WO2022200176A1 - Procédé de réduction de (di)amines aromatiques dans des mousses de polyuréthane - Google Patents

Procédé de réduction de (di)amines aromatiques dans des mousses de polyuréthane Download PDF

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Publication number
WO2022200176A1
WO2022200176A1 PCT/EP2022/057038 EP2022057038W WO2022200176A1 WO 2022200176 A1 WO2022200176 A1 WO 2022200176A1 EP 2022057038 W EP2022057038 W EP 2022057038W WO 2022200176 A1 WO2022200176 A1 WO 2022200176A1
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component
isocyanate
weight
din
acid
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PCT/EP2022/057038
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German (de)
English (en)
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Joern Beaujean
Sebastian SCHLECHT
Matthaeus Gossner
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Covestro Deutschland Ag
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Priority to EP22712003.7A priority Critical patent/EP4314104A1/fr
Publication of WO2022200176A1 publication Critical patent/WO2022200176A1/fr

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    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
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Definitions

  • the present invention relates to a process for producing polyurethane foams using vvoonn emission-reducing compounds, the polyurethane foams themselves and the use of the emission-reducing compounds.
  • Additives for reducing aromatic amines are known from the prior art.
  • ⁇ , ⁇ -unsaturated carboxylic acids, ⁇ , ⁇ -unsaturated carboxylic acid derivatives, ⁇ , ⁇ -unsaturated ketones and/or ⁇ , ⁇ -unsaturated aldehydes are disclosed for the reduction of aromatic amines in the production of polyurethane foams, such as for example hydroxyethyl acrylate.
  • Another group for reducing aromatic amines are, for example, lactams, as disclosed in DE 199 28 687 A1 and in WO 2020/084003 A1.
  • a compound as claimed in claim 1 is not used in any of these disclosures.
  • the object of the present invention is to provide a process for producing polyurethane foams with a reduced proportion of aromatic amines, in a preferred embodiment a reduced proportion of the total emissions, by reducing the emission of the additive.
  • A1 an isocyanate-reactive component
  • P is a polyether polyol with an OH functionality of 2 to 8 and a number average molecular weight of 200 to 4000 g/mol, measured according to DIN 55672-1 of August 2007,
  • R 1 , R 2 each independently represent a substituted or unsubstituted C 1 - to C 8 - alkyl group or a substituted or unsubstituted aryl group
  • n represents the number of OH groups of P which is represented by the group -OC(O) - CH 2 -C (X) - R 1 are replaced and is at least 1, with
  • the present invention also provides the polyurethane foams obtainable by the process described and the use of the compound of the formula (I) for reducing the proportion of aromatic amines.
  • polyols selected from the group consisting of polyether polyols, polyester polyols, polyether ester polyols, polycarbonate polyols and polyether-polycarbonate polyols can be used as isocyanate-reactive components.
  • Polyester polyols and/or polyether polyols are preferred.
  • the compounds of component A1 can have an amine and/or hydroxyl number of between 15 and 4000 mg KOH/g and a functionality of 1 to 8.
  • the compounds of component A1 preferably have a number-average molecular weight of 2000 g/mol to 15000 g/mol, in particular 3000 g/mol to 12000 g/mol and particularly preferably 3500 g/mol to 6500 g/mol. If more than one compound of component A1 is used, the mixture of compounds of component A1 can preferably have a hydroxyl number of between 20 and 200 mg KOH/g, in particular 25 to 100 mg KOH/g.
  • “Functionality” in the context of the present invention denotes the theoretical average functionality (number of functions in the molecule that are reactive toward isocyanates or toward polyols) calculated from the known starting materials and their quantitative ratios.
  • the number-average molar mass M n (also: molecular weight) is determined by gel permeation chromatography in accordance with DIN 55672-1 (March 2007).
  • Polyetherester polyols which can be used are those compounds which contain ether groups, ester groups and OH groups.
  • Organic dicarboxylic acids having up to 12 carbon atoms are preferably used to prepare the polyetherester polyols, preferably aliphatic dicarboxylic acids having 4 to 6 carbon atoms or aromatic dicarboxylic acids, which are used individually or as a mixture. Examples include suberic acid, azelaic acid, decanedioic acid, malonic acid, phthalic acid, pimelic acid and sebacic acid and, in particular, glutaric acid, fumaric acid, succinic acid, adipic acid, phthalic acid, terephthalic acid and isoterephthalic acid called.
  • organic dicarboxylic acids In addition to organic dicarboxylic acids, it is also possible to use derivatives of these acids, for example their anhydrides and their esters and half-esters with low molecular weight, monofunctional alcohols having 1 to 4 carbon atoms.
  • the proportionate use of the above bio-based starting materials, in particular fatty acids or fatty acid derivatives (oleic acid, soybean oil etc.) is also possible and can have advantages, for example with regard to storage stability of the polyol formulation, dimensional stability, fire behavior and compressive strength of the foams.
  • Polyether polyols obtained by alkoxylating starter molecules such as polyhydric alcohols are used as a further component for the production of the polyetherester polyols.
  • the starter molecules are at least difunctional, but may also contain proportions of higher-functional, in particular trifunctional, starter molecules.
  • Starter molecules are, for example, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentenediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,10-decanediol, 2-methylpropane-1,3-diol, neopentyl glycol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2-butene-1,4-diol and 2-butyne-1,4-diol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, di- and trifunctional polyether polyols.
  • the polyether polyols preferably have an OH functionality of 2 to 4 and a molecular weight M n in the range from 62 to 4500 g/mol and in particular a molecular weight M n in the range from 62 to 3000 g/mol. Starter molecules with functionalities other than OH can also be used alone or in a mixture.
  • Polyetheresterpolyols can also be produced by the alkoxylation, in particular by ethoxylation and/or propoxylation, of reaction products obtained by reacting organic dicarboxylic acids and their derivatives and components with Zerewitinoff-active hydrogens, in particular diols and polyols.
  • organic dicarboxylic acids and their derivatives and components with Zerewitinoff-active hydrogens, in particular diols and polyols.
  • Zerewitinoff-active hydrogens in particular diols and polyols.
  • derivatives of these acids that can be used are their anhydrides.
  • the polyester polyols of component Al can, for example, polycondensates of polyhydric alcohols, preferably diols, atoms having 2 to 12 carbon atoms, preferably having 2 to 6 carbon atoms, and polycarboxylic acids, such as. B. di-, tri- or even tetracarboxylic acids or hydroxycarboxylic acids or lactones, aromatic dicarboxylic acids or mixtures of aromatic and aliphatic dicarboxylic acids are preferably used.
  • the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols can also be used to prepare the polyester.
  • carboxylic acids are: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, tetrahydrophthalic acid, Hexahydrophthalic acid, cyclohexanedicarboxylic acid, tetrachlorophthalic acid, itaconic acid, malonic acid, 2-methylsuccinic acid, 3,3-diethylglutaric acid, 2,2-dimethylsuccinic acid, dodecanedioic acid, endomethylenetetrahydrophthalic acid, dimer fatty acid, trimer fatty acid, citric acid, trimellitic acid, benzoic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid and terephthalic acid.
  • carboxylic acids such as dimethyl terephthalate
  • the carboxylic acids can be used either individually or as a mixture.
  • the carboxylic acids used are preferably adipic acid, sebacic acid and/or succinic acid, particularly preferably adipic acid and/or succinic acid.
  • hydroxycarboxylic acids which can be used as reactants in the preparation of a hydroxyl-terminated polyester polyol are lactic acid, malic acid, hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid, hydroxystearic acid and the like.
  • Suitable lactones include caprolactone, butyrolactone and homologues.
  • bio-based starting materials and/or their derivatives can also be used for the production of polyester polyols, e.g. B. Castor oil, polyhydroxy fatty acids, ricinoleic acid, hydroxyl-modified oils, grape seed oil, black cumin oil, pumpkin seed oil, borage seed oil, soybean oil, wheat seed oil, rapeseed oil, sunflower seed oil, peanut oil, apricot kernel oil, pistachio oil, almond oil, olive oil, macadamia nut oil, avocado oil, sea buckthorn oil, sesame oil, hemp oil, Hazelnut oil, primrose oil, wild rose oil, safflower oil, walnut oil, fatty acids, hydroxyl-modified and epoxidized fatty acids and fatty acid esters, for example based on myristoleic acid, palmitoleic acid, oleic acid, vaccenic acid, petroselinic acid, gadoleic acid, erucic acid, nervonic acid, lino
  • Esters of ricinoleic acid with polyhydric alcohols are particularly preferred.
  • diols examples include ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols such as polyethylene glycol, also 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol and isomers, neopentyl glycol or
  • Hydroxypivalic Acid Neopentyl Glycol Ester. Ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol or mixtures of at least two of the diols mentioned, in particular mixtures of 1,4-butanediol, 1,5-pentanediol and 1, 6-hexanediol.
  • polyols such as trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate can also be used, glycerol and trimethylolpropane being preferred.
  • monohydric alkanols can also be used.
  • Polyether polyols used according to the invention are obtained by production methods known to those skilled in the art, such as, for example, by anionic polymerization of one or more alkylene oxides having 2 to 4 carbon atoms with alkali metal hydroxides, such as sodium or potassium hydroxide, alkali metal alkoxides, such as sodium methylate, sodium or potassium ethylate or potassium isopropylate, or amine alkoxylation -Catalysts, such as dimethylethanolamine (DMEOA), imidazole and/or imidazole derivatives, using at least one starter molecule which contains 2 to 8, preferably 2 to 6, bonded reactive hydrogen atoms.
  • alkali metal hydroxides such as sodium or potassium hydroxide
  • alkali metal alkoxides such as sodium methylate, sodium or potassium ethylate or potassium isopropylate
  • amine alkoxylation -Catalysts such as dimethylethanolamine (DMEOA), imidazole and/or
  • alkylene oxides examples include tetrahydrofuran, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, styrene oxide and preferably ethylene oxide and 1,2-propylene oxide.
  • the alkylene oxides can be used individually, alternately one after the other, or as mixtures.
  • Preferred alkylene oxides are propylene oxide and ethylene oxide, and particular preference is given to copolymers of propylene oxide with ethylene oxide.
  • the alkylene oxides can be reacted in combination with CO 2 .
  • starter molecules are: water, organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid and terephthalic acid, aliphatic and aromatic, optionally N-mono-, N,N- and N,N'-dialkyl-substituted diamines having 1 to 4 carbon atoms in the alkyl radical , such as optionally mono- and dialkyl-substituted ethylenediamine, diethylenetriamine, triethylenetetramine, 1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5- and 1,6-hexamethylenediamine, phenylenediamines, 2,3-, 2,4- and 2,6-tolylenediamine and 2,2'-, 2,4'- and 4,4'-diaminodiphenylmethane.
  • organic dicarboxylic acids such as succinic acid, adipic acid, phthalic acid
  • dihydric or polyhydric alcohols such as ethanediol, 1,2- and 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, paraformaldehyde, triethanolamine, bisphenols, glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose.
  • Polycarbonate polyols which can be used are polycarbonates containing hydroxyl groups, for example polycarbonate diols. These arise in the reaction of carbonic acid derivatives, such as diphenyl carbonate, dimethyl carbonate or phosgene, with polyols, preferably diols.
  • diols examples include ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bishydroxymethylcyclohexane, 2- Methyl-1,3-propanediol, 2,2,4-trimethylpentanediol-1,3, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenols and lactone-modified diols of the type mentioned above.
  • polyether-polycarbonate diols which are obtainable, for example, by copolymerization of alkylene oxides, such as propylene oxide, with CO 2 .
  • Polymer polyols, PHD polyols and PIPA polyols can also be used in component A1 as isocyanate-reactive components.
  • Polymer polyols are polyols containing proportions of solid polymers produced by free radical polymerization of suitable monomers such as styrene or acrylonitrile in a base polyol.
  • PHD (polyhydrazodicarbonamide) polyols are produced, for example, by in situ polymerization of an isocyanate or an isocyanate mixture with a diamine and/or hydrazine (or hydrazine hydrate) in a polyol, preferably a polyether polyol.
  • the PHD dispersion is preferably prepared by reacting an isocyanate mixture of 75 to 85% by weight of 2,4-tolylene diisocyanate (2,4-TDI) and 15 to 25% by weight of 2,6-tolylene diisocyanate (2,6 -TDI) with a diamine and/or hydrazine hydrate in a polyether polyol prepared by alkoxylating a trifunctional starter (such as glycerol and/or trimethylolpropane).
  • a trifunctional starter such as glycerol and/or trimethylolpropane
  • PIPA polyols are polyether polyols modified by polyisocyanate polyaddition with alkanolamines, the polyether polyol preferably having a functionality of 2.5 to 4.0 and a hydroxyl number of 3 mg KOH/g to 112 mg KOH/g (molecular weight 500 g/mol to 18000 g/mol).
  • isocyanate-reactive components with a toe-opening effect, such as, for example, copolymers of ethylene oxide and propylene oxide with an excess of ethylene oxide or aromatic diamines such as diethyltoluenediamine.
  • component A1 can contain, for example, graft polyols, polyamines, polyamino alcohols and polythiols.
  • the isocyanate-reactive components described also include those compounds with mixed functionalities
  • polyethers which have at least two hydroxyl groups and an OH number of 20 to 50 mg KOH/g, the OH groups consisting of at least 80 mol % of primary OH groups (determined by means of 1 H-NMR (e.g. Bruker DPX 400, deuterochloroform)).
  • the OH number is particularly preferably from 25 to 40 mg KOH/g, very particularly preferably from 25 to 35 mg KOH/g.
  • compounds having at least two isocyanate-reactive hydrogen atoms and an OH number of 280 to 4000 mg KOH/g, preferably 400 to 3000 mg KOH/g, particularly preferably 1000 to 2000 mg KOH/g are additionally used in component A1.
  • These are to be understood as meaning compounds containing hydroxyl groups and/or amino groups and/or thiol groups and/or carboxyl groups, preferably Compounds containing hydroxyl groups and/or amino groups, which serve as chain extenders or crosslinking agents.
  • These compounds generally have 2 to 8, preferably 2 to 4, isocyanate-reactive hydrogen atoms.
  • ethanolamine, diethanolamine, triethanolamine, sorbitol and/or glycerol can be used.
  • Component A1 can consist of one or more of the abovementioned isocyanate-reactive components; component A1 preferably contains polyethers containing at least two hydroxyl groups, optionally mixed with polyesters containing at least two hydroxyl groups.
  • component A1 contains:
  • A11l Compounds containing isocyanates-reactive hydrogen atoms with an NH number according to DIN 53176 in the version of November 2002 and/or OH number according to DIN 53240-1 in the version of June 2013 from 15 to ⁇ 120 mg KOH/g, optionally
  • Water or carboxylic acids and mixtures thereof, for example, are used as the chemical blowing agent A2.1. These react with isocyanate groups to form the propellant gas, for example in the case of water, carbon dioxide is formed and in the case of z. B. formic acid produces carbon dioxide and carbon monoxide. At least one compound selected from the group consisting of formic acid, N,N-dialkylcarbamic acid, oxalic acid, malonic acid and ricinoleic acid is preferably used as the carboxylic acid. The ammonium salts of these acids are also suitable. Water is particularly preferably used as the chemical blowing agent. For example, low-boiling organic compounds such as e.g. B.
  • hydrocarbons ethers, ketones, carboxylic acid esters, carbonic acid esters, halogenated hydrocarbons.
  • organic compounds which are inert to the isocyanate component B and have boiling points below 100° C., preferably below 50° C., at atmospheric pressure. These boiling points have the advantage that the organic compounds evaporate under the influence of the exothermic polyaddition reaction.
  • Examples of such preferably used organic compounds are alkanes such as heptane, hexane, n- and isopentane, preferably technical mixtures of n- and isopentanes, n- and isobutane and propane, cycloalkanes such as cyclopentane and/or cyclohexane , Ethers such as furan, dimethyl ether and diethyl ether, ketones such as acetone and methyl ethyl ketone, carboxylic acid alkyl esters such as methyl formate, dimethyl oxalate and ethyl acetate and halogenated hydrocarbons such as methylene chloride, dichloromonofluoromethane, difluoromethane, trifluoromethane, difluoroethane, tetrafluoroethane, chlorodifluoroethane, 1,1-dichloro- 2,2,2-trifluoroethane, 2,
  • (hydro)fluorinated olefins such as HFO 1233zd(E) (trans-1-chloro-3,3,3-trifluoro-1-propene) or HFO 1336mzz(Z) (cis-1,1 ,1,4,4,4-hexafluoro-2-butene) or additives such as FA 188 from 3M (1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)pent- 2-en).
  • HFO 1233zd(E) trans-1-chloro-3,3,3-trifluoro-1-propene
  • HFO 1336mzz(Z) cis-1,1 ,1,4,4,4-hexafluoro-2-butene
  • additives such as FA 188 from 3M (1,1,1,2,3,4,5,5,5-nonafluoro-4-(trifluoromethyl)pent- 2-en).
  • Mixtures of two or more of the organic compounds mentioned can also be used.
  • the component contains A2
  • component A2 20 to 15% by weight (based on the total mass of component A) physical blowing agents. Particular preference is given to using water as component A2.
  • Auxiliaries and additives are used as component A3, such as a) catalysts (activators), b) surface-active additives (surfactants), such as emulsifiers and foam stabilizers, in particular those with low emissions such as products from the Tegostab ® LF series, c) additives such as reaction retardants ( For example, acidic substances such as hydrochloric acid or organic acid halides), cell regulators (such as paraffins or fatty alcohols or dimethylpolysiloxanes), pigments, dyes, flame retardants (such as tricresyl phosphate), stabilizers against aging and weathering, plasticizers, fungistatic and bacteriostatic substances, fillers (such as barium sulphate, diatomaceous earth, soot or whiting) and release agents.
  • reaction retardants For example, acidic substances such as hydrochloric acid or organic acid halides), cell regulators (such as paraffins or fatty alcohols or dimethylpolysiloxanes),
  • Preferred catalysts are aliphatic tertiary amines (e.g. trimethylamine, tetramethylbutanediamine), cycloaliphatic tertiary amines (e.g. 1,4-diaza(2,2,2)bicyclooctane), aliphatic amino ethers (e.g. dimethylaminoethyl ether and N,N,N-trimethyl-N- hydroxyethyl bisaminoethyl ether), cycloaliphatic amino ethers
  • N-ethylmorpholine aliphatic amidines, cycloaliphatic amidines, urea, derivatives of urea (such as aminoalkylureas), in particular (3-dimethylaminopropylamine)urea) and tin catalysts (such as dibutyltin oxide, dibutyltin dilaurate, tin octoate).
  • Particularly preferred catalysts are (i) urea, derivatives of urea and/or (ii) the abovementioned amines and amino ethers, characterized in that the amines and amino ethers contain a functional group which reacts chemically with the isocyanate.
  • the functional group is a hydroxyl group, a primary or secondary amino group.
  • P is a polyether polyol with an OH functionality of 2 to 8 and a number average molecular weight of 200 to 4000 g/mol, measured according to DIN 55672-1 of August 2007,
  • R 1 , R 2 each independently represent a substituted or unsubstituted C 1 - to C 8 - alkyl group or a substituted or unsubstituted aryl group
  • n represents the number of OH groups of P represented by the group -OC(O)- CH 2 -C(X)-R 1 are replaced and at least 1 is used to reduce the proportion of aromatic (di)amines, preferably toluenediamine (TDA) and/or methylenedianiline (MDA).
  • TDA toluenediamine
  • MDA methylenedianiline
  • the compound of formula (I) can, for example, by reacting a polyether polyol P with a ß-keto carboxylic acid ester and optionally subsequent reaction with a primary amine R 2 -NH 2 are prepared.
  • the polyether polyol P can be obtained as described in component A1.
  • the polyether polyol P has an OH functionality of 2 to 8, preferably 2 to 4 and particularly preferably 2 to 3.
  • the molecular weight of the polyether polyol P is 200 to 4000 g/mol, preferably 200 to 2000 g/mol and particularly preferably 200 to 800 g/mol.
  • the polyether polyol P has an equivalent weight of 50 to 500 g/mol, particularly preferably an equivalent weight of 50 to 500 g/mol and an OH functionality of 2 to 6.
  • the equivalent weight is based on the number-average molecular weight of the Polyetherpolyol P determined.
  • Acetoacetate esters, 3-oxopentanoic esters, 3-oxohexanoic esters, 4-methyl-3-oxopentanoic esters, benzylacetoacetate esters, 3-oxo-5-phenylpentanoic esters can be used as ⁇ -ketocarboxylic acid esters.
  • the .beta.-ketocarboxylic acid ester is preferably an acetoacetate ester, particularly preferably a C.sub.1 -C.sub.6 -alkyl ester of acetoacetic acid.
  • R 1 is preferably a substituted or unsubstituted C 1 - to C 8 - alkyl group, preferably a CI to C6 alkyl group, in particular a methyl, ethyl, propyl, or isopropyl group.
  • the primary amine R 2 -NH 2 has a substituted or unsubstituted C 1 to C 8 alkyl group or a substituted or unsubstituted aryl group.
  • R 2 is preferably an unsubstituted or substituted C 1 - to C 8 -alkyl group, particularly preferably a C 1 - to C 8 -alkyl group which has a tertiary amine as a substituent.
  • n OH groups of the polyether polyol P are replaced by the group -OC(O)-CH 2 -C(X)-R 1 , where n is at least 1.
  • the compound of the formula (I) is preferably a polyether polyol P in which only one free OH group is present or all OH groups are replaced by the group -OC(O)-CH 2 -C(X)- R1 have been replaced.
  • P is a polyether polyol having an OH functionality of 2 to 6 and an equivalent weight of 50 to 500 g/mol
  • R 1 , R 2 each independently represent a substituted or unsubstituted C 1 - to C 4 - alkyl group, and only one or two free OH groups are present.
  • Component A4 is preferably used in a proportion of 0.20 to 10% by weight, particularly preferably 0.3 to 5% by weight, based in each case on the total mass of component A.
  • Component B is preferably used in a proportion of 0.20 to 10% by weight, particularly preferably 0.3 to 5% by weight, based in each case on the total mass of component A.
  • Aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates are used as component B, for example those of the formula (II)
  • n is an integer between 2-4, preferably 2 or 3
  • Q is an aliphatic hydrocarbon radical having 2-18, preferably 6-10 carbon atoms, a cycloaliphatic hydrocarbon radical having 4-15, preferably 6-13 carbon atoms or an araliphatic hydrocarbon radical having 8-15, preferably 8-13 carbon atoms .
  • component B contains toluylene diisocyanate (“TDI”), diphenylmethane diisocyanate, polyphenylpolymethylene polyisocyanate or a mixture of the compounds mentioned.
  • TDI toluylene diisocyanate
  • other polyisocyanates can be used, such as polyphenylpolymethylene polyisocyanates, such as those produced by aniline-formaldehyde condensation and subsequent phosgenation (“crude MDI”) and polyisocyanates containing carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups (“modified polyisocyanates”).
  • modified polyisocyanates which are derived from 2,4- and/or 2,6-tolylene diisocyanate or from 4,4'- and/or 2,4'-diphenylmethane diisocyanate.
  • component B at least one compound is preferably selected from the group consisting of 2,4- and 2,6-
  • Toluylene diisocyanate 4,4'- and 2,4'- and 2,2'-diphenylmethane diisocyanate and polyphenylpolymethylene polyisocyanate ("multi-nuclear MDI") are used.
  • the polyurethane foams obtained according to the invention are preferably flexible polyurethane foams or semirigid polyurethane foams.
  • the reaction components are treated according to the known method
  • One-step process, the prepolymer process or the semi-prepolymer process are implemented, often using mechanical equipment.
  • the polyurethane foams can be produced as molded foams or also as block foams, it being possible for the molded foams to be produced in a hot-curing or cold-curing manner.
  • the invention therefore relates to a process for the production of polyurethane foams, the polyurethane foams produced by this process and their use for the production of molded parts or block goods, and the molded parts or block goods themselves.
  • the polyurethane foams obtainable according to the invention are used, for example, in the following areas: furniture upholstery, textile inserts, mattresses, automobile seats, headrests, armrests, sponges and components, as well as seat and instrument paneling, and have indexes of 100 or less, preferably 50 to 90, particularly preferably 65 to 85.
  • the isocyanate index (also known as index or isocyanate index) is the quotient of the amount of substance [mol] of isocyanate groups actually used and the amount of substance [mol] of isocyanate-reactive groups actually used, multiplied by 100:
  • the NCO value (also: NCO content, isocyanate content) is determined using EN ISO 11909:2007. Unless otherwise stated, these are the values at 25°C.
  • the invention relates to a process for the production of polyurethane foams, the components
  • auxiliaries and additives such as a) catalysts, b) surface-active additives, c) pigments and/or flame retardants,
  • P is a polyether polyol with an OH functionality of 2 to 8 and a number average molecular weight of 200 to 4000 g/mol, measured according to DIN 55672-1 of August 2007,
  • R 1 , R 2 each independently represent a substituted or unsubstituted C 1 - to C 8 - alkyl group or a substituted or unsubstituted aryl group
  • n represents the number of OH groups of P which is represented by the group -OC(O)- CH 2 -C(X)- R 1 are replaced and is at least 1, with
  • Polyphenyl polymethylene polyisocyanate or a mixture of said compounds are reacted with one another at an isocyanate index of 100 or less.
  • the raw density and molded part density was determined in accordance with DIN EN ISO 845 in the October 2009 version.
  • the test specimens had a volume of 80x80x40 mm 3 .
  • the hydroxyl number was determined in accordance with DIN 53240-1 in the June 2013 version.
  • the content of aromatic amines in the foam was determined for the examples in Table 1 by extraction with 0.1% acetic acid according to Skarping (A. Marand, D. Karlsson, M. Dalene, G. Skarping, Analytica Chimica Acta, 2004. 510, 109-119 J R Johnson, D Karlsson, M Dalene, G Skarping, Analytica Chimica Acta, 2010. 678(1), 117-123), but different from the cited literature without subsequent derivatization. After demolding, the TDA and MDA content of the samples was determined for the first time after 4 hours.
  • Examples 3 and 4 The samples were then stored openly for a total of 48 hours (Examples 3 and 4) or 72 hours (Examples 1, 2 and 6 to 9) before the second analysis was carried out (Table 1: "after storage”).
  • the specification NN ⁇ 0.06 means that the measured value is below the detection limit and the specification ⁇ 0.2 means that the measured value is below the limit of quantification.
  • VOC and FOG values for the examples in Table 2 were measured in accordance with the Technical Rule VDA 278 of the Association of the Automotive Industry "Thermal desorption analysis of organic emissions for the characterization of non-metallic automotive materials” in the October 2011 version.
  • Al.1-1 Polyether polyol having an OH number of 28 mg KOH/g, prepared by alkoxylating glycerol with a mixture of ethylene oxide and propylene oxide in a proportion of 87/13
  • Al.1-2 polyol containing filler with 21.6% polyurea dispersion (PHD) as filler and 78.4% of a polyether polyol based on glycerol, ethylene oxide and propylene oxide with a number-average molecular weight of 4007 g/mol and an OH number of 28 mg KOH/g
  • PLD polyurea dispersion
  • Al.1-3 Polyether polyol based on glycerol, ethylene oxide and propylene oxide with a very high proportion of ethylene oxide groups and an OH number of 37 mg KOH/g
  • Al.1-4 Polyether polyol with an OH number of 31 mg KOH/g
  • Al.1-5 Dispersion of styrene-acrylonitrile copolymer (42% by weight) in a glycerol-started polypropylene oxide-polyethylene oxide block copolymer (OH number 20 mg KOH/g)
  • Al.2-1 polyether polyol mixture, catalytically active, OH number 127 mg KOH/g
  • Al.2-2 polyether polyol mixture with a functionality of 1.8 and an OH number of 410 mg KOH/g
  • A3-1 Silicone stabilizer (Niax® L-3222, commercial product from Momentive Performance
  • A3-2 tertiary amine catalyst (Polycat® 58, commercial product from Evonik)
  • A3-3 amine catalyst (Dabco® NE 1091, commercial product from Evonik)
  • A3-4 Silicone stabilizer (Tegostab® B 8736 LF2, commercial product from Evonik)
  • A3-5 33% by weight of triethylenediamine in dipropylene glycol (Dabco 33 LV, commercial product from
  • A3-8 Bis[2-dimethylamino)ethyl]ether (70 wt%) in dipropylene glycol (30 wt%), Niax®
  • A4-1 Additive based on a polyether polyol with a number average molecular weight of
  • B-2 Isocyanate mixture of 80% by weight 2,4-TDI and 20% by weight 2,6-TDI
  • the isocyanate is weighed into a suitable beaker and emptied again (flow time: 3 s). This beaker, which is still wet on the inside walls, is tared and refilled with the specified amount of isocyanate. The isocyanate becomes the other Components added (flow time: 3 s). The resulting mixture of isocyanate and the other components is mixed intensively for 5 seconds using an agitator (from Pendraulik). To form a molded foam (Tables 1 and 2), the reaction mixture is poured into an aluminum box mold with a volume of 10 dm 3 at 40° C., with a release agent being applied. The mold is closed and locked. After 10 minutes, the latch is opened and released.
  • Table 1 show the effect of the process according to the invention with the additives A4-1 and A4-2 on the proportion of aromatic (di-)amine in the polyurethane foam determined using the Skarping method. Irrespective of the index, the process according to the invention leads to polyurethane foams with lower proportions of aromatic (di-)amine before and after storage of the polyurethane foams.
  • Example 9 Due to the catalytically active imine group in additive A4-2, the amount of catalyst in Example 9 had to be adjusted compared to Comparative Example 8, so that a polyurethane foam with the same molding density is obtained.
  • Table 2 shows the effect of the process according to the invention on formulations based on isocyanate B-2 in accordance with VDA 278.
  • a polyurethane foam without an additive A4 (Example 10) has a total TDA emission of 210 ppm.
  • the use of various amounts of additive A4 in polyurethane foams leads to emissions of TDA of only 22 to 119 ppm (Examples 11 to 13).
  • Table 3 shows the reduction of aromatic (di)amine in the production of viscoelastic polyurethane foams.
  • component A4-1 the use of component A4-1 according to the invention leads to a significant reduction in aromatic (di-)amines in the foam compared to reference example 14.

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Abstract

La présente invention concerne un procédé de production de mousses de polyuréthane consistant à faire réagir un composant A contenant un composant A1 réactif à l'isocyanate, un agent de gonflement A2 contenant de l'eau, éventuellement un agent auxiliaire A3 et un additif, un composé A4 de formule P[-O-C(O)-CH2-C(X)-R1]n (I), dans laquelle P représente un polyol de polyéther présentant une fonctionnalité OH de 2 à 8 et un poids moléculaire moyen en nombre de 200 à 4.000 g/mol, mesuré conformément à la norme DIN 55672-1 d'août 2007, X représente =O ou =N-R2, R1 et R2 représentent, indépendamment l'un de l'autre, un groupe alkyle en C1 à C8 substitué ou non substitué, et n représente le nombre de groupes OH de P qui sont remplacés par le groupe -O-C(O)-CH2-C(X)-R1 et est d'au moins 1, avec le composant B, un isocyanate contenant du diisocyanate de toluène, du diisocyanate de diphénylméthane, un polyisocyanate de polyméthylène polyphényle, ou des mélanges desdits composés, à un indice d'isocyanate de 100 ou moins. L'invention concerne également des mousses de polyuréthane selon le procédé, l'utilisation des mousses de polyuréthane et l'utilisation du composant A4.
PCT/EP2022/057038 2021-03-23 2022-03-17 Procédé de réduction de (di)amines aromatiques dans des mousses de polyuréthane WO2022200176A1 (fr)

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DE19928687A1 (de) 1999-06-23 2000-12-28 Basf Ag Polyisocyanat-Polyadditionsprodukte
WO2001057104A2 (fr) * 2000-01-31 2001-08-09 Bayer Antwerpen N.V. Mousses de polyurethanne viscoelastiques
EP0629607B1 (fr) * 1993-06-16 2001-10-31 Bayer Ag Composés contenant un groupement amino tertiaire, procédé pour leur préparation et leur utilisation comme catalysateur
EP2628756B1 (fr) * 2012-02-15 2015-01-28 Bayer Intellectual Property GmbH Mousses semi-dures à base de polyuréthane, leur fabrication et leur utilisation
US20190367695A1 (en) * 2017-02-20 2019-12-05 Dow Global Technologies Llc Polyurethanes having reduced aldehyde emissions
WO2020084003A1 (fr) 2018-10-24 2020-04-30 Basf Se Mousses de polyuréthane à teneur réduite en amines aromatiques

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0629607B1 (fr) * 1993-06-16 2001-10-31 Bayer Ag Composés contenant un groupement amino tertiaire, procédé pour leur préparation et leur utilisation comme catalysateur
DE19919826A1 (de) 1999-04-30 2000-11-02 Basf Ag Verfahren zur Herstellung von Polyurethanschaumstoffen
DE19928687A1 (de) 1999-06-23 2000-12-28 Basf Ag Polyisocyanat-Polyadditionsprodukte
WO2001057104A2 (fr) * 2000-01-31 2001-08-09 Bayer Antwerpen N.V. Mousses de polyurethanne viscoelastiques
EP2628756B1 (fr) * 2012-02-15 2015-01-28 Bayer Intellectual Property GmbH Mousses semi-dures à base de polyuréthane, leur fabrication et leur utilisation
US20190367695A1 (en) * 2017-02-20 2019-12-05 Dow Global Technologies Llc Polyurethanes having reduced aldehyde emissions
WO2020084003A1 (fr) 2018-10-24 2020-04-30 Basf Se Mousses de polyuréthane à teneur réduite en amines aromatiques

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