1, 053,500 discloses a process for producing polyurethanes by using isocyanates encapsulated in a protective layer.
  • WO 02/31013 and WO 03/085021 disclose that the encapsulation of catalysts with wax, the curing behavior of polyurethane reactions can be significantly accelerated, without the starting time is adversely affected.
  • the encapsulated catalyst scavenger can be activated in different ways.
  • the capsules are opened by shearing forces during mixing.
  • the capsules are opened by irradiation of ultrasonic waves or microwaves.
  • the protective layer is selected so that the encapsulation is opened by the heat of reaction.
  • the protective layer (ii-c) a melting temperature of 50 0 C to 200 0 C, more preferably from 60 0 C to 150 0 C, more preferably from 70 ° C to 130 0 C and in particular from 75 0 C to 120 0 C on.
  • the protective layer (ii-c) is a wax, which can preferably be melted by the heat of reaction.
  • wax means a naturally or artificially produced substance
  • the waxes of the present invention are generally in solid form at 20 C. In solid form, they are preferably kneadable or solid to brittle, but not glassy.
  • the waxes of the present invention are already little of relatively low viscosity above the melting point and preferably not stringy. preferably, they briefly have 10 0 C above the melting point a viscosity of less than 20,000 mPas, measured according to DIN 53019, in. This relatively low viscosity above the melting point distinguishes waxes from "classic" plastics.
  • waxes includes natural waxes, chemically modified waxes and synthetic waxes, provided that they meet the above criterion of the polar groups.
  • Natural waxes include vegetable waxes such as montan wax, animal waxes such as beeswax, mineral waxes and petrochemical waxes such as petrolatum.
  • Chemically modified waxes include, for example, hard waxes such as montan ester waxes.
  • Synthetic waxes include, but are not limited to, polar alkane waxes, such as wax alcohols, especially higher molecular weight, water-insoluble fatty alcohols, preferably greater than 12 carbon atoms, such as lignoceryl alcohol, ceryl alcohol, myricyl alcohol, melissyl alcohol, and polyalkylene oxides such as polyethylene oxide, poly THF, polyvinyl ether waxes, polyolefin copolymer waxes, and oxidized polyolefin waxes.
  • polar alkane waxes such as wax alcohols, especially higher molecular weight, water-insoluble fatty alcohols, preferably greater than 12 carbon atoms, such as lignoceryl alcohol, ceryl alcohol, myricyl alcohol, melissyl alcohol, and polyalkylene oxides such as polyethylene oxide, poly THF, polyvinyl ether waxes, polyolefin copolymer waxes, and oxidized polyolefin waxe
  • wax comprises relatively high molecular weight fatty acids, preferably having at least 9 carbon atoms, such as behenic acid, tetracosanoic acid and cerotic acid, which may optionally be esterified with alcohols, and high molecular weight polyesters having a molecular weight of> 1000 g / mol, preferably> 1500 g / mol are obtainable by reacting di- or polycarboxylic acids having 2 to 20 carbon atoms with di- or polyalcohols having 2 to 30 carbon atoms, the corresponding acids or alcohols being aliphatic and / or may contain aromatic structural units. It is likewise possible to use mixtures of the abovementioned waxes.
  • the wax used has a melting temperature of 50 0 C to 200 0 C, more preferably from 60 0 C to 150 ° C, even more preferably from 70 ° C to 130 0 C and in particular from 75 0 C to 120 0 C on.
  • the waxes used contain one or more polar groups in order to increase the compatibility between wax and catalyst starting material (ii-a).
  • Polar groups are groups that have a different electronegativity from them compared to a pure hydrocarbon group.
  • oxygen atoms, nitrogen atoms, sulfur atoms and optionally halogen atoms may serve as a basis for polar groups.
  • Pure alkane or paraffin waxes are preferably not used as protective layer (ii-c) since they have no polar groups in the sense of the preferred embodiments described above.
  • the waxes are generally polymeric substances.
  • the polar groups may be present at the end and / or within the polymer. Examples of polar groups are acid, amine, imine, amide, ether, ester, acetate, keto, aldehyde, optionally urethane, urea, thiol or alcohol group.
  • the waxes used in the present invention have a heat of fusion of 45 to 260 joules / gram, preferably from 80 to 220 joules / gram, especially from 130 to 180 joules / gram.
  • the heat of fusion is measured according to the ISO 11357-3 by the DSC method (differential scanning calorimetry).
  • polar polyolefin waxes are used.
  • Polyolefins which are preferably used are: polyethylene, polypropylene, polybut-1-enes and copolymers of ethylene with 0 to 20 mol% of propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene or 1-hexene. undecene.
  • the average molecular weight M w of these polyolefin waxes is from 500 to 20,000 g / mol, preferably from 2,000 to 15,000 g / mol and more preferably from 3,000 to 10,000 g / mol.
  • Polar groups can generally be introduced into a wax by different process steps.
  • a preferred method is to partially degrade the wax, for example, by atmospheric oxygen or peroxide compounds, thereby obtaining so-called oxidized polyolefin waxes.
  • peroxide compounds for example, hydrogen peroxide (H 2 O 2 ) or dialkyl peroxides can be used.
  • H 2 O 2 hydrogen peroxide
  • dialkyl peroxides can be used.
  • oxidized polyolefin waxes which have an acid number of not more than 50, preferably from 10 to less than 50.
  • Another preferred method is to use polar comonomers such as acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or vinyl acetate, which can be optionally saponified, thereby obtaining so-called copolymer polyolefin waxes.
  • polar comonomers such as acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or vinyl acetate, which can be optionally saponified, thereby obtaining so-called copolymer polyolefin waxes.
  • ethylene-vinyl acetate waxes having an M w of from 2,000 to 15,000 g / mol, in particular from 3,000 to 10,000 g / mol, and a content of from 0.1 to 25% by weight of vinyl acetate, particularly preferably from 1 to 15 % By weight of vinyl acetate, based on the total weight of the copolymer.
  • ethylene-acrylic acid-acrylate terpolymer waxes are used.
  • These have an acrylic acid content of 0.1 to 20 wt .-%, preferably from 1 to 5 wt .-% and an acrylate content of 0.1 to 40 wt .-%, preferably from 1 to 20 wt .-%, with the proviso that the total content of acrylate and acrylic acid is less than 50% by weight, preferably less than 40% by weight, based on the total weight of the terpolymer.
  • polyether waxes are used. These generally have a molecular weight M w of 10,000 to 50,000 g / mol, preferably from 15,000 to 35,000 g / mol.
  • Polyvinyl ether waxes for example poly-octadecyl vinyl ethers or corresponding polyethers which have a C16, C17, C19, C20, C21 or C22 radical instead of an octadecyl radical are particularly suitable.
  • montan waxes and montan ester waxes are used. These are based on long-chain fatty acids, generally composed of hydrocarbon chains having 20 to 40 carbon atoms, preferably having 30 to 36 carbon atoms.
  • polyethylene oxide or polypropylene or polybutylene oxides or mixed polymers composed of ethylene oxide, and / or propylene oxide and / or butylene oxide and further alkylene oxides are used.
  • the waxes have incorporable functional groups. After melting, they are able to react with the remaining isocyanate groups and can thus be incorporated into the polymeric network.
  • the supported catalyst scavengers (ii-a) In order to prepare the supported catalyst scavengers in deactivated form (ii), generally the supported catalyst scavengers (ii-a) (ie the catalyst scavengers (ii-a) applied to the support (ii-b) as described above) liquid wax or polymers dissolved or suspended.
  • a solubilizer may be added to give a better solution of the supported catalyst tracer (ii-a and ii-b) in the wax.
  • the mixture of liquid wax and supported catalyst scavenger (ii-a and ii-b) is now preferably cooled and dispersed in a polar liquid.
  • a dispersant may be added to the melt, resulting in advantageous dispersion.
  • a polar liquid is generally suitable any liquid in which the wax is insoluble.
  • Water or a compound having at least two isocyanate-reactive hydrogen atoms is preferably used.
  • a polyol, in particular a polyetherol, is preferably used as the component, particularly preferably the polyol used in the preparation of the polyurethanes of the invention. The use of this polyol is advantageous since it does not introduce any foreign matter into the system and, in the case of cellular products, a possible destabilization of the foam by foreign substances can be avoided.
  • solubilizers it is generally possible to use compounds which are e.g. Hydrogen bonds to the catalyst starting materials (ii-a) can build up and thereby improve the compatibility with the surface of the supported catalyst material.
  • polar polymers such as e.g. Polyethylene oxide or polypropylene oxide or mixed polyethers of ethylene oxide and propylene oxide, polyesters Polyvinyl alcohols Polyimines.
  • the solubilizer is usually used in an amount of 0.1 to 10 wt .-%, preferably 0.5 to 5 wt .-%, based on the weight of wax and catalyst starting material.
  • Suitable dispersants are generally amphiphilic molecules which have a hydrophobic part compatible with the wax and a hydrophilic part compatible with the polar liquid.
  • stearic acid can be used.
  • the dispersant is usually added in an amount of 0.1 to 20 wt .-%, preferably 1 to 10 wt .-%, based on the weight of wax and catalyst starting material used.
  • the liquid mixture of catalyst starting material and heated wax can be brought into a suitable, particulate form directly by spraying in an air stream, preferably a cold air stream, so that a, preferably granular, powder is obtained .
  • an apparatus similar to a spray dryer is suitable, but is preferably operated with a cold air flow.
  • the catalyst system dispersed in the polar liquid can also be freeze-dried. The catalyst dispersion is first frozen and the dispersant removed in vacuo. A dry powder is obtained.
  • the average particle diameter of the resulting deactivated, supported catalyst scavenger (ii) can be adjusted.
  • encapsulate or "encapsulate” in the context of this invention encapsulation or encapsulation in the strict sense, ie in the middle of the particulate Katalysatorfangstoffteilchens is exclusively supported catalyst material (ii-a), with
  • a particle of the supported catalyst scavenger (ii) of the present invention can be usually exemplified by a catalyst core wax-shell model, and preferably does not consist of a wax matrix in which the supported catalyst scavenger is dispersed.
  • the supported catalyst scavenger in deactivated form (ii) is usually used in an amount of 0.001 wt .-% to 20.0 wt .-%, preferably from 0.01 to 10.0 wt .-% and particularly preferably from 0.1 wt % to 8.0% by weight, based on the total weight of the polyurethane.
  • the molar ratio of polyurethane catalyst (i) to catalyst starting material (ii-a) is 1 to 80,000, preferably 1 to 15,000, more preferably 1 to 7,500, particularly preferably 1 to 1000 and in particular 1 to 500.
  • the constituents polyisocyanates (a), compounds with isocyanate-reactive hydrogen atoms (b) and the catalyst system (c) according to the invention comprising polyurethane catalyst (i) and supported catalyst scavenger in deactivated form (ii) have now been described.
  • the isocyanate component and / or polyol component may further contain blowing agent (d) and additives (e).
  • blowing agents it is possible to use generally known chemically or physically active compounds.
  • chemically acting blowing agent water can preferably be used.
  • physical blowing agents are inert (cyclo) aliphatic hydrocarbons having 4 to 8 carbon atoms which evaporate under the conditions of polyurethane formation. The amount of blowing agent used depends on the desired density of the foams.
  • the propellant is in an amount of 0.1 to 20 wt .-%, preferably from 0.2 to 15 wt .-%, more preferably from 0.3 to 10 wt .-% and in particular of 0.5 to 5 wt .-%, based on the weight of components (a) and (b) used.
  • additives (e) may be added.
  • additives (e) are surface-active substances, foam stabilizers, cell regulators, external and internal release agents, dyes, pigments, flame retardants, hydrolysis stabilizers, oxidation inhibitors, abrasion improvers, fungistatic and bacteriostatic substances, light stabilizers, plasticizers.
  • the substances mentioned are usually used in an amount of 0.01 to 10 wt .-%, particularly preferably from 0.1 to 5 wt .-%, based on the total weight of the polyurethane.
  • a component (s) fillers and reinforcing agents such as glass fibers, chalk, barite can be used. These are usually used in an amount of 1 to 50 wt .-%, particularly preferably from 5 to 30 wt .-%, based on the total weight of the polyurethane.
  • polyurethanes of the invention are thus obtainable by reacting components (a) and (b) in the presence of (c) and optionally (d) and (e).
  • the polyurethanes according to the invention are preferably low in emissions, in particular low in emissions at elevated temperature.
  • the polyurethanes according to the invention have an emission value of less than 40 ppm, more preferably less than 20 ppm, in particular between 1 and 15 ppm, according to the DaimlerChrysler thermal desorption method (PB VWT 709).
  • the resulting polyurethanes are characterized in that they have advantageous dynamic mechanical properties after hydrolysis aging.
  • the polyurethanes of the invention have the same good emission properties by more than 20% better tear and tensile strengths compared to flexible polyurethane foams, which can be built with catalysts such.
  • catalysts such as 2-dimethylamino-ethoxy-ethanol or N- (2-hydroxyethoxyethyl) - 2-azanorboman
  • the compression set residues after hydrolysis aging, when using these supported catalyst scavengers and using non-incorporable catalysts, are over 40% better than comparable foams using incorporable catalysts such as 2-dimethylaminoethoxy-ethanol or N- (2-hydroxyethoxyethyl) -2-azanorbornane ,
  • the content of aromatic amines, especially 2,4-MDA, is up to 500% better when using these substances and catalysts, such as bis-dimethylaminoethyl ether, than comparable foams which comprise the incorporable catalysts, such as 2-dimethylaminoethoxyethanol or N- (2-hydroxyethoxyethyl) - Use 2-azanorbornane.
  • catalysts such as bis-dimethylaminoethyl ether
  • the invention further provides a process for preparing the polyurethanes according to the invention by reacting an isocyanate component with a polyol component, characterized in that the reaction, the catalyst system according to the invention containing catalyst (i) and supported catalyst scavenger (ii) in deactivated form, wherein the catalyst scavenger is activated , is added.
  • the polyisocyanate component and polyol component are reacted in amounts such that the equivalence ratio of NCO groups of the (a) polyisocyanates to the sum of the reactive hydrogen atoms of components (b) is 1: 0.5 to 1: 3.50 (corresponding to an isocyanate index of 50 to 350), preferably 1: 0.65 to 1: 1, 30 and more preferably from 1: 0.9 to 1: 1, 15.
  • the starting components are usually mixed at a temperature of 0 C to 80 C, preferably 15 to 60 C and reacted.
  • the starting components can be reacted in a mold.
  • the mixing can be done, for example, mechanically by means of the low-pressure technique or the high-pressure technique, or by other mixing methods used in conventional PUR processing machines.
  • the polyurethanes according to the invention can be compact or cellular depending on the choice of components (a) to (e).
  • the polyurethanes are soft, hard, semi-rigid or integral foams or compact, preferably thermoplastic polyurethanes and / or cast elastomers.
  • the polyisocyanate polyaddition products can be prepared as moldings, for example as dashboards, seat foam, carpet backing foam, etc.
  • the invention further relates to the use of the polyurethane according to the invention for the production of interior equipment of transport.
  • Preferred means of transport are motor vehicles, ships, trains and aircraft.
  • Examples of the interior fittings are seats, instrument panels, side and door side panels, center consoles armrests and glove boxes, headliners, acoustic foams, carpet backing foams.
  • the invention also relates to the use of the polyurethane according to the invention production of furniture, such as a couch, for the production of carpets or for the production of mattresses.
  • the invention thus also an instrument panel, car seat, carpet or mattress containing polyurethane according to the invention.
  • the dashboard according to the invention is constructed from an outer layer, a polyurethane foam according to the invention, and optionally a carrier element.
  • a polyurethane foam according to the invention and optionally a carrier element.
  • instrument panels are often referred to as instrument panels.
  • the outer layer materials are usually used which give the dashboard a decorative appearance, such as plastic films, plastic skins, textiles and / or leather.
  • the thickness of the outer layer is generally 0.5 to 3 mm, preferably 0.7 to 1.4 mm.
  • the polyurethane foams of the invention are used.
  • the layer of polyurethane foam usually has a thickness of 0.5 millimeters (mm) to 60 mm, preferably from 5 mm to 18 mm.
  • the polyurethane according to the invention is preferably a polyurethane semi-rigid foam.
  • a carrier element usually all materials come into question, which positively influence the mechanical properties of the resulting composite element. Examples include wood fiber support members, glass fiber reinforced thermoplastics, or Duromer support members.
  • the support elements usually have a thickness of 1.0 mm to 15 mm, preferably from 1, 5 mm to 4 mm.
  • the invention further relates to a car seat, comprising a polyurethane foam according to the invention.
  • a polyurethane foam according to the invention is preferably a Flexible polyurethane foam bonded to an outer skin. Alternatively, it may also be a polyurethane integral foam.
  • the foam according to the invention in this case preferably has a density of from 20 to 250 g / l, preferably from 40 g / l to 200 g / l.
  • the density of the polyurethane foam is to be understood as meaning the average density over the entire resulting foam, ie in the case of molded foams, this specification refers to the average density of the entire foam including core and outer layer.
  • the invention furthermore relates to a carpet or a mattress comprising a polyurethane foam according to the invention.
  • a polyurethane foam according to the invention is preferably a flexible polyurethane foam.
  • the foam according to the invention in this case preferably has a density of from 15 to 200 g / l, preferably from 20 g / l to 130 g / l.
  • the starting materials described as components (a) to (e) are produced by different producers.
  • the catalyst system (c) containing the polyurethane catalyst (i) and a supported catalyst scavenger in deactivated form (ii) may also be sold singly and independently of the components (a) and (b) and optionally (d) and (e) ,
  • the invention therefore relates to a catalyst system comprising a polyurethane catalyst (i) and a supported catalyst scavenger in deactivated form (ii); and its use for the production of low-emission polyurethanes.
  • a catalyst system comprising a polyurethane catalyst (i) and a supported catalyst scavenger in deactivated form (ii); and its use for the production of low-emission polyurethanes.
  • the preferred embodiments described above for the polyurethanes according to the invention are also used for the catalyst system according to the invention.
  • the supported catalyst scavenger in deactivated form (ii) as described above is a supported catalyst scavenger surrounded by a protective layer.
  • the invention therefore also relates to a supported catalyst starting material which is surrounded by a protective layer. Surrounding with a protection view is also referred to as "encapsulating” or “encapsulating”.
  • the supported catalyst getter (ii-a) is encapsulated in a material having a melting temperature of 50 to 200 0 C.
  • the supported catalyst starting material (ii-a) is encapsulated in a wax having a melting temperature of 50 to 200 ° C.
  • the encapsulated, supported catalyst starting material according to the invention is used for the production of low-emission polyurethanes.
  • the above description for preferred embodiments of the polyurethane according to the invention also applies to the encapsulated catalyst according to the invention.
  • the invention provides a process for the reduction of emission from polyurethanes, characterized in that already in the preparation of the polyurethane, a polyurethane catalyst (i) and a supported catalyst scavenger in deactivated form (ii) is added to the reaction of isocyanate component with polyol component, wherein the deactivated supported catalyst scavenger (ii) is activated during the reaction, so that in the resulting polyurethane foam, a catalyst-catalyst-complex (iii) is present.
  • the catalyst-catalyst complex (iii) is such that it can not substantially be emitted from the polyurethane.
  • the process makes it possible to provide polyurethanes which on the one hand have low emissions and on the other hand have advantageous properties with respect to hydrolytic aging.
  • Advantageous mechanical and dynamic properties are, for example, resilience, compression set, tear resistance, tensile strength, hardness and / or moduli of elasticity.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne des polyuréthannes, en particulier des polyuréthannes à faible taux d'émission possédant de bonnes propriétés dynamiques mécaniques après vieillissement hydrolytique, lesquels polyuréthannes s'obtiennent en faisant réagir un composant isocyanate avec un composant polyol. L'invention se caractérise en ce qu'un catalyseur au polyuréthanne (i) et un piège à catalyseur supporté sous forme désactivée (ii) sont ajoutés avant la mise en réaction, le piège à catalyseur supporté (ii) pouvant être activé thermiquement. Cette invention concerne également un procédé de production du polyuréthanne selon l'invention ainsi que son utilisation dans la fabrication de la garniture intérieure de véhicules automobiles, de meubles, de tapis ou de matelas.
PCT/DE2007/000204 2006-02-09 2007-02-05 Polyuréthannes à faible taux d'émission WO2007090376A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006005938.7 2006-02-09
DE102006005938A DE102006005938A1 (de) 2006-02-09 2006-02-09 Emissionsarme Polyurethane

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WO2007090376A1 true WO2007090376A1 (fr) 2007-08-16

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EP2332999A1 (fr) * 2008-09-26 2011-06-15 DIC Corporation Catalyseur de réaction d'uréthanisation et procédé de fabrication de composé d'uréthane

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DE102015000393A1 (de) 2014-01-21 2015-07-23 Frank Becher Verfahren zur Herstellung von geschlossen-porigen Erzeugnissen mit hohlen Zellen, mittels dessen der Druck in den Zellen kontrolliert während des Aufschäumens erhöht oder reduziert werden kann, sowie Erzeugnisse, die nach diesem Verfahren hergestellt werden

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WO2002098940A1 (fr) * 2001-06-01 2002-12-12 Huntsman Petrochemical Corporation Perfectionnements apportes a la catalyse de mousse d'urethanne
WO2003085021A1 (fr) * 2002-04-10 2003-10-16 Basf Aktiengesellschaft Systemes catalyseurs contenant des catalyseurs incorpores dans de la cire

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Publication number Priority date Publication date Assignee Title
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EP2332999A4 (fr) * 2008-09-26 2012-04-04 Dainippon Ink & Chemicals Catalyseur de réaction d'uréthanisation et procédé de fabrication de composé d'uréthane

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