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WO2020016117A1 - Procédé de préparation de polyisocyanates oligomères - Google Patents

Procédé de préparation de polyisocyanates oligomères Download PDF

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Publication number
WO2020016117A1
WO2020016117A1 PCT/EP2019/068781 EP2019068781W WO2020016117A1 WO 2020016117 A1 WO2020016117 A1 WO 2020016117A1 EP 2019068781 W EP2019068781 W EP 2019068781W WO 2020016117 A1 WO2020016117 A1 WO 2020016117A1
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Prior art keywords
solvent system
catalyst
hdi
solvent
phase
Prior art date
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German (de)
English (en)
Inventor
Thomas Ernst MÜLLER
Christoph Gürtler
Reinhard Halpaap
Frank Richter
Pedro SA GOMES
Carla Quarantelli
Walter Leitner
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Covestro Deutschland AG
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Covestro Deutschland AG
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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
    • C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing isocyanurate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
    • C08G18/168—Organic compounds
    • 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
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates

Definitions

  • the present invention relates to a process for the catalyzed oligomerization of di- or polyfunctional monomers (hereinafter: monomers) to form an oligomeric polyisocyanate in the presence of a catalyst and a two-phase solvent system pair comprising a first solvent system and a second solvent system.
  • monomers di- or polyfunctional monomers
  • the oligomerization of diisocyanates such as especially hexamethylene diisocyanate (HDI) to low molecular weight oligomers is characterized by a classic consecutive reaction sequence in which a diisocyanate monomer molecule (A) with another monomer molecule (with uretdione formation, ideal structure: A2) or two other monomer molecules (under isocyanurate - and / or hninooxadiazindione Guess, ideal structures A 3 ) reacts.
  • US 5,298,431 describes a multistage process for isolating a cyclotrimerized isocyanate from a mixture comprising this cyclotrimerized isocyanate and higher
  • the method comprises the steps of: (a) contacting the mixture with a liquid solvent to obtain a solvent-containing mixture; (b) extracting the solvent-containing mixture by liquid-liquid extraction to separate the mixture into an extract and a residue, the extract being a
  • the highly purified polyisocyanates are well suited for the production of foams, elastomers, adhesives, lacquers and paints.
  • EP 0 550 908 A2 relates to a process for the isolation of isocyanate isomers in pure or enriched form from at least two polyisocyanate mixtures containing isocyanate isomers by liquid-liquid extraction using a two-phase system consisting of a non-polar and a polar phase containing hydrogen halide.
  • the isomer separation on the MDI with its isomers 4,4'- and 2,4'-MDI is specifically described.
  • DE 10 2004 06 0131 A1 relates to a process for the preparation of polyisocyanates from diisocyanates and their use.
  • the process is a continuous process for the partial trimerization of (cyclo) aliphatic isocyanates in the presence of at least one catalyst and is distinguished by the fact that the process is carried out at least partially in at least two back-mixed reaction zones.
  • the reaction was previously stopped after partial conversion by deactivating the catalyst and the HDI monomer was separated from the product mixture by means of vacuum rectification and returned to the reactor.
  • the higher the conversion in the oligomerization reaction the greater the proportion of higher oligomers. Due to the distillative step, such a process is associated with a high energy input and with a thermal load on the process products and starting materials.
  • the object of the present invention is to provide a process for isocyanate oligomerization in which the desired oligomeric polyisocyanate can be obtained in a higher degree of purity, that is to say with a higher proportion of ideal structure than comparable products obtained by prior art processes.
  • a process for the preparation of oligomeric polyisocyanates comprising the step of reacting an isocyanate to an oligomeric polyisocyanate in the presence of a catalyst, wherein the reaction is carried out in the presence of a two-phase solvent system pair comprising a first solvent system and a second solvent system, the first solvent system being a linear, branched or cyclic, optionally partially or perfluorinated alkane (preferably all isomeric pentanes, hexanes, heptanes, octanes, Deans, undecanes, dodecanes, tridecanes, tetradecanes, pentadecanes, hexadecanes, cyclohexane, tetralin and any mixtures with one another), chloroaromatics and / or bromoaromatics (such as p-dibromobenzene) and the second solvent system comprises a
  • the solvent system pair forms two phases if a phase boundary between the two liquid phases can be seen with the naked eye.
  • the first and second solvent systems each contain a solvent such that the two pairs of solvent systems show a miscibility gap within a certain temperature range.
  • the first and second solvent systems can each be present as mixtures of solvents, so that the two pairs of solvent systems show a miscibility gap within a certain temperature range.
  • the more polar, second solvent system has a miscibility gap with the nonpolar first solvent system.
  • the isocyanates are oligomerized. This is preferably a trimerization and particularly preferably an isocyanurate and / or iminooxadiazinedione formation.
  • Suitable starting materials for the oligomerization are, for example, hexamethylene diisocyanate (HDI), 1,8-octane diisocyanate, 4-isocyanatomethyl-1, 8-octane diisocyanate, 1.10-decane diisocyanate, 1.11-undecane diisocyanate, 1.12-dodecane diisocyanate, 2-methyl 1,5-diisocyanatopentane, 1,3- and 1,4-cyclohexane diisocyanate, norbornane diisocyanate, 1,3- and 1,4-bisisocyanatomethylcyclohexane, 1,3- and 1,4-bis (isocyanatoethyl) cyclohexane, 2,4- and 4,4-diisocyanatodicyclohexyl methane, 1-isocyanato-l-methyl-4 (3) -isocyanatomethylcyclohexane (IMCI), iso
  • monoisocyanates such as e.g. Methyl, ethyl, 1- and / or 2-propyl, butyl (all isomers), pentyl (all isomers) and / or hexyl isocyanates (all isomers) and their higher homologues individually or in any mixture with one another and with the The above di- and triisocyanates may be included.
  • the starting material in the first solvent system and the more polar oligomeric polyisocyanate accumulate in the second solvent system.
  • little starting material is present in the second solvent system and is therefore missing as a reaction partner for the further reaction of the oligomeric polyisocyanates to undesired higher oligomers.
  • isocyanate trimerization after the reaction of a diisocyanate monomer molecule (A) with two other monomer molecules to form an isocyanurate (A3), further isocyanate (A) is missing to form higher molecular weight oligomers (A5 + ).
  • the catalyst is present to a greater extent in the first solvent system than in the second solvent system.
  • Suitable catalysts can be identified by determining their partition coefficients in the desired solvent system pair and synthesized in such a way that a high solubility in the first solvent system is guaranteed. Due to the fact that the catalyst is primarily in the non-polar first solvent system, it is not available or is only available to a limited extent for the catalysis of the further reaction of the oligomeric polyisocyanate in the polar second solvent system. This also improves the selectivity of the process with regard to the desired ideal structure formation without expecting further undesired subsequent reactions of the same to produce higher molecular weight products.
  • the proportions of the catalyst in the first and second solvent systems can be expressed, for example, as mass ratios or using the distribution coefficient.
  • the distribution coefficient here means the ratio of the mass fractions of the present component between the non-polar first solvent system and the polar second solvent system.
  • the distribution coefficient of the catalyst should be less than the distribution coefficient of the oligomers, preferably less than the distribution coefficient of the starting materials.
  • the partition coefficient K x «-HePtan / x Acetomt rii of HDI 0.189 and that of the isocyanurate A3 (ideal structure) is 0.038.
  • the catalyst should then have a distribution coefficient greater than 0.038, preferably greater than 0.189.
  • the more the catalyst partitions into the non-polar first solvent system i.e. the greater the partition coefficient of the catalyst, the more selectively the oligomerization can be stopped at the level of the ideal structures, since there is more catalyst in the educt-rich phase and less in the oligomer-rich phase, where it would promote the undesired further reaction of the oligomers. Furthermore, a high solubility of the catalyst in the non-polar phase makes it easier to separate the catalyst from the oligomeric products.
  • Suitable catalysts are onium salts of phosphorus, nitrogen or sulfur with counterions, which are anions of acids with a pK a value below 4.5, preferably below 3.5.
  • Suitable counterions are, for example, the carboxylates of the carboxylic acids and aromatic and aliphatic alcoholates.
  • Preferred counterions are acetate, propionate, 3,3,3-trifluoropropionate, butyrate, capronate, octanoate, laurate, palmitate, stearate, isobutyrate, ethyl hexanoate, pivalate, neodecanoate, phenolate, cresylate, fluoride, hydrogen (di- and poly)!
  • Luoride or hydroxide.
  • Anions of nitrogen heterocycles such as imidazoles, triazoles and tetrazoles are also suitable.
  • Cyclic phosphines with substituents from the group consisting of linear or branched alkyl, cycloalkyl and alkenyl are likewise suitable, linear or branched alkyl and cycloalkyl being preferred. Also suitable are those polycyclic phosphorus-containing heterocycles which are formed when radicals are attached to cyclooctadiene by free radicals. The common name for such phosphines is Phobane.
  • the monomer can be represented in both phases.
  • the concentration of HDI in the polar phase is not negligible.
  • a technical advantage of the procedure according to the invention is the energy saving in comparison with the known processes and the lower temperature load on the oligomers and, if appropriate, unreacted monomers, since in the event of a subsequent separation only solvents need to be converted into the gas phase and not the high-boiling monomers such as, for example, diisocyanates.
  • the process also enables the catalyst to be recycled in a recycle stream.
  • a further energy saving results from the fact that the conversion of the monomer can be driven to higher conversions in comparison with the known methods without the gel point being exceeded. This is made possible by the separation of the oligomers, in particular the ideal structures, during the reaction and the resulting slowdown or at least partial prevention of their further reaction. Turnover, based on the amount of substance of the monomer used, is possible between 30% and 99.9% or between
  • the partition coefficient of the catalyst between the first solvent system and the second solvent system is
  • the catalyst is present in the first solvent system in> 1.1 times to ⁇ 9 times the amount compared to the second solvent system.
  • the distribution coefficient is preferably> 1.1 to ⁇ 4.
  • the reaction is carried out in batch mode.
  • the volume ratio of first to second solvent system is> 1: 1 to ⁇ 50: 1.
  • the volume ratio is preferably> 5: 1 to ⁇ 10: 1.
  • the isocyanate comprises 1,6-hexamethylene diisocyanate. Its oligomers can be used for a wide range of applications, particularly in the manufacture of polyurethane coatings. With the exception of technically unavoidable impurities, only 1,6-hexamethylene diisocyanate is preferably present in the isocyanate used.
  • a further embodiment of the method according to the invention relates to the case that the first solvent system comprises linear, branched and / or cyclic alkanes and the second solvent system comprises acetonitrile.
  • linear, branched or cyclic alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, 2,2,4-trimethylpentane, cyclohexane and / or tetralin are particularly favorable with acetonitrile, since low-boiling azeotropes can be formed (Smallwood, IM, Handbook of Organic Solvent Properties, Elsevier, 1996).
  • the choice of solvent systems which form azeotropes can save energy when distilling off the non-polar solvent system from the oligomeric products or when distilling off the polar solvent system from the unreacted starting material in comparison to a solvent system pair which does not form an azeotrope , to lead.
  • concentrations of the monomer between 5 and 40% by weight are preferred, so that the two-phase nature of the overall system is not impaired by phase mediation of the monomer and / or the oligomers formed.
  • reaction temperatures in the range from 30 ° C. to 60 ° C. have proven to be advantageous.
  • the reaction is carried out up to a conversion of> 10% by weight to 30% by weight, based on the mass of the isocyanate originally present.
  • This conversion is preferably> 15% to ⁇ 25% by weight and particularly preferably> 20 to ⁇ 22% by weight.
  • the degree of conversion can be determined, for example, by titration of the NCO groups in a reaction sample, by means of IR or NMR spectroscopy and by means of HPLC. With the same turnover, one can achieve increased selectivity with respect to trimer products compared to conventional processes.
  • the catalyst is used in a proportion of> 0.1 mol% to ⁇ 35 mol%, based on the mass of the polyisocyanate originally present.
  • a proportion of> 1 mol% to ⁇ 30 mol% is particularly favorable.
  • a preferred class of catalysts is based on polyhedral oligomeric silsesquioxanes, which is explained in more detail below.
  • the catalyst comprises polyhedral oligomeric silsesquioxanes of the general formula (I):
  • RI, R2, R3, R4, R5, R6, R7 and R8 are independently selected from groups (Ia) and / or (Ib) with the proviso that at least one of the radicals RI, R2, R3, R4, R5 , R6, R7 and R8 is selected from group (Ib):
  • A ortho-, meta- or para-C R, where R has the meaning given above;
  • R9 N (R10) (R11), P (R10) (R11), N (R10) (R11) (R12) X, P (R10) (R11) (R12) X,
  • RIO, RI 1 and R12 are independently alkyl or aryl
  • X is carboxylate, alcoholate, hydrogen carbonate, or carbene and M is ammonium, phosphonium, an alkali or alkaline earth metal cation.
  • This choice of the catalyst is based on the knowledge that its solubility or its distribution coefficient can be influenced in a two-phase system by a modular structure consisting of a non-polar partial structure and a catalytically active partial structure.
  • the non-polar and the catalytically active partial structure can carry opposite ionic charges and be held together by means of electrostatic interactions. It is also possible for the two substructures to be connected to one another by a covalent bond.
  • the non-polar partial structure of the catalyst is formed in the present invention by the substituted silsesquioxane structure.
  • the catalytically active substructure is bound via one or more substituents as described above.
  • the catalytic partial structure comprises an ionic or non-ionic nucleophile that catalyzes the starting oligomerization.
  • Non-ionic catalytically active partial structure is given if one or more of the substituents RI to R8 are - (CH2) n -P (alkyl) 2.
  • the exocyclic Si positions which are not substituted by catalytically active partial structures are preferred Substituents R2 to R8 both in the ionic and in the non-ionic case by ao-butyl, cyclohexyl and / or ao-octyl groups, particularly preferably by ao-butyl groups.
  • the substituent R9 is a further substituent according to formula (I).
  • the fact that the distribution of the catalyst in a two-phase system can be influenced means that a process can be carried out which, instead of exclusively separating the starting material by distillation, permits extraction which takes place at the same time as the catalyzed reaction or is carried out downstream of the catalyzed reaction.
  • a process can be implemented in which the catalyst and the starting material are preferably in the non-polar phase and the oligomeric polyisocyanate is preferably in the polar phase. To obtain the desired oligomer, only the polar solvent has to be distilled off after phase separation. Reactive extraction processes can also be implemented.
  • Alkyl acyclic aliphatic hydrocarbon residues that do not contain any C-C multiple bonds.
  • Alkyl is preferably selected from the group consisting of methyl, ethyl, propyl, 2-propyl, n-butyl, isobutyl, sec-butyl, isobutyl, n-pentyl, ao-pentyl, Pentyl, nI Iexyl, nI Ieptyl, n-octyl, n-nonyl and / or n-decyl.
  • Cycloalkyl cyclic aliphatic (cycloaliphatic) hydrocarbons with in particular 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, where the hydrocarbons can be saturated or unsaturated (but not aromatic), unsubstituted or mono- or polysubstituted.
  • the cycloalkyl radicals can furthermore be bridged once or several times, for example in the case of adamantyl, bicyclo [2.2.1] heptyl or bicyclo [2.2.2] octyl.
  • Cycloalkyl is preferably selected from the group comprising cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, cyclopentenyl, cyclohexenyl, cycloheptenyl and / or cyclooctenyl.
  • Alkenyl acyclic aliphatic hydrocarbon radicals which have at least one C-C double bond.
  • Alkenyl is preferably selected from the group comprising ethenyl (vinyl), propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl and / or decenyl.
  • Alkynyl acyclic aliphatic hydrocarbon radicals which have at least one CC triple bond.
  • Alkynyl is preferably selected from the group comprising ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl and / or decynyl.
  • Aryl aromatic hydrocarbons with up to 14 ring members, especially phenyls and naphthyls. Each aryl radical can be unsubstituted or mono- or polysubstituted, and the aryl substituents can be the same or different and can be in any desired position of the aryl.
  • Aryl is preferably selected from the group containing phenyl, 1-naphthyl and 2-naphthyl, which can each be unsubstituted or substituted one or more times.
  • a particularly preferred aryl is phenyl, unsubstituted or mono- or polysubstituted.
  • Heteroaryl a 5- or 6-membered cyclic aromatic radical which contains at least 1, optionally also 2, 3, 4 or 5 heteroatoms, where the heteroatoms are each independently selected from the group S, N and O and the heteroaryl Radical may be unsubstituted or mono- or polysubstituted; in the case of substitution on the heteroaryl, the substituents can be identical or different and can be in any desired position of the heteroaryl.
  • the heteroaryl radical is selected from the group consisting of benzofuranyl, benzoimidazolyl, benzothienyl, benzothiadiazolyl, benzothiazolyl, benzotriazolyl, benzooxazolyl, benzooxadiazolyl, quinazolinyl, quinoxalinyl, carbazolyl, quinoluryl, furlylenzylyl, diblenzylanyl, diblenzylanyl, diblenzylanyl, diblenzylanyl, diblenzylanyl, diblenzylanyl, dibenzylyl, furlylenzylyl, dibenzylyl, furlenzylyl, dibenzylyl, furl , furl, furlenzylyl, dibenzylyl, furl , furl, furl, furl, furl, furl, furl, furl, furl, furl, furl, furl, furl,
  • heterocyclyl radicals from the group comprising azetidinyl, aziridinyl, azepanyl, azocanyl, diazepanyl, dithiolanyl, dihydroquinolinyl, dihydropyrrolyl, dioxanyl, dioxolanyl, dioxepanyl, dihydroindenyl, dihydropyridolino, dihydrofolidino, morpholinyl, oxiranyl, oxetanyl, pyrrolidinyl, piperazinyl, 4-methyl piperazinyl, hydropyridinyl piperidinyl, pyrazolidinyl, pyranyl, tetrahydropyrrolyl, tetrahydropyranyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, Tetrahydroindolinyl, tetrahydrofuranyl, t
  • Perfluoroalkenyl alkenyl radicals as defined above, where all hydrogen atoms have been replaced by fluorine atoms.
  • Perfluoroalkynyl alkynyl radicals as defined above, where all hydrogen atoms have been replaced by fluorine atoms.
  • Alkoxy alkyl group attached via an oxygen atom as defined above.
  • Perfluoroalkyl alkyl radicals as defined above, where all hydrogen atoms have been replaced by fluorine atoms.
  • Perfluoroalkoxy alkoxy radicals as defined above, where all hydrogen atoms have been replaced by fluorine atoms.
  • Polyoxyalkylene polyether groups obtained from the polymerization of alkylene oxide units, in particular polymers, copolymers and block copolymers of ethylene oxide and propylene oxide.
  • Carboxylate salts of carboxylic acids, especially of alkyl and aryl carboxylic acids.
  • R2, R3, R4, R5, R6, R7 and R8 are ao-butyl
  • X is selected from the group comprising
  • R14-0 with R14 phenyl or 2,6-bis (l, l-dimethylethyl) -4-methylphenyl.
  • Catalyst 8 (SQ + 2,6-bis (l, l-dimethylethyl) -4-methylphenyl-0)
  • Proazaphosphatranes are another suitable class of catalyst.
  • the catalyst comprises 2,8,9-trialkyl-2,5,8,9-tetraaza-l-phosphabicyclo [3.3.3] undecane, 2,8,9-tricycloalkyl-2,5, 8,9-tetraaza-l-phosphabicyclo [3.3.3] undecane and / or 2,8,9-triaralkyl-2,5,8,9-tetraaza-l-phosphabicyclo [3.3.3] undecane, the Substituents in the 2-, 8- and 9-position can be the same or different.
  • CI-CIO radicals which can be linear or branched, preferably branched, come as alkyl substituents, C4-C12 radicals which can in turn be substituted by alkyl radicals and cycloalkyl radicals and benzyl radicals which in turn can be substituted by alkyl or alkoxy radicals, in question.
  • This catalyst preferably comprises 2,8,9-tri-o-methoxybenzyl-2,5,8,9-tetraaza-1-phosphabicyclo [3.3.3] undecane, 2,8,9-tricyclopentyl-2,5,8, 9-tetraaza-l-phosphabicyclo [3.3.3] undecane, 2,8,9-triisopropyl-2,5,8,9-tetraaza-l-phosphabicyclo [3.3.3] undecane and / or 2.8, 9-tri-iec-butyl-2,5,8,9-tetraaza-l-phosphabicyclo [3.3.3] undecane.
  • the last-mentioned compound is shown by way of example in the following formula (II):
  • 1,6-diisocyanatohexane 1,6-diisocyanatohexane
  • 1,6-HDI 1,6-diisocyanatohexane
  • isocyanurate of 1,6-HDI 1,3,5-tris (6-isocyanatohexyl) -1,3,5 -triazinane- 2,4,6-trione
  • asymmetrical trimer A mixture of the isocyanurate of 1,6-HDI ("symmetrical trimer") and the iminooxadiazinedione of 1,6-HDI ("asymmetrical trimer") in a ratio of> 95: 1 and traces of higher oligomers is referred to below as 1.6- Designated HDI trimer.
  • the quaternary salt obtained was isolated by removing the solvent in a partial vacuum. The residue was then dissolved in 50 ml of dichloromethane and a suspension of the corresponding silver carboxylate Ag + CH3 (CH2) s-COO (2.791 g, 10 mmol) in 100 ml of water was added. The mixture was stirred at room temperature for 8 hours. The mixture was then filtered, the organic phase separated and dried over sodium sulfate.
  • the end product SQ + CI h (CI h) ⁇ s— COO was obtained after removal of the solvent in a partial vacuum and characterized by means of high-resolution mass spectroscopy, infrared spectroscopy and multinuclear NMR spectroscopy, the protons and carbon spectra in each of which are characterized in the Figures marked with letters were clearly assigned by comparison with literature data based on displacement and integral.
  • the mass spectra were measured by electrospray ionization on a Thermo Fisher Scientific Orbitrap XL.
  • the samples were dissolved in CHCL, the solution was diluted with MeOH (containing 0.1% acetic acid) and injected using a syringe pump via the direct inlet into the ESI source system (electrospray voltage 4 kV, current 0.7 mA, volume flow Sheath Gas 5 arb, volume flow of surge gas 5 arb, capillary temperature 300 ° C, capillary voltage 0.05 V, tube lens voltage 150 V).
  • the detection was carried out with an Orbitrap ion trap.
  • the infrared spectra were measured on a Bruker alpha FT-fR spectrometer, the samples in each case being applied in bulk to the ATR crystal.
  • the spectra were measured in the range from 4000 to 400 cm 1 with a resolution of 4 cm 1 by averaging 32 individual spectra against air as the background spectrum (averaging 100 individual spectra).
  • the 31 P ⁇ 1 H ⁇ NMR spectra were measured at 161.9 MHz in CDCL on a Bruker AV400 Ultrashield.
  • the 11 NMR spectra were measured at 400 MHz in CDCL on a Bruker AV400.
  • the chemical shifts were calibrated relative to
  • splitting is specified as a singlet (s), two singlets (2xs), three singlets (3xs), doublet (d), triplet (t), multiplet (m) or broad signal (b).
  • FT-fR 2911 (m), 1558 (s), 1465 (s), 1366 (s), 1228 (m), 1060 (b), 835 (s), 738 (m), 471 (m) cm 1 .
  • Table 1 -3b Chemical shift and assignment of the characteristic signals for catalyst 3 (SQ + CH 3 (CH 2 ) 8 -COO-) in the 3 C f 1 11 ⁇ NMR spectra.
  • the concentrations of HDI, trimer and higher oligomers were determined by HPLC chromatography.
  • 0.1 g of the sample to be measured was diluted to a volume of 5 ml with acetonitrile. From this solution, 0.5 ml was diluted to a volume of 5 ml with acetonitrile. From this solution were 0.1 ml with 0.4 ml of a solution of 250 mg MPP in 50 ml of acetonitrile and 0.5 ml of a solution of 4.07 g of dichlorobenzene in 391.53 g of acetonitrile added. The solution was shaken for 30 seconds.
  • the HPLC method was calibrated with solutions of pure 1,6-HDI and the isocyanurate of 1,6-HDI.
  • the symmetrical and the asymmetrical 1,6-HDI trimer were integrated together.
  • the same response factor was assumed for the higher oligomers as for 1,6-HDI trimer.
  • the conversion was calculated from the amount no of 1,6-HDI in the sample taken after 10 seconds and the amount n t of 1,6-HDI measured at time t according to the formula (PI) ,
  • FIG. 1 is a phase diagram for the system n-I ieptane / acetonitrile / I, 6-111) I
  • FIG. 2 is a phase diagram for the system n-I ieptane / acetonitrile / I, 6-1 IDI-Trimcr
  • FIG. 3 is a phase diagram for the system nI Icptan / 1, 6- 111) 1/1, 6-1 IDI- ' l rimcr
  • FIG. 4 a plot of the content of 1,6-HDI in the two phases of a two-phase system mixture of n-heptane / acetonitrile / 1,6-HDI
  • FIG. 5 a plot of the content of 1,6-HDI trimer in the two phases of a two-phase system mixture of n-heptane / acetonitrile / 1,6-HDI trimer
  • FIG. 6 shows the time course of the turnover of a trimerization of 1,6-HDI
  • FIG. 7 shows the trimer selectivity as a function of the conversion in the trimerization of 1,6-HDI using SQ + Ac
  • phase diagram for the ternary system n-I Ieptane / Acetomtril / I, 6-1 IDI was determined experimentally at temperatures of 30 ° C and 60 ° C using turbidity titration.
  • Ternary mixtures were prepared by weighing defined amounts of n-I ieptane, acetonitrile and 1,6-HDI into sample vessels. The sample vessels were each closed, heated to 30 ° C. and stirred for 2 hours. If turbidity was observed, the mixture was cooled, further 1,6-HDI was added and the mixture was stirred at 30 ° C. for a further 2 hours. The addition of 1,6-HDI was repeated until a clear solution was obtained. The sample was then weighed and the total amount of 1,6-HDI added was determined. The series of measurements was then repeated at 60 ° C.
  • the upper dashed curve (square data points) describes the boundary observed at 30 ° C between single-phase (1P) and two-phase (2P) mixtures.
  • the boundary between single-phase and two-phase mixtures in the investigated system at 60 ° C is indicated by the lower curve (solid line; upright squares as data points).
  • the lower curve solid line; upright squares as data points).
  • Example 2 Analogously to Example 1, a phase diagram for the ternary system n-I Icptaii / Accton i tri 1/1, 6-HDI trimer at temperatures of 30 ° C and 60 ° C was determined experimentally using turbidity titration. Ternary mixtures were prepared by weighing defined amounts of n-I ieptane, aceto nitrile and 1,6-HDI trimer into sample vessels. The sample vessels were each closed, heated to 30 ° C. and stirred for 2 hours. If a clear solution was observed, the mixture was cooled, further n-I-ieptane was added and the mixture was stirred at 30 ° C. for a further 2 hours.
  • n-I ieptane was repeated until turbidity was observed.
  • the sample was then weighed and the total amount of n-I ieptane added was determined.
  • the series of measurements was then repeated at 60 ° C.
  • the upper corner was defined via the phase behavior of binary mixtures, which was also measured using turbidity titration.
  • 1,6-HDI trimer was added to n-heptane until turbidity was observed.
  • the phase behavior from example 1 was known for binary mixtures of n-heptane and acetonitrile.
  • the 1,6-HDI trimer used is referred to in the axis label as "(HDIL".
  • the results are shown in FIG. 2.
  • the upper, dashed curve (triangular data points) describes the boundary between single-phase (1P ) and two-phase (2P) Mixtures.
  • the boundary between single-phase and two-phase mixtures in the examined system at 60 ° C is indicated by the lower, solid curve (upright squares as data points). There is a phase below the respective curve and two phases above the curve.
  • n-I Ieptane / 1, 6-111) 1/1, 6- HDI trimer was determined experimentally at 60 ° C. using turbidity titration.
  • Ternary mixtures were prepared by weighing defined amounts of n-I ieptane, 1,6-HDI and 1,6-HDI trimer into sample vessels. The sample vessels were each closed, heated to 60 ° C. and stirred for 2 hours. If a clear solution was observed, the mixture was cooled, further 1,6-HDI was added and the mixture was stirred at 30 ° C. for a further 2 hours. The addition of 1,6-HDI was repeated until turbidity was observed. The sample was then weighed and the total amount of 1,6-HDI added was determined.
  • the 1,6-HDI trimer used is designated "(HDiL") in the axis label.
  • the results are shown in FIG. 3.
  • the curve describes the boundary observed at 60 ° C. between single-phase (1P) and two-phase (2P) mixtures There is a phase below the respective curve and two phases above the curve.
  • Ternary mixtures of acetonitrile, 1,6-HDI and 1,6-HDI trimer are miscible in the entire range and form only one phase.
  • 1,6-HDI partition coefficient of 1,6-HDI
  • a mixture of 1.42 g n-heptane, 1.65 g acetonitrile and various amounts of 1,6-HDI (0.11347, 0.18034, 0.28166, 0 , 35709, 0.4407 or 0.55099 g) equilibrated with stirring for 2 hours at 30 ° C or 60 ° C.
  • the two phases were then separated from one another and a sample was taken from each of the two phases for HPLC chromatography.
  • 1,6-HDI trimer To determine the partition coefficient of the 1,6-HDI trimer, a mixture of 1.42 g of n-heptane, 1.65 g of acetonitrile and various amounts of 1,6-HDI trimer (0.05798, 0.16823, 0 , 18819, 0.20261, 0.2964, 0.31701 or 0.42409 g) equilibrated with stirring for 2 hours at 30 ° C or 60 ° C. The two phases were then separated from one another and a sample was taken from each of the two phases for HPLC chromatography.
  • the results are shown in FIG. 5 reproduced.
  • the mass fractions of 1,6-HDI trimer in the respective phase are indicated on the x and y axes.
  • the upper dashed curve (triangular data points) describes the distribution curve of 1,6-HDI observed at 30 ° C between the n-heptane-rich phase and the acetonitrile-rich phase.
  • the lower dashed curve (upright squares as data points) describes the distribution curve observed at 60 ° C.
  • the partition coefficient K x «-HePtan / x Acetomt rii of 1.6-HDI trimer is calculated to be 0.0094 at 30 ° C and 0.038 at 60 ° C.
  • 1,6-HDI trimer is therefore preferably soluble in the acetonitrile-rich phase.
  • a comparison with the partition coefficient of 1,6-HDI from example 3 shows that the 1,6-HDI trimer partitions much more strongly into the acetonitrile-rich phase than the 1,6-HDI.
  • TTPU partition coefficient of TTPU
  • Table 1 Mass fractions of 1,6-HDI (A), trimer (A3) and higher oligomers (A5, A7 and A9) determined by HPLC chromatography when converting HDI in a two-phase mixture of nI Ieptau and acetonitrile using the TTPU Derivative 2,8,9-tri-.v «.-Butyl-2,5,8,9-tetraa / .a- 1 -phosphabicyclo
  • the solvent system pair was dispensed with and 1,6-HDI in bulk in the presence of the TTPU derivative 2,8,9-tri -. "? C.-butyl-2,5,8,9-tetraaza-l-phosphabicyclo [ 3.3.3] undecan as cataly- implemented.
  • the 1,6-HDI 2.0 g was weighed into a 100 ml round-bottom flask in Ar countercurrent and heated to 60 ° C. with stirring with a magnetic stirrer (500 rpm).
  • the catalyst TTPU (0.02 g) was then added. A first sample was taken 10 seconds after the catalyst had been added.
  • the isocyanate content of the mixture determined by means of NCO titration in accordance with DIN 53185, was 33.1%, from which 0.0110 s 1 resulted as the value for the turnover frequency (TOF) (average mol of NCO groups converted per mol of catalyst used). From the second-order rate constant (1.301 mol 1 min 1 ), the initial reaction rate is calculated to be 164.1 mol HDi mol catalyst 1 s 1 .
  • Table 2 Mass fractions of 1,6-HDI (A), trimer (A3) and higher oligomers (A5, A7 and A9) determined by HPLC chromatography in the conversion of HDI in bulk using the TTPU derivative 2,8,9 -Tri -iec.-butyl-2,5,8,9-tetraaza- 1 -phosphabicyclo [3.3.3] - undecane as a catalyst.
  • FIG. 6 is a plot of the turnover of 1,6-HDI (U) against the reaction time (t).
  • the upper, dashed curve square data points
  • the lower, solid curve upright squares as data points
  • FIG. 7 is a plot of the selectivity (S) of the formation of the isocyanurate trimer as a function of the conversion (U) of the respective reaction. Again, the top one is in dashed lines Curve (square data points) the comparative example and the lower, solid curve (upright squares as data points) relates to example 8 according to the invention.
  • the reaction rate expressed by the conversion of 1,6-HDI originally present, is slower than in the reaction in bulk of the comparative example.
  • the selectivity for trimer formation is significantly greater. With sales of up to 20% and more, essentially only the trimer is formed. Based on the same conversion, the desired oligomeric polyisocyanate 1,6-HDI trimer is thus obtained in the two-phase reaction system of Example 8 in higher purity, that is to say with a higher ideal structure fraction, than the corresponding oligomer mixture of the comparative example in reaction in bulk.

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  • Health & Medical Sciences (AREA)
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Abstract

L'invention concerne un procédé de préparation de polyisocyanates oligomères, comprenant l'étape consistant à faire réagir un isocyanate pour former un polyisocyanate oligomère en présence d'un catalyseur, la réaction étant mise en oeuvre en présence d'une paire de systèmes de solvant formant deux phases, le premier système de solvant comprenant un alcane linéaire, ramifié ou cyclique, des chloro-aromatiques et/ou des bromo-aromatiques, et le deuxième système de solvant comprenant un solvant qui est choisi dans le groupe constitué par les nitriles, les carbonates cycliques, les éthers cycliques, les sulfones, les sulfoxydes, les alcanes halogénés (l'halogène n'étant pas le fluor) et/ou les dialkyléthers d'oxydes d'oligoéthylène. Le catalyseur est choisi de manière à se trouver en plus grande proportion dans le premier système de solvant que dans le deuxième système de solvant.
PCT/EP2019/068781 2018-07-16 2019-07-12 Procédé de préparation de polyisocyanates oligomères Ceased WO2020016117A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021078930A1 (fr) 2019-10-24 2021-04-29 Basf Se Élimination de diisocyanate aliphatique monomère présent dans un polyisocyanate aliphatique à l'aide de capteurs

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WO2021078930A1 (fr) 2019-10-24 2021-04-29 Basf Se Élimination de diisocyanate aliphatique monomère présent dans un polyisocyanate aliphatique à l'aide de capteurs

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