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WO2008068197A1 - Préparations de polyisocyanate - Google Patents

Préparations de polyisocyanate Download PDF

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Publication number
WO2008068197A1
WO2008068197A1 PCT/EP2007/063067 EP2007063067W WO2008068197A1 WO 2008068197 A1 WO2008068197 A1 WO 2008068197A1 EP 2007063067 W EP2007063067 W EP 2007063067W WO 2008068197 A1 WO2008068197 A1 WO 2008068197A1
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WIPO (PCT)
Prior art keywords
acid
polyisocyanate
preparations according
weight
alkoxyalkanecarboxylic
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PCT/EP2007/063067
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German (de)
English (en)
Inventor
Carl Jokisch
Harald Schäfer
Horst Binder
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Basf Se
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Publication of WO2008068197A1 publication Critical patent/WO2008068197A1/fr

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    • 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
    • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds

Definitions

  • the present invention relates to novel stabilized polyisocyanate preparations.
  • Polyisocyanates which are used for coatings and coatings are generally reaction products of isocyanates, usually of diisocyanates. These are modified by urethanization, urea formation, allophanatization, biuretization, trimerization and dimerization and similar reaction possibilities.
  • the polyisocyanates obtained in this way often contain no or very little free starting isocyanate. But they still contain free NCO groups, which still have a high reactivity, which should be used for later application. However, such polyisocyanate preparations must be stable and stable over long periods of time.
  • EP 341516 B1 describes polyisocyanates which are stabilized with the aid of chloroalkanoic acids comprising at least three carbon atoms. Examples are 2- and 3-chloropropionic acid.
  • a stabilizer is intended to fulfill a number of functions: it should be reaction accelerators and catalysts which were previously used, if appropriate, in reactions or with reaction partners, e.g. Polyethers or polyesters are unintentionally but inevitably introduced, bind and render ineffective;
  • stabilizer in the present application does not mean the polyurethane foam stabilizers which have long played a major role in isocyanate chemistry and are surface-active agents, for example based on polysiloxanes.
  • US 3914269 describes weak acids with a pKa of 4 to 12 for the decomposition of carbodiimide structures in a reaction mixture of a phosgenation of aromatic amines.
  • EP 643042 A describes the stabilization of a phosgene-free process diisocyanate with a mixture of stabilizers, which also contains acids.
  • the object of the present invention was to provide further possibilities for the stabilization of polyisocyanates, in particular to reduce an increase in viscosity during storage.
  • At least one alkoxyalkanoic acid (A) at least one alkoxyalkanoic acid (A)
  • the polyisocyanates (P) used according to the invention are oligomers of aromatic, aliphatic or cycloaliphatic isocyanates (D), preferably aliphatic or cycloaliphatic, which in this document is referred to briefly as (cyclo) aliphatic, particularly preferred are aliphatic isocyanates.
  • Aromatic isocyanates are those containing at least one aromatic ring system.
  • Cycloaliphatic isocyanates are those which contain at least one cycloaliphatic ring system.
  • Aliphatic isocyanates are those which contain exclusively straight or branched chains, ie acyclic compounds.
  • the isocyanates (D) are preferably diisocyanates which carry exactly two isocyanate groups. In principle, however, it may also be monoisocyanates having an isocyanate group.
  • higher isocyanates having an average of more than 2 isocyanate groups are also considered.
  • triisocyanates such as triisocyanato, 2,4,6-triisocyanatotoluene, triphenylmethane triisocyanate or 2,4,4'-triisocyanato-diphenyl ether or the mixtures of di-, tri- and higher polyisocyanates suitable for example by phosgenation of corresponding aniline / Formaldehyde condensates are obtained and represent methylene bridges Polyphenylpolyiso- cyanate.
  • the diisocyanates are preferably isocyanates having 4 to 20 C-
  • customary diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1, 4, 1, 3 or 1, 2-diisocyanatocyclohexane, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, 1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane ( Isophorone
  • Di (isocyanatocyclohexyl) methane most preferred are isophorone diisocyanate and hexamethylene diisocyanate, particularly preferred is hexamethylene diisocyanate.
  • isophorone diisocyanate and hexamethylene diisocyanate, particularly preferred is hexamethylene diisocyanate.
  • isocyanates There may also be mixtures of said isocyanates.
  • a preferred mixture is composed of 1, 6-hexamethylene diisocyanate and isophorone diisocyanate.
  • Isophorone diisocyanate is usually present as a mixture, namely the cis and trans isomers, usually in the ratio of about 60:40 to 80:20 (w / w), preferably in the ratio of about 70:30 to 75:25 and most preferably in the ratio of about 75:25.
  • Dicyclohexylmethane-4,4'-diisocyanate may also be present as a mixture of the different cis and trans isomers.
  • (cyclo) aliphatic diisocyanates eg such as 1,6-hexamethylene diisocyanate (HDI), isomeric aliphatic diisocyanates having 6 carbon atoms in the alkylene radical, 4,4'- or 2,4'-
  • Di (isocyanatocyclohexyl) methane and 1-isocyanato-S-isocyanato-methyl-S ⁇ - trimethylcyclohexane are prepared by reacting the (cyclo) aliphatic diamines with, for example, urea and alcohols to (cyclo) aliphatic Biscarbaminklareestern and their thermal cleavage into the corresponding diisocyanates and alcohols.
  • the synthesis is usually carried out continuously in a cyclic process and optionally in the presence of N-unsubstituted carbamic acid esters, dialkyl carbonates and other by-products recycled from the reaction process.
  • Diisocyanates obtained in this way generally have a very low or even non-measurable proportion of chlorinated compounds, which leads to favorable color numbers of the products.
  • the diisocyanates (D) have a total hydrolyzable chlorine content of less than 200 ppm, preferably less than 120 ppm, more preferably less than 80 ppm, most preferably less than 50 ppm, especially less than 15 ppm and especially less than 10 ppm. This can be measured, for example, by ASTM D4663-98. However, it is of course also possible to use diisocyanates (D) with a higher chlorine content, for example up to 500 ppm.
  • mixtures of such diisocyanates obtained by reaction of the (cyclo) aliphatic diamines with, for example, urea and alcohols and cleavage of the resulting (cyclo) aliphatic biscarbamic acid esters may also be obtained.
  • those with diisocyanates obtained by phosgenation of the corresponding amines may also be obtained.
  • the polyisocyanates (P) to which the isocyanates (D) can be oligomerized are usually characterized as follows:
  • the NCO functionality of such compounds is generally at least 1, 8 and may be up to 8, preferably 1, 8 to 5 and particularly preferably 2 to 4.
  • the polyisocyanates (P) are preferably the following compounds:
  • isocyanurate polyisocyanates of aromatic, aliphatic and / or cycloaliphatic diisocyanates Particular preference is given here to the corresponding aliphatic and / or cycloaliphatic isocyanato-isocyanurates and in particular those based on hexamethylene diisocyanate and isophorone diisocyanate.
  • the isocyanurates present are in particular tris-isocyanatoalkyl or tris-isocyanatocycloalkyl
  • Isocyanurates which are cyclic trimers of diisocyanates, or mixtures with their higher, more than one isocyanurate homologues.
  • the isocyanato-isocyanurates generally have an NCO content of 10 to 30 wt .-%, in particular 15 to 25 wt .-% and an average NCO functionality of 2.6 to 8.
  • uretdione diisocyanates having aromatic, aliphatic and / or cycloaliphatic bonded isocyanate groups, preferably aliphatically and / or cycloaliphatically bonded and in particular those derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • Uretdione diisocyanates are cyclic dimerization products of diisocyanates.
  • the uretdione diisocyanates can be used as the sole component or in a mixture with other polyisocyanates, in particular those mentioned under 1).
  • biuret polyisocyanates having aromatic, cycloaliphatic or aliphatic bound, preferably cycloaliphatic or aliphatic bound isocyanate groups, in particular tris (6-isocyanatohexyl) biuret or mixtures thereof with its higher homologues.
  • These biuret-containing polyisocyanates generally have an NCO content of 18 to 22 wt .-% and an average NCO functionality of 2.8 to 4.5.
  • diisocyanate for example hexamethylene diisocyanate or isophorone diisocyanate
  • O monohydric or polyhydric alcohols
  • These urethane and / or allophanate-containing polyisocyanates generally have an NCO content of 12 to 24 wt .-% and an average NCO functionality of 2.5 to 4.5.
  • oxadiazinetrione-containing polyisocyanates preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such oxadiazinetrione-containing polyisocyanates are accessible from diisocyanate and carbon dioxide.
  • polyisocyanates containing iminooxadiazinedione groups preferably derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • iminooxadiazine-dione-containing polyisocyanates can be prepared from diisocyanates by means of special catalysts.
  • Hyperbranched polyisocyanates as are known, for example, from DE-A1 10013186 or DE-A1 10013187.
  • the polyisocyanate (P) is selected from the group consisting of isocyanurates, biurets, urethanes and allophanates, preferably from the group consisting of isocyanurates, urethanes and allophanates, more preferably from the group consisting of isocyanurates and allophanates.
  • the isocyanates (D) but also polyisocyanates (P) with at least one monohydric or polyhydric alcohol (O) are reacted, such as methanol, ethanol, isopropanol, n-propanol, n-butanol , isobutanol, sec-butanol, tert-butanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol), 2-ethylhexanol, n-pentanol, stearyl alcohol, cetyl alcohol, Lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1,3-propanediol monomethyl ether, cyclopentanol, cyclohexanol, cycloo
  • the proportion of alcohol (O) can be up to 50% by weight, preferably up to 40, particularly preferably up to 30 and very particularly preferably up to 25% by weight, based on the isocyanate (D).
  • only a small proportion of alcohol (O) can be used based on the isocyanate (D), for example 0.25-10% by weight, preferably 0.5-8, particularly preferably 0.75-5 and most preferably 1-3% by weight.
  • the alcohol (O) is a compound having at least one, preferably exactly one isocyanate-reactive group and at least one, for example one to six, preferably one to five, particularly preferably one to four and all particularly preferably one, two or three free-radically polymerizable unsaturated groups, preferably acrylate or methacrylate groups.
  • Isocyanate-reactive groups may be e.g. Hydroxy, mercapto, amino or monosubstituted imino, preferably hydroxy or amino, more preferably hydroxy.
  • Examples of such compounds are, for example, monoesters of methacrylic acid or preferably acrylic acid with diols or polyols which preferably have 2 to 20 C atoms and at least two hydroxyl groups, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol , 1, 1-dimethyl-1, 2-ethanediol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol, 1, 2, 1, 3 or 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, 1 , 6-hexanediol, 2-methyl-1, 5-pentanediol, 2-ethyl-1, 4-butanediol, 1, 4-dimethylolcyclohexane, 2,2-bis (4-hydroxycyclohexyl) propane, glycerol, trimethyl
  • the unreacted isocyanate is usually separated from the polyisocyanate after its preparation, preferably via a thin-film distillation.
  • the content of unreacted, monomeric isocyanate in the polyisocyanate (P) is generally below 1% by weight, preferably below 0.7% by weight, more preferably below 0.5% by weight, very particularly preferably below 0.3% by weight. and in particular less than 0.1% by weight.
  • alkoxyalkanoic acid (A) used in accordance with the invention is alkanecarboxylic acids which carry one or more alkyloxy radicals, preferably an alkoxy radical.
  • the alkanecarboxylic acids are preferably from 1 to 10, preferably 2 to 6, more preferably 2 to 4, most preferably 2 or 3 carbon atoms straight-chain or branched alkanecarboxylic acids.
  • alkanecarboxylic acids are formic acid, acetic acid, propionic acid, n-butanoic acid, isobutyric acid, pentanoic acid, 2-methylpentanoic acid, n-hexanoic acid, 2-ethylhexanoic acid or 3-propylheptanoic acid, preferably acetic acid, propionic acid, n-butanoic acid or isobutyric acid, particularly preferably acetic acid or propionic acid and most preferably acetic acid.
  • the alkyl groups of the alkyloxy radicals preferably have 1 to 4, particularly preferably 1 to 3, very particularly preferably 1 to 2 and in particular 1 carbon atom.
  • Examples are methoxy, ethoxy, isopropoxy, n-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy, preferred are methoxy, ethoxy, isopropoxy and n-butoxy, particularly preferred are methoxy and ethoxy and most preferred is methoxy.
  • Exemplary individuals are 3-methoxybutanoic acid, 3-methoxypropanoic acid, 2-methoxypropanoic acid, 3-methoxy-2-methylpropanoic acid, methoxyacetic acid, 3-ethoxybutanoic acid, 3-ethoxypropanoic acid, 2-ethoxypropanoic acid, 3-ethoxy-2-methylpropanoic acid and ethoxyacetic acid.
  • 3-methoxypropanoic acid, 2-methoxypropanoic acid, methoxyacetic acid, 3-ethoxypropanoic acid and ethoxyacetic acid are particularly preferred.
  • 3-methoxypropanoic acid, 2-methoxypropanoic acid, methoxyacetic acid and ethoxyacetic acid very particular preference is given to ethoxyacetic acid and methoxyacetic acid and in particular methoxyacetic acid.
  • Preferred alkyloxyalkanecarboxylic acids (A) have a pKa in the aqueous system of from 2.5 to 4.5, preferably from 2.75 to 4.0.
  • alkyloxyalkanecarboxylic acids (A) have a logP of from -1 to +1, preferably from -0.75 to +0.75.
  • the calculations of logP values are carried out with the program Molgen 3.0, Evaluation Copy, ⁇ 1994 P. Baricic, M. Mackov.
  • the calculation of the logP values is carried out after optimization of the structures with an MM2 force field using the Crippen fragmentation method as described in A.K. Ghose, A. Pritchett, G.M. Crippen, J. Comput. Chem., 9, 80-90, 1988.
  • Alkyloxyalkancarbon yarnren (A) have a solubility in the polyisobutene cyanate (P) at 25 0 C of at least 100 ppm by weight to, preferably at least 1 wt%.
  • the solubility refers to solutions of the polyisocyanates (P) in the solvent (L).
  • the addition of the alkyloxyalkanecarboxylic acid (A) is generally carried out in the already prepared polyisocyanates (P) after distillative removal of the monomeric isocyanate.
  • P polyisocyanates
  • This can be done, for example, by metering the alkyloxyalkanecarboxylic acid (A) into a pump, for example into a filling or circulating pump. If desired, the pump may be followed by a static mixer, which is usually not necessary.
  • the addition is preferably carried out at room temperature (23 0 C) to 30 0 C.
  • the reaction is stopped by deactivating the catalyst by adding the compound (A).
  • the conversion can be chosen differently depending on the isocyanate used. In general, a conversion of 10 to 60% (based on the NCO content before the reaction) is desired, preferably 10 to 40%.
  • the addition of the Alkyloxyalkancarbonklare (A) is usually carried out at the reaction temperature, but can also be carried out at higher or lower temperature, for example up to 30 0 C lower, preferably up to 20 0 C lower and more preferably up to 10 0 C lower.
  • the compound (A) in a molar ratio of, for example, 0.5 to 30, more preferably from 0.6 to 3, most preferably 0.8 to 2, based on the amount of catalyst used.
  • the polyisocyanate preparation may optionally contain at least one solvent in which the resulting polyisocyanate (P) is formulated after removal of the unreacted isocyanate (D). It would also be conceivable that the preparation of the polyisocyanate (P) from the isocyanate (D) in a solvent (L) is performed. In the latter case, the solvent (L) can be distilled off with the isocyanate (D) or the mixture of polyisocyanate (P), isocyanate (D) and solvent (L) can be further used.
  • solvents examples include aromatic and / or (cyclo) aliphatic hydrocarbons and mixtures thereof, halogenated hydrocarbons, esters and ethers.
  • aromatic hydrocarbons (cyclo) aliphatic hydrocarbons, alkanoic acid alkyl esters, alkoxylated alkanoic acid alkyl esters and mixtures thereof.
  • Particularly preferred are mono- or polyalkylated benzenes and naphthalenes, Alkanklarealkylester and alkoxylated Alkanklarealkylester and mixtures thereof.
  • Preferred aromatic hydrocarbon mixtures are those which comprise predominantly aromatic C 7 - to C 20 -hydrocarbons and may have a boiling range of from 10 to 300 ° C., particular preference is given to toluene, o-, m- or p- XyIoI, trimethylbenzene isomers, tetramethylbenzene isomers, ethylbenzene, cumene, tetrahydronaphthalene and mixtures containing such.
  • Solvesso® brands from ExxonMobil Chemical, Particularly Solvesso® 100 (CAS No. 64742-95-6, predominantly C9 and Cio aromatics, boiling range about 154 -. 178 0 C), 150 (boiling range about 182 -. 207 0 C) and 200 (CAS No. 64742-94-5), Shellsol® grades from Shell, Caromax® (eg Caromax® 18) from Petrochem Carless and hydrosol from DHC (eg as hydrosol ® A 170). Hydrocarbon mixtures of paraffins, cycloparaffins and aromatics are also available under the designations crystal oil (for example, crystal oil 30, boiling range about 158-198 0 C or crystal oil. 60: CAS No.
  • hydrocarbon mixtures are generally more than 90% by weight, preferably more than 95, more preferably more than 98% and very particularly preferably more than 99% by weight. It may be useful to use hydrocarbon mixtures with a particularly reduced content of naphthalene.
  • the content of aliphatic hydrocarbons is generally less than 5, preferably less than 2.5 and more preferably less than 1% by weight.
  • Halogenated hydrocarbons are, for example, chlorobenzene and dichlorobenzene or isomeric mixtures thereof.
  • Esters include, for example, n-butyl acetate, ethyl acetate, 1-methoxypropyl acetate-2 and 2-methoxyethyl acetate.
  • Ethers are, for example, THF, dioxane and the dimethyl, ethyl or n-butyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol.
  • Examples of (cyclo) aliphatic hydrocarbons are decalin, alkylated decalin and isomer mixtures of straight-chain or branched alkanes and / or cycloalkanes, for example petroleum ether or ligroin.
  • Such mixtures can be prepared in a volume ratio of 5: 1 to 1: 5, preferably in a volume ratio of 4: 1 to 1: 4, more preferably in a volume ratio of 3: 1 to 1: 3 and most preferably in a volume ratio of 2: 1 to 1: 2
  • Preferred examples are butyl acetate / xylene, methoxypropyl acetate / xylene 1: 1, butyl acetate / solvent naphtha 100 1: 1, butyl acetate / Solvesso® 100 1: 2 and crystal oil 30 / Shellsol® A 3: 1.
  • the other stabilizers may be primary or secondary stabilizers.
  • Primary stabilizers (S1) are those compounds which are usually active as antioxidant and / or radical scavenger. Suitable primary stabilizers for the purposes of the invention are preferably phenolic antioxidants, ie compounds which contain at least one sterically hindered phenolic group.
  • phenolic antioxidants which may be mentioned are 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol) butylphenol), 2,2'-thiobis (4-methyl-6-t-butylphenol), 4,4'-thio-bis (3-methyl-6-t-butylphenol), 4,4'-butylidene bis (6-t-butyl-3-methylphenol), 4,4'-methylidenebis (2,6-di-t-butylphenol), 2,2'-methylenebis [4-methyl-6 - (1-methylcyclohexyl) phenol], tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate] methane, 1, 3,5-trimethyl-2,4,6- tris (3, 5-d it-butyl-4-hydroxybenzyl) benzene, N,
  • octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (4-methyl-6-t.butylphenol), triethylene glycol bis-3- (t-butyl-4-hydroxy-5-methylphenyl) propionate, tetrakis [methylene-3 - (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and especially 2,6-di-t-butyl-4-methylphenol and 3,5-di-tert-butyl-4-hydroxy anisole.
  • nitrogen-containing stabilizers preferably aromatic amines substituted by alkyl, cycloalkyl and / or aryl radicals, for example 4,4'-di-t.octyldiphenylamine, 4,4'-di- ( ⁇ , ⁇ -dimethylbenzyl ) -diphenylamine, phenyl-.beta.-naphthylamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-phenyl-2-naphthylamine and / or phenyl-2-aminonaphthalene.
  • nitrogen-containing stabilizers preferably aromatic amines substituted by alkyl, cycloalkyl and / or aryl radicals
  • nitrogen-containing stabilizers preferably aromatic amines substituted by alkyl, cycloalkyl and / or aryl radicals
  • the sterically hindered phenols and aromatic amines can each be used individually or in the form of mixtures. It is also possible to use mixtures of at least one sterically hindered phenol and at least one aromatic amine.
  • secondary stabilizers which can be used as sole stabilizers or preferably together with the primary stabilizers, it is expedient to use compounds which are usually active as peroxide splitter and / or reducing agent.
  • Suitable secondary stabilizers according to the invention are e.g. phosphorus-containing compounds, preferably triesters of phosphorous acid, e.g. Trialkyl phosphites and triaryl phosphites, and thioethers.
  • phosphorous acid esters e.g. Distearyl pentaerythritol diphosphite, tris (nonylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl-4,4'-biphenylene diphosphonite, tris (2,4-di-t-butylphenyl) phosphite, neophen - Tylglykoltriethylenglykol diphosphite, diisodecylpentaerythritol diphosphite, Tristea- rylphosphit, Trilaurylphosphit, Diisodecylphenylphosphit, Tributylphosphit, Trioc- tylphosphit and triphenyl phosphite, which is preferably used, proven.
  • Distearyl pentaerythritol diphosphite tris
  • thioethers examples include: 2-methyl-1-propenyl tert-dodecyl thioether, cyclohexylidenemethyl n-dodecyl thioether, 3-cyclohexen-1-ylidenemethyl-n-octadecyl thioether, 3-cyclohexene-1-ylidenemethyl ether.
  • n-dodecylthioethers 3-cyclohexeno (1) -ylidenemethyl-n-octylthioethers, 3-cyclohexeno (1) -ylidenemethylcyclohexylthioethers, 3-methyl- (3) -cyclohexeno (1) -ylidenemethyl-n- dodecylthioether, 3-cyclohexeno (1) -ylidene-methyl-p-tolylthioether, 3-cyclohexeno (1) -ylidenemethylbenzylthioether, and preferably 3-cyclohexeno (1) -ylidenemethyl-n-dodecylthioether and 1 -hexenyl-n -dodecylthioether.
  • the secondary stabilizers from the group of organic phosphites and thioethers which are suitable according to the invention can, like the primary stabilizers, be used individually or mixed with one another. However, it is also possible to use mixtures of at least one organic phosphite and at least one thioether.
  • the polyisocyanate preparations are usually composed as follows:
  • Stabilizers S: primary stabilizer (S1): 0 to 1000 ppm, preferably 20 to 500 ppm and in particular 50 to 200 ppm, based on the weight of the polyisocyanate (P) and / or secondary stabilizer (S2): 0 to 1000 ppm , preferably 20 to 800 ppm and in particular 100 to 400 ppm, based on the weight of the polyisocyanate (P), with the proviso that the sum always yields 100% by weight.
  • S1 primary stabilizer
  • S2 secondary stabilizer
  • catalyst traces from the production of the polyisocyanate and optionally the catalyst used to stop the reaction, as well as residues of unreacted isocyanate can be contained in the preparation.
  • the polyisocyanate preparations according to the invention can be used for the production of polyurethanes and polyurethane paints, for example for one-component, two-component, radiation-curable or powder coating coatings for coating various substrates, such.
  • substrates such as wood, wood veneer, paper, cardboard, cardboard, textile, leather, nonwoven, plastic surfaces, glass, ceramics, mineral building materials, metals or coated metals.
  • the inventive polyisocyanate preparations can be used in particular in primers, fillers, (pigmented) topcoats, basecoats and clearcoats in the field of car repair or large-vehicle painting.
  • Such coating compositions are particularly suitable for applications in which particularly high application safety, outdoor weathering resistance, appearance, solvent resistance, chemical resistance and water resistance are required, such as in vehicle refinish and large vehicle painting.
  • Such coating compositions are suitable as or in exterior coatings, ie those applications that are exposed to daylight, preferably of building parts, interior coatings, coatings on (large) vehicles and aircraft and industrial applications, bridges, buildings, electricity pylons, tanks, containers, pipelines, Power plants, chemical plants, ships, cranes, piles, sheet piling, fittings, pipes, fittings, flanges, couplings, halls, roofs and structural steel.
  • the coating compositions of the invention are used as or in automotive clearcoat and topcoat (s).
  • Further preferred fields of application are can coating and coil coating. They are particularly suitable as primers, fillers, pigmented topcoats and clearcoats in the field of industrial, wood, automotive, in particular OEM paintwork, or decorative lacquering.
  • the coating compositions are particularly suitable for applications in which particularly high application safety, outdoor weathering resistance, appearance, scratch resistance, solvent resistance and / or chemical resistance are required. Due to their low color number and high color stability, they are of particular interest for coating compositions for clearcoats.
  • the inventively stabilized Polyisocyanatzurened show during storage a lower increase in viscosity than unstabilized Polyisocyanatzurened and a slightly improved color.
  • HDI 1,6-hexamethylene diisocyanate
  • a portion of the product was treated at room temperature (23 0 C) with 300 ppm methoxyacetic acid and stored at 50 0 C for 10 weeks. Another part was stored at 50 ° C without added acid.

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne des préparations de polyisocyanates stabilisées de façon nouvelle.
PCT/EP2007/063067 2006-12-04 2007-11-30 Préparations de polyisocyanate WO2008068197A1 (fr)

Applications Claiming Priority (2)

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EP06125330 2006-12-04
EP06125330.8 2006-12-04

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WO2008068197A1 true WO2008068197A1 (fr) 2008-06-12

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013060614A1 (fr) 2011-10-28 2013-05-02 Basf Se Compositions de durcisseurs de couleur stable contenant des polyisocyanates de diisocyanates (cyclo)aliphatiques
WO2013060809A2 (fr) 2011-10-28 2013-05-02 Basf Se Procédé de production de polyisocyanates de diisocyanates (cyclo)aliphatiques résistants à la floculation dans les solvants
US8802771B2 (en) 2010-11-22 2014-08-12 Dow Global Technologies Llc Two component polyurethane coating compositions comprising isocyanurate compositions from bis(isocyanatomethyl) cyclohexane and from aliphatic diisocyanates
US9617402B2 (en) 2011-10-28 2017-04-11 Basf Se Process for preparing polyisocyanates which are flocculation-stable in solvents from (cyclo)aliphatic diisocyanates
EP3560975B1 (fr) 2018-04-25 2021-04-07 Covestro Intellectual Property GmbH & Co. KG Polyisocyanates et antioxygènes hydrophilisés ioniques
EP3560976B1 (fr) 2018-04-25 2021-05-26 Covestro Intellectual Property GmbH & Co. KG Polyisocyanates hydrophilisés ionique et capteurs de radicaux libres et/ou décomposeur de peroxydes
WO2021151774A1 (fr) 2020-01-30 2021-08-05 Basf Se Compositions d'agent de durcissement à couleur stable comprenant des polyisocyanates hydrodispersables
CN114605287A (zh) * 2022-03-31 2022-06-10 中国科学院过程工程研究所 一种用于提高非光气xdi稳定性的复配稳定剂及其制备方法和应用
WO2022128925A1 (fr) 2020-12-18 2022-06-23 Basf Se Compositions de durcisseur de couleur stable contenant des polyisocyanates de diisocyanates (cyclo)aliphatiques

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0341516A1 (fr) * 1988-05-11 1989-11-15 Bayer Ag Polyisocyanates stabilisés
EP0643042A1 (fr) * 1993-09-13 1995-03-15 BASF Aktiengesellschaft Mélanges de polyisocyanates stables préparés par un procédé sans phosgène, un procédé pour leur préparation et leur emploi

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0341516A1 (fr) * 1988-05-11 1989-11-15 Bayer Ag Polyisocyanates stabilisés
EP0643042A1 (fr) * 1993-09-13 1995-03-15 BASF Aktiengesellschaft Mélanges de polyisocyanates stables préparés par un procédé sans phosgène, un procédé pour leur préparation et leur emploi

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8802771B2 (en) 2010-11-22 2014-08-12 Dow Global Technologies Llc Two component polyurethane coating compositions comprising isocyanurate compositions from bis(isocyanatomethyl) cyclohexane and from aliphatic diisocyanates
WO2013060614A1 (fr) 2011-10-28 2013-05-02 Basf Se Compositions de durcisseurs de couleur stable contenant des polyisocyanates de diisocyanates (cyclo)aliphatiques
WO2013060809A2 (fr) 2011-10-28 2013-05-02 Basf Se Procédé de production de polyisocyanates de diisocyanates (cyclo)aliphatiques résistants à la floculation dans les solvants
WO2013060809A3 (fr) * 2011-10-28 2014-01-30 Basf Se Procédé de production de polyisocyanates de diisocyanates (cyclo)aliphatiques résistants à la floculation dans les solvants
US9617402B2 (en) 2011-10-28 2017-04-11 Basf Se Process for preparing polyisocyanates which are flocculation-stable in solvents from (cyclo)aliphatic diisocyanates
EP3560975B1 (fr) 2018-04-25 2021-04-07 Covestro Intellectual Property GmbH & Co. KG Polyisocyanates et antioxygènes hydrophilisés ioniques
EP3560976B1 (fr) 2018-04-25 2021-05-26 Covestro Intellectual Property GmbH & Co. KG Polyisocyanates hydrophilisés ionique et capteurs de radicaux libres et/ou décomposeur de peroxydes
WO2021151774A1 (fr) 2020-01-30 2021-08-05 Basf Se Compositions d'agent de durcissement à couleur stable comprenant des polyisocyanates hydrodispersables
WO2022128925A1 (fr) 2020-12-18 2022-06-23 Basf Se Compositions de durcisseur de couleur stable contenant des polyisocyanates de diisocyanates (cyclo)aliphatiques
CN114605287A (zh) * 2022-03-31 2022-06-10 中国科学院过程工程研究所 一种用于提高非光气xdi稳定性的复配稳定剂及其制备方法和应用

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