WO2024165361A1 - Préparation de polyisocyanates contenant des groupes iminooxadiazinedione et leur utilisation - Google Patents

Préparation de polyisocyanates contenant des groupes iminooxadiazinedione et leur utilisation Download PDF

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WO2024165361A1
WO2024165361A1 PCT/EP2024/052076 EP2024052076W WO2024165361A1 WO 2024165361 A1 WO2024165361 A1 WO 2024165361A1 EP 2024052076 W EP2024052076 W EP 2024052076W WO 2024165361 A1 WO2024165361 A1 WO 2024165361A1
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process according
proceeding
group
cyclo
diisocyanate
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PCT/EP2024/052076
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English (en)
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Frederic Lucas
Sabrina Kraeh
Oliver Trapp
Max Julian SIEBERT
Diego Raimondo STAGNO
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Basf Se
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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
    • C08G18/06—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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7875—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
    • C08G18/7887—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring having two nitrogen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/30—Only oxygen atoms
    • C07D251/34—Cyanuric or isocyanuric esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D273/00—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00
    • C07D273/02—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00 having two nitrogen atoms and only one oxygen atom
    • C07D273/04—Six-membered rings
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate groups

Definitions

  • the present invention relates to a novel process for preparing polyisocyanates containing iminooxadiazinedione groups by a partial trimerization of (cyclo)aliphatic diisocyanate in the presence of at least one oligomerization catalyst and at least one fluorinated alcohol having not more than one hydrogen atom at the alpha-position for each hydroxyl group and to the use of the thus obtainable polyisocyanates containing iminooxadiazinedione groups as a polyisocyanate component in polyurethane coatings.
  • EP-A 962455, 962454, 896009, 798299, 447074, 379914, 339396, 315692, 295926 and 235388 disclose processes which lead to products with a high proportion of iminooxadiazinedione groups (asymmetric isocyanate trimers).
  • Suitable catalysts are, for example, fluoride or poly(hydrogen)fluoride [F- x (HF) m ], preferably with quaternary phosphonium cations as counterions, wherein m is a number between 0.001 till 20, preferably 0.5 till 5, very preferably 1.
  • EP2976373 discloses a catalyst kit comprising a trimerization catalyst for the asymmetric trimerization of polyisocyanates and a catalyst poison for the trimerization catalyst.
  • Possible catalyst poisons i.e. , stoppers, are quite generally anhydrous acids having a pKa value below 3.2.
  • Catalyst should be employable over a wide temperature range, should have a good solubility in the reaction mixture and should have less tendency to decompose in unwished components
  • This object is achieved by a process for preparing polyisocyanates containing iminooxadiazinedione groups by at least reacting at least one (cyclo)aliphatic diisocyanate in the presence of at least one oligomerization catalyst and at least one fluorinated alcohol having not more than one hydrogen atom at the alpha-position for each hydroxyl group.
  • a further object of the present invention relates to the use of the thus obtainable polyisocyanates containing iminooxadiazinedione groups as a polyisocyanate component in polyurethane coatings.
  • Oligomerization catalysts may be salts known to be catalytically active with respect to isocyanates. Preference is being given to salts containing an anion selected from the group of alkoxide, fluoride, hydrogen polyfluoride of the formula n [F ’ (HF) m ], hydrogen sulfate, cyanide, hydroxide, alkanoate, carboxylate, carbonate, heterocycles having at least one negatively charged nitrogen atom in the ring, especially azolate, imidazolate, triazolate, tetrazolate, or mixtures of these.
  • salts containing an anion selected from the group of alkoxide, fluoride, hydrogen polyfluoride of the formula n [F ’ (HF) m ], hydrogen sulfate, cyanide, hydroxide, alkanoate, carboxylate, carbonate, heterocycles having at least one negatively charged nitrogen atom in the ring, especially azolate, imidazolate, triazolate, tetrazolate,
  • Especially preferred anions are selected from the group of carboxylates, hydroxides, alkanoates, alkoxides and carbonates.
  • Oligomerization catalysts could be also organic bases such as HMDS (hexamethyldisilazane), tributylphosphine and dimethylaminopyridine
  • Suitable cations may in principle be any species known to be catalytically active with respect to isocyanates. These cations may ensure good solubility in the isocyanate medium. Preference is being given to tetraalkylammonium, tetraalkylphosphonium, guanidinium, sulfonium, imidazoli- um, benzotriazolium and pyridinium. Especially preferred are cations according to formula (II) wherein
  • X is nitrogen or phosphorus
  • R 1 , R 2 , R 3 and R 4 may each independently be the same or different and are each a straightchain or branched optionally substituted, preferably not substituted Ci- to C2o-alkyl group, an optionally substituted, preferably not substituted Cs- to Ci2-cycloalkyl group, an optionally substi- tuted, preferably not substituted C7- to Cw-aralkyl group, or an optionally substituted, preferably not substituted Ce-Cw-aryl group, or two or more of the R 1 to R 4 radicals together form a 4-, 5- or 6-membered alkylene chain or, together with a nitrogen atom, form a 5- or 6-membered ring which may also contain an additional nitrogen or oxygen atom as a bridge member, or together form a multimembered, preferably six-membered, polycyclic system, preferably bicyclic system, which may also contain one or more additional nitrogen atoms, oxygen atoms or oxygen and nitrogen atoms as bridge members.
  • Ci- to C2o-alkyl group is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, nonyl, dodecyl, eicosyl, decyl, 1 ,1 -di methyl propyl, 1 ,1 -dimethylbutyl or 1 ,1 ,3,3-tetramethylbutyl, an optionally substituted C5- to Ci2-cycloalkyl group is cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl
  • Ce- to Ci2-aryl optionally interrupted by one or more oxygen atoms and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups or substituted by functional groups, aryl, alkyl, aryloxy, alkyloxy, halogen, heteroatoms and/or heterocycles is, for example tolyl, xylyl, 4- di-phenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dime- thyl-phenyl, trimethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, tert-butylphenyl, do- decyl-phenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropyl
  • R 1 to R 4 are in each case independently methyl, ethyl, 2-hydroxyethyl, 2-hydroxy- propyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, phenyl, a- or p-naphthyl, benzyl, cyclopentyl or cyclohexyl.
  • R 1 to R 4 radicals may be, for example, 1 ,4-butylene, 1 ,5-pentylene, 3-oxa-1 ,5-pentylene, 3-aza-1 ,5-pentylene or 3-methyl-3-aza-1 ,5-pentylene.
  • R 1 to R 4 radicals are each independently methyl, ethyl, 2-hydroxyethyl, 2-hydroxy- propyl, propyl, isopropyl, n-butyl, tert-butyl, hexyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, phenyl and benzyl, particular preference is given to methyl, ethyl, n-butyl, octyl, decyl, dodecyl, phenyl and benzyl, very particular preference is given to methyl, ethyl, n-butyl, octyl, decyl, dodecyl and in particular methyl, n-butyl, octyl, decyl and dodecyl.
  • radicals R 1 to R 4 are hydrocarbons without any atoms other than carbon or hydrogen.
  • ammonium cations are tetraoctylammonium, tetramethylammonium, tetraethylammonium, tetra-n-butylammonium, trimethylbenzylammonium, triethylbenzylammonium, tri-n-butylbenzylammonium, trimethylethylammonium, trimethyloctylammonium, trimethyldecylammonium, trimethyldodecylammonium, benzyldimethyloctylammonium, benzyldimethyldecylammonium, benzyldimethyldodecylammonium, tri-n-butylethylammonium, triethylmethylammonium, tri-n-butylmethylammonium, diisopropyldiethylammonium, diisopropylethylme- thylammonium, diisoprop
  • Preferred alkylammonium ions are tetraoctylammonium, tetramethylammonium, tetraethylammonium and tet- ra-n-butylammonium, particular preference is given to tetramethylammonium and tetraethylammonium and very particular preference is given to tetra-n-butylammonium.
  • Y is a linear or branched C2-C20 segment which is substituted by a hydroxyl group in the 2 position to the charge-bearing nitrogen atom and optionally bears further substituents and is optionally interrupted by heteroatoms from the group of oxygen, sulfur, nitrogen and aromatic rings and optionally has further rings
  • the N-bonded substituents R5 and R6 are either independently identical or different, substituted or unsubstituted, optionally branched, aliphatic C1-C20 radicals, aromatic C6-C20 radicals or araliphatic C7-C20 radicals or the N-bonded substituents R5 and R6 form a ring segment X with one another for which the same or different definition given above for Y is applicable, with the proviso that X has a hydroxyl group as substituent in the 2 position to the charge-bearing nitrogen atom or
  • the sum of carbon atoms in the radicals R 1 to R 4 is at least 11 , particularly preferred at least 13, very particularly preferred at least 15 .
  • one radical out of the four radicals R 1 to R 4 is a substituted Ci-C2o-alkyl the other three radicals being hydrocarbons.
  • ammonium cations are 2-hydroxyethyl trimethylammonium, 2-hydroxypropyl trimethylammonium, 2-hydroxyethyl triethylammonium, 2-hydroxypropyl triethylammonium, 2-hydroxyethyl tri-n-butylammonium, 2-hydroxypropyl tri-n-butylammonium, 2-hydroxyethyl dimethyl benzyl ammonium, 2-hydroxypropyl dimethyl benzyl ammonium, N-(2-hydroxyethyl),N- methyl morpholinium, N-(2-hydroxypropyl),N-methyl morpholinium or 3-hydroxy quinuclidine, preferably 2-hydroxyethyl trimethylammonium, 2-hydroxypropyl trimethylammonium, 2-hydroxy- ethyl dimethyl benzyl ammonium and 3-hydroxy quinuclidine, very preferably 2-hydroxyethyl trimethylammonium and 2-hydroxypropyl trimethylammonium and particularly preferably 2-hyl
  • Ammonium ions containing ring systems are, for example, methylated, ethylated or benzylated piperazines, piperidines, morpholines, quinuclidines or triethylenediamines.
  • Preferred phosphonium ions are tetramethyl phosphonium, tetrabutyl phosphonium, tetraoctyl phosphonium, and tetradecyl phosphonium, trihexyl(tetradecyl)phosphonium, triisobu- tyl(methyl)phosphonium, tributyl(tetradecyl)phosphonium, tri-n-butylethylphosphonium, tribu- tyl(octyl)phosphonium, tetra-n-butylphosphonium and mixtures thereof.
  • preferred is tetra-n-butyl phosphonium.
  • Tetrabutyl phosphonium, tetrabutyl ammonium and trimethylbenzyl ammonium are the most preferred cations.
  • the inventive process is preferably carried out at a temperature of from 20° C to 120° C, preferably 40-90 °C, very preferably 50-80 °C.
  • oligomerization catalysts which can be used in accordance with the invention can be prepared by known processes, e.g., as described in EP1727842.
  • the fluorinated alcohol having not more than one hydrogen atom at the alpha-position for each hydroxyl group.
  • the fluorinated alcohol may contain one or more hydroxyl groups, preferably one or two hydroxyl groups and more preferably one hydroxyl group.
  • the fluorinated alcohol is a monoalcohol.
  • the term "monoalcohol” means a compound containing one aliphatically, cycloaliphatically, araliphatically, or aromatically bound hydroxyl group.
  • the fluorinated alcohol may contain one or more fluoroalkyl groups.
  • Fluoroalkyl groups are alkyl groups in which one or more hydrogens have been substituted for fluorine.
  • the fluorine content of the fluorinated alcohol is at least 30 wt%.
  • the fluorinated alcohol contains not more than one hydrogen atom at the alphaposition for each hydroxyl group and no additional C-H bond.
  • the molecular weight of the fluorinated alcohol is less than 600 g/mol, preferably less than 400 g/mol.
  • the fluorinated alcohol is selected from the group consisting of 1 ,1 , 1 ,3, 3, 3- hexafluoro-2-propanol (HFIP), tetrahydroxy-1 ,4-quinon, 2, 3, 4, 5, 6, 2', 3', 4', 5', 6'- decafluorobenzhydrol, 1 ,3-Difluoro-2-propanol, 1 ,1 ,3,3-tetrafluoro-2-propanol, 1 , 1 ,3,3- tetrafluoro-2-propanol, 2,2,3,3-tetrafluorocyclopropanol, 1 ,1 ,1 ,3,3,4,4,5,5,5-decafluoro-2- pentanol, 1 ,3,3-trifluoro-2-butanol, 1 ,1 ,1 ,3-tetrafluoro-3-methyl-2-butanol, 1 , 3,4,4, 4-pentafluoro
  • fluorinated alcohols that are fully fluorinated.
  • the fluorinated alcohols are used in the process according to the invention in an amount of from 0.01wt% to 20 wt%, preferably from 0.02wt% to 10 wt%, very preferably from 0.05wt% to 8 wt%, most preferably from 0.1 wt% to 6 wt% based on the (cyclo)aliphatic diisocyanates.
  • the oligomerization catalyst may be used in substance, as solution or as suspension.
  • the oligomerization catalyst is dissolved in a solvent before the addition to the (cyclo)aliphatic diisocyanate.
  • the oligomerization catalyst is dissolved in the fluorinated alcohol before the addition to the (cyclo)aliphatic diisocyanate.
  • a solution having a dilution of generally 99 - 20%, preferably 99 - 50%, more preferably 99 - 70% and most preferably 99 - 80% by weight catalyst content is established.
  • solvents are those in which the catalyst has a good solubility.
  • Preferred solvents are alcohols, toluene, xylene, cyclic ethers, carboxylic esters and ketones or mixtures.
  • Very preferred solvents are alcohols comprising methanol, isopropanol or containing at least 6 carbon atoms, more preferred 2-ethyl hexan-1-ol and 2-propyl heptan-1-ol.
  • the fluorinated alcohol is mixed with the (cyclo)aliphatic diisocyanate before the addition of the oligomerization catalyst.
  • the oligomerization catalysts used may also be mixtures with other known oligomerization catalysts, and these may be mixed in broad ratios, for example in ratios of from 90:10 to 10:90, preferably from 80:20 to 20:80 and more preferably from 60:40 to 40:60.
  • the oligomerization catalysts are appropriately used in very small effective amounts which can be determined experimentally in a simple manner.
  • the oligomerization catalysts are used in the process according to the invention in an amount of from 1 ppm to 1 %, preferably from 20 ppm to 500 ppm, very preferably from 50 ppm to 500 ppm, most preferably from 50 ppm to 300 ppm based on the (cyclo)aliphatic diisocyanates.
  • the process according to the invention is appropriately carried out at a temperature in the range from 20 to 120°C and reaction times of 10 min to 6 hours, preferably of from 20 min to 3 hours, more preferably of from 20 min to 2 hours.
  • a temperature in the range from 20 to 120°C and reaction times of 10 min to 6 hours, preferably of from 20 min to 3 hours, more preferably of from 20 min to 2 hours.
  • discoloration of the polyisocyanates containing iminooxadiazinedione groups may occur, for example in the case of prolonged reaction times.
  • the temperature is preferably such that the reactivity of the catalyst is sufficiently high.
  • the temperature is preferably such that the share of iminooxadiazinedione versus standard isocyanurate is not dropping too far.
  • the optimum temperature range is given above.
  • the oligomerization may be carried out continuously, semicontinuously or batchwise, preferably continuously.
  • the isocyanate to be trimerized is at least partly, preferably fully, initially charged and the at least one catalyst is added slowly and/or in portions, then brought to the desired reaction temperature, and the remainder of the catalyst is added, if appropriate in portions.
  • An alternative preparation variant proceeds as follows: a batchwise process is performed in a stirred reactor.
  • the mixture of diisocyanate and catalyst is initially charged typically at approx. 40°C.
  • the oligomerization is initiated by increasing the temperature of the reaction mixture to from 50 to 120°C, preferably to from 50 to 80°C.
  • the catalyst may also be metered in after the diisocyanate has attained the temperature necessary for the reaction.
  • the oligomerization is generally exothermic.
  • the catalyst is preferably dissolved in a suitable solvent and to use it in this form.
  • the continuous oligomerization may appropriately be carried out continuously in a reaction coil with continuous, simultaneous metering of diisocyanate and the catalyst at from 40 to 120°C and within from 30 seconds to 4 hours.
  • a reaction coil having a small diameter leads to the achievement of high flow rates and consequently good mixing. It is also advantageous to heat the diisocya- nate/catalyst mixture to from approx. 50 to 60°C before entry into the reaction coil. For more precise metering and optimal mixing of the catalyst, it is also advantageous to dissolve the catalyst in a suitable solvent.
  • suitable solvents are those in which the catalyst has a good solubility.
  • the continuous trimerization may also be carried out in a multiple reactor cascade.
  • the reaction is stopped in the last reactor of the cascade or in e.g., a static mixer.
  • the reaction is carried out under a gas or gas mixture which is inert under the reaction conditions, for example those having an oxygen content of below 2%, preferably below 1%, more preferably below 0.5% by volume, most preferably no oxygen.
  • a gas or gas mixture which is inert under the reaction conditions, for example those having an oxygen content of below 2%, preferably below 1%, more preferably below 0.5% by volume, most preferably no oxygen.
  • oxygen content of below 2%, preferably below 1%, more preferably below 0.5% by volume, most preferably no oxygen.
  • nitrogen, argon, nitrogen-noble gas mixtures particular preference is given to nitrogen.
  • the oligomerization reaction may be ended, for example, by deactivating the oligomerization catalyst.
  • the catalyst poison contains at least one acid having a pKa value below 4.0, preferably below 2.0.
  • Suitable catalyst poisons are inorganic acids or acid esters, for example hydrogen chloride, phosphorous acid, dialkyl phosphorous acids, preferably bis-2-ethyl-hexyl phosphorous acid and bis-butyl-phosphorous acid, phosphoric acid, carbonyl halides, preferably acetyl chloride or benzoyl chloride, sulfonic acids, or esters, preferably methanesulfonic acid, p-toluene sulfonic acid, methyl, or ethyl p-toluene sulfonate, p-dodecyl benzenesulfonic acid, m-chloroperbenzoic acid.
  • inorganic acids or acid esters for example hydrogen chloride, phosphorous acid, dialkyl phosphorous acids, preferably bis-2-ethyl-hexyl phosphorous acid and bis-butyl-phosphorous acid, phosphoric acid, carbonyl halides,
  • the catalyst poison acid ester containing phosphorus or sulfur very preferably the catalyst poison is para-toluene sulfonic acid or p-dodecyl benzenesulfonic acid.
  • the catalyst poisons may, based on the oligomerization catalysts, be used in equivalent or excess amounts, and the smallest effective amount, which can be determined experimentally, is preferred simply for economic reasons.
  • the catalyst poison is used in a ratio to the oligomerization catalyst of 0.7:1 - 1.5:1 mol/mol and very particularly preferably 0.9:1 - 1.2:1 mol/mol, most preferably 1 :1.
  • the addition of the catalyst poison depends upon the type of the catalyst poison.
  • liquid catalyst poisons such as dibutylphosphate or di-2-ethylhexyl-phosphate may be added as a solution in a solvent.
  • Solid catalyst poisons are preferably added in diluted form as a solution or suspension, preferably as a solution.
  • Solvents preferably are reactive towards NCO groups.
  • alcohols are used as solvents.
  • the alcohol may be a primary, secondary, or tertiary alcohol.
  • Primary alcohols are for example 2-ethyl-1-butanol, 2-ethyl-hexane-1-ol; n-octane- 1-ol; nonane-1-ol; 2-n-propyl-n-heptane-1-ol; n- decane-1-ol; iso-decane-1 -ol [C9-C11 -alcohol mixture (C10 rich; “iso-decane-ol)]; 2-butyl- octane-1-ol; undecane-1-ol; iso-tridecane-1 -ol; 2-hexyl-decane-ol, dodecane-1-ol, 1-tridecyl alcohol, tetradecane- 1-ol, pentadecyl alcohol, hexadecyl alcohol, octadecyl alcohol. Alcohols
  • Secondary alcohols are for example 3-decane-ol or 4-decane-ol.
  • the alcohol is a primary alcohol.
  • Preferred alcohols are 2-ethyl hexane-ol and 2-n- propyl heptane- 1-ol, very preferred 2-ethyl-hexane-1-ol.
  • the alcohol may be monofunctional, difunctional or trifunctional.
  • Difunctional alcohols are for example 2-ethyl-1,3-hexane-diol, neopentyl glycol, 1,6- hexane-diol, 1,7-heptane-diol, 1,8-octa- ne-diol, 1,9-nonane-diol and 1 ,10-decane-diol; branched aliphatic diols such as 3-methyl[1]1,5- pentane-diol, 2-methyl-1,8-octane-diol, and 2,2-diethyl-1,3-propane-diol; cyclic aliphatic diols such as 1,2-cyclohex[1]ane-diol, 1,4-cyclohexane-diol, 1 ,2-cyclohexane-dimethanol, 1,4-
  • primary alcohols and secondary alcohols are possible as well, preferably the mixture of 2-ethyl-hexane-1-ol or 2-n-propyl-n-heptane-1-ol with 2-ethyl-1,3-hexane-diol, preferably the first one.
  • the alcohol is monofunctional.
  • the alcohol may be linear or branched, preferably the alcohol is branched.
  • the alcohol may be aliphatic or cycloaliphatic.
  • a cyclic alcohol may be cyclo hexane-diol or cy- clohexane-dimethanol.
  • Preferably the alcohol is aliphatic.
  • the alcohols may be alkoxylated, for example, ethoxylated, propoxylated or butoxylated. Preferably the alcohol is not alkoxylated.
  • Alkoxylated alcohols may be for example triethyleneglycol, dipropyleneglycol, 2-butoxyethanol 2-butoxypropanol, triethyleneglycol monoethylether, diethyleneglycol monopropylether, ethyleneglycol monopentylether, dipropyleneglycol monoethylether, propyleneglycol monopropylether, propyleneglycol monopentylether, poly-THF as poly THF 250, poly-THF 650, poly-THF 1000, poly-THF 1800, poly-THF 1000 poly-THF 2000, poly-THF 2900, 2,2,4-trimethyl-1 ,3- pentane-diol, 1,4-cyclohexane-dimethanol, 1,3-cyclohexane-dimethanol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
  • the alcohol may be saturated or unsaturated.
  • Unsaturated alcohols may be for example cis-9- hexadecenol or c/s,c/s-9,12-octadecadien-1-ol.
  • Preferably the alcohol is saturated.
  • the solution may contain further solvents, e.g., further alcohols, toluene, xylene, cyclic ethers, carboxylic esters and ketones or mixtures thereof. In the preferred form, only alcohol is used.
  • the alcohols used may also be mixtures of alcohols.
  • the catalyst poisons are generally added at ambient temperature but might be preheated to the reaction temperature.
  • the polyisocyanates containing iminooxadiazinedione groups which are prepared by the process according to the invention may be freed of any solvent or diluent present and/or preferably of excess, unconverted (cyclo)aliphatic diisocyanates in a manner known per se, for example by thin-film distillation at a temperature of from 100 to 180°C, if appropriate under reduced pressure, if appropriate additionally while passing through inert stripping gas, or extraction, so that the polyisocyanates containing iminooxadiazinedione groups are obtainable with a content of monomeric diisocyanates of, for example, below 1.0% by weight, preferably below 0.5% by weight, more preferably below 0.3% by weight, even more preferably below 0.2% by weight and in particular not more than 0.1% by weight.
  • the polyisocyanates containing iminooxadiazinedione groups are suitable, for example, for coatings, preparing PU foams, cellular or compact elastomers, casting
  • the polyisocyanates containing iminooxadiazinedione groups are suitable, for example, for preparing PU foams, cellular or compact elastomers, casting compositions and adhesives.
  • the monomer-free and monomer- containing polyisocyanates containing iminooxadiazinedione groups may also be modified in a manner known per se by introducing, for example, urethane, allophanate, urea, biuret, isocy- anurate and/or carbodiimide groups, and/or the isocyanates may be capped with suitable capping agents.
  • the polyisocyanates containing iminooxadiazinedione groups have a content of iminooxadiazinedione groups of at least 25 mol%, preferably at least 30 mol%, based on the total weight of polyisocyanates.
  • the process according to the invention can be used to oligomerize any organic diisocyanates having aliphatic, cycloaliphatic, or aliphatic and cycloaliphatic isocyanate groups or mixtures thereof.
  • Suitable aliphatic diisocyanates have advantageously from 3 to 16 carbon atoms, preferably from 4 to 12 carbon atoms, in the linear or branched alkylene radical, and suitable cycloaliphatic diisocyanates have advantageously from 4 to 18 carbon atoms, preferably from 6 to 15 carbon atoms, in the cycloalkylene radical. Examples include:
  • the (cyclo)aliphatic diisocyanates used are preferably hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI), 5-isocyanato-1-(isocyanatomethyl)- 1 ,3,3-trimethylcyclohexane (IPDI), 2-methyl pentane 1 ,5-diisocyanate, 2,4,4-trimethyl-1 ,8- hexane diisocyanate, 2,2,4-trimethyl-1 ,6-hexane diisocyanate and 4-isocyanatomethyl-1.8- octane, very preferably hexamethylene 1 ,6-diisocyanate (HDI) and 1 ,5-diisocyanatopentane (PDI).
  • HDI hexamethylene diisocyanate
  • PDI pentamethylene diisocyanate
  • IPDI 5-isocyanato-1-(isocyanatomethyl)- 1 ,
  • oligomerization catalysts also catalyze the trimerization of aromatic isocyanates but are preferred for (cyclo)aliphatic isocyanates.
  • the inventive process may be used for the oligomerization of (cyclo)aliphatic diisocyanates prepared by any processes, for example by a phosgene-free process route or one proceeding with the use of phosgene.
  • the (cyclo)aliphatic diisocyanates which can be used in accordance with the invention may be prepared by any processes, for example by phosgenating the appropriate diamines and thermally dissociating the dicarbamoyl chlorides formed as an intermediate.
  • (Cyclo)aliphatic diisocyanates prepared by phosgene-free processes do not contain any chlorine compounds as byproducts and therefore contain, because of the preparation, a fundamentally different byproduct spectrum.
  • the (cyclo)aliphatic diisocyanates which can be used in the process according to the invention and are obtainable by a phosgene-free process and especially by thermal dissociation of (cycloaliphatic dicarbamic esters are not restricted, and preference is given in particular to selecting diisocyanates obtainable by thermal dissociation of (cyclo)aliphatic dicarbamic esters from the group of hexamethylene 1 ,6-diisocyanate (HDI), 1 ,5-diisocyanatopentane (PDI), 2-butyl-2- ethylpentamethylene 1 ,5-diisocyanate and 1-isocyanato-3-isocyanatomethyl-3,5,5- trimethylcyclohexane.
  • HDI hexamethylene 1 ,6-diisocyanate
  • PDI 1 ,5-diisocyanatopentane
  • isocyanate monomers which have a total chlorine content of 800 ppm by weight or less, preferably 400 ppm by weight or less, most preferably 200 ppm by weight or less.
  • isocyanate monomers which have a hydrolyzable chlorine content of 100 ppm by weight or less, more preferably 50, 25, respectively 20 ppm by weight or less.
  • Polyisocyanates containing iminooxadiazinedione groups and prepared by these process variants are suitable preferentially for producing polyurethane coatings, for example textile and leather coatings, for polyurethane dispersions and adhesives, and find use in particular as a polyisocyanate component in one- and two-component polyurethane systems for high-grade, weather-resistant polyurethane coatings. These preferably are high-solids or water borne coatings.
  • Polyisocyanates containing iminooxadiazinedione groups and prepared by these process variants may be used in combination with aspartic esters.
  • Coating formulations obtained are suitable for coating substrates such as wood, wood veneer, paper, cardboard, paperboard, textile, film, leather, nonwoven, plastics surfaces, glass, ceramic, mineral building materials, such as molded cement blocks and fiber-cement slabs, or metals, which in each case may optionally have been precoated or pretreated.
  • substrates such as wood, wood veneer, paper, cardboard, paperboard, textile, film, leather, nonwoven, plastics surfaces, glass, ceramic, mineral building materials, such as molded cement blocks and fiber-cement slabs, or metals, which in each case may optionally have been precoated or pretreated.
  • Coating compositions of this kind are suitable as or in interior or exterior coatings, i.e., in those applications where there is exposure to daylight, preferably of parts of buildings, coatings on (large) vehicles and aircraft, and industrial applications, utility vehicles in agriculture and construction, decorative coatings, bridges, buildings, power masts, tanks, containers, pipelines, power stations, chemical plants, ships, cranes, posts, sheet piling, valves, pipes, fittings, flanges, couplings, halls, roofs, and structural steel, wood, furniture, windows, doors, woodblock flooring, can coating and coil coating, for floor coverings, such as in parking levels or in hospitals and in particular in automotive finishes, as OEM and refinish application.
  • ppm and percentage data used in this document relate, unless stated otherwise, to percentages by weight and ppm by weight.
  • F-Alcohol 1 Hexafluoro-2-propanol (HFIP)
  • Viscosity 660 mPa.s
  • Viscosity 1140 mPa.s

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  • Organic Chemistry (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

L'invention concerne un procédé de préparation de polyisocyanates contenant des groupes iminooxadiazinedione, consistant à faire réagir au moins un diisocyanate (cyclo)aliphatique en présence d'au moins un catalyseur de gomérisation et d'au moins un alcool fluoré ne comportant pas plus d'un atome d'hydrogène en position alpha pour chaque groupe hydroxyle.
PCT/EP2024/052076 2023-02-09 2024-01-29 Préparation de polyisocyanates contenant des groupes iminooxadiazinedione et leur utilisation WO2024165361A1 (fr)

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EP0235388A2 (fr) 1985-12-28 1987-09-09 MITSUI TOATSU CHEMICALS, Inc. Procédé pour la préparation de polymères résistant à la chaleur
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