WO2020016119A1 - Procédé d'oligomérisation d'isocyanates à l'aide de catalyseurs de silsesquioxane polyèdres - Google Patents

Procédé d'oligomérisation d'isocyanates à l'aide de catalyseurs de silsesquioxane polyèdres Download PDF

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WO2020016119A1
WO2020016119A1 PCT/EP2019/068783 EP2019068783W WO2020016119A1 WO 2020016119 A1 WO2020016119 A1 WO 2020016119A1 EP 2019068783 W EP2019068783 W EP 2019068783W WO 2020016119 A1 WO2020016119 A1 WO 2020016119A1
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catalyst
hdi
group
coo
butyl
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PCT/EP2019/068783
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German (de)
English (en)
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Thomas Ernst MÜLLER
Christoph Gürtler
Reinhard Halpaap
Frank Richter
Pedro SA GOMES
Carla Quarantelli
Burkhard KÖHLER
Walter Leitner
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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
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1883—Catalysts containing secondary or tertiary amines or salts thereof having heteroatoms other than oxygen and nitrogen
    • 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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
    • B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/123—Organometallic polymers, e.g. comprising C-Si bonds in the main chain or in subunits grafted to the main chain
    • B01J31/124—Silicones or siloxanes or comprising such units
    • B01J31/125—Cyclic siloxanes

Definitions

  • the present invention relates to a process for the oligomerization of isocyanates, comprising the step of reacting in particular a low molecular weight mono-, di- or triisocyanate (mixture) to form an oligomeric polyisocyanate in the presence of a polyhedral silsesquioxane catalyst.
  • the invention further relates to the use of such silsesquioxanes for the production of polyisocyanates and to selected silsesquioxanes themselves.
  • 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.
  • the target product for technical use is an oligomer mixture with a high ideal structure content.
  • the higher molecular weight oligomers are less desirable because they bring about a higher viscosity of the overall system with a reduced isocyanate group content, based on the weight of the oligomer mixture.
  • a mechanistic study on cyclooligomerization can be found, for example, in IT Horvath, FU Richter et al., Angew. Chem. Int. Ed. 2005, 45, pages 107-110.
  • An overview of isocyanate oligomerizations can be found in J. Prakt. Chem./Chem. Ztg. 1994, 336, pages 185-200.
  • the reaction has so far mostly been terminated after partial conversion by deactivating the catalyst and the monomer has been removed from the product mixture, e.g. by distillation, separated and reused.
  • the process is particularly associated with a high energy input and low space-time yield if low-viscosity and thus high ideal structure-containing polyisocyanates are to be obtained.
  • DE 38 06 276 A1 describes a process for the preparation of polyisocyanates containing isocyanurate groups by trimerization of part of the isocyanate groups of hexamethylene diisocyanate using quaternary ammonium hydroxides as a trimerization catalyst, Termination of the trimerization reaction at the desired degree of trimerization by adding a catalyst poison and / or thermal deactivation of the catalyst and removal of unreacted hexamethylene diisocyanate.
  • the hexamethylene diisocyanate used as the starting material is freed of carbon dioxide to a residual content of less than 20 ppm (weight).
  • the catalyst is used in an amount of less than 0.03% by weight based on the weight of the hexamethylene diisocyanate.
  • the polyisocyanates thus obtainable, optionally in the form blocked with blocking agents for isocyanate groups, as the isocyanate component in polyurethane coatings.
  • DE 100 65 176 Al discloses a catalyst and a process for producing low-viscosity and color-reduced isocyanurate-containing polyisocyanates.
  • the process involves the partial trimerization of aliphatic and / or cycloaliphatic diisocyanates and the subsequent removal of excess diisocyanate.
  • the trimerization takes place in the presence of 0.02 to 2% by weight, based on the weight of the diisocyanate used, of at least one trimerization catalyst of the quaternary benzylammonium compound type.
  • DE 198 24 490 A1 relates to a process for the preparation of polyisocyanates containing hninooxadiazinedione groups, the process products thus produced and their use in processes for the production of polyisocyanates with at least 30 mol% of iminooxadiazinedione groups (asymmetric trimers), based on the total amount of isocyanurate and iminooxadiazinedione groups, by catalytically induced trimerization of organic di- or polyisocyanates with a (average) molecular weight of 140 to 600 g / mol with independently aliphatic, cycloaliphatic and / or araliphatic isocyanate groups, quaternary ammonium or phosphonium fluorides are used as the trimerization catalyst.
  • asymmetric trimers iminooxadiazinedione groups
  • EP 0 351 873 B1 discloses a process for the preparation of polyisocyanurates, which is characterized in that an aliphatic or alicyclic diisocyanate compound comprising hexamethylene diisocyanate as the main component in the presence of 20 to 200 ppm, based on the weight of the isocyanate compound, of an alkanolammonium carboxylate is used as the isocyanurizing catalyst ,
  • EP 0 668 271 A1 describes a process for the preparation of polyisocyanates containing isocyanurate groups by partial trimerization of (cyclo) aliphatic diisocyanates in the presence of at least one trimerization catalyst from the group of tetraalkylammonium alkyl carbonates and betaine structured (quaternary ammonium alkyl) carbonates.
  • EP 0 896 009 A1 discloses a process for the preparation of polyisocyanates, characterized in that isocyanates of the formula (OCN-CH2) X, in which X represents optionally branched, optionally cyclic, optionally further heteroatoms and heteroatom groups (N, O, S) and at least one further C3-C2o substituent containing NCO group, by polymerization in the presence of hydrogen polyfluorides of the formula M n + n [F _ ⁇ (HF) m ], in which M represents an n-fold charged cation or a Summarized n-fold cation mixture stands and m> 0.1, as
  • Oligomerization catalyst can be produced.
  • EP 2 100 885 A1 relates to the use of heterocycles containing trivalent phosphorus as a ring member as catalysts for the isocyanate modification and a process for the preparation of trimer-type polyisocyanates. In the process of making
  • R 1 is an optionally cyclic, aliphatic Ci-Cso radical, which may be mono- or polyunsaturated and / or mono- or poly-C1-C20 alkyl or alkoxy-substituted.
  • R 2 and R 3 form with each other and with the phosphorus atom a saturated cycloaliphatic C t -C ö radical which can be substituted one or more times C1-C20 alkyl or alkoxy and / or bicyclic.
  • US 5,905,151 relates to a process for the trimerization of organic polyisocyanates in the presence of thermally active catalyst systems.
  • the catalyst systems comprise (a) compounds selected from the group: 1) lithium salts of aliphatic or organic carboxylic acids, 2) lithium salts of hydroxyl group-containing compounds, the hydroxyl groups being bonded directly to an organic ring and 3) lithium hydroxide and are used together with (b) an organic compound containing at least one hydroxyl group.
  • No. 5,258,482 describes a process for producing a polyisocyanate mixture with an NCO content of 10 to 47% by weight and which isocyanurate and allophanate groups in a molar ratio of monoisocyanurates to monoallophanates of 10: 1 to 1: 5.
  • the process comprises the steps: a) catalytic trimerization of part of the isocyanate groups of a mixture of 1,6-hexamethylene diisocyanate and a cyclic organic diisocyanate with (cyclo) aliphatically bound isocyanate groups in a molar ratio of 10:90 to 90:10; b) adding 0.001 to 0.5 mol per mol of the organic diisocyanate of a monoalcohol having at least one carbon atom and having a molecular weight of up to 2500 before or during the trimerization step a); and c) ending the trimerization reaction at the desired degree of conversion by adding a catalyst poison and / or by thermally deactivating the catalyst.
  • WO 1999/023128 Al deals with the use of a cationic hydrogen carbonate as a cyclotrimerization catalyst for isocyanates. This is either as such or complexed and has an ionic or molecular diameter of more than 1 angstroms, preferably more than 1.5 angstroms, and is at least partially soluble in the reaction medium.
  • a process for the production of polyisocyanurates by catalytic cyclotrimerization of isocyanates is also described, a catalytic system with a quaternary ammonium salt with imidazole as cocatalyst being used.
  • WO 2005/087828 A1 describes a process for the preparation of polyisocyanates containing isocyanurate groups by at least partially trimerizing (cyclo) aliphatic diisocyanates. The process is characterized in that the reaction is carried out in the presence of at least one trimerization catalyst selected from the group of the ammonium salts of a-hydroxycarboxylates substituted with four hydrocarbon radicals.
  • Silsesquioxanes in general are known from the literature. For example, BmSisOii-para-phenylene-CHiOH and the corresponding carboxylic acid in Liu, Hongzhi; Kondo, Shin-Ichi; Takeda, Nobuhiro; Unno, Masafumi, European Journal of Inorganic Chemistry, 2009, 10, pages 1317-1319. From Janssen, Michele; Müller, Christian; Vogt, Dieter; Wilting, Jos Angewandte Chemie International Edition, 2010, vol. 49, 42, pages 7738 - 7741 the ( I Bu 7 Si 8 Oi 2 -CH 2 CH 2 -para-phenylene-) 3 P is known.
  • silsesquioxanes for the oligomerization of isocyanates and the control of the solubility behavior of catalysts for the oligomerization of isocyanates by using a silsequioxane substituent are not known.
  • the present invention was based on the object of providing a process for the preparation of oligomeric polyisocyanates from starting materials in the sense of the definition given at the outset, which is not known or to a lesser extent than previously known, with the disadvantages of the prior art processes mentioned Isocyanate oligomerization is afflicted.
  • a process for the oligomerization of isocyanates comprising the step of reacting a starting material to form an oligomeric polyisocyanate in the presence of a catalyst, which is characterized in that 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 ö R t , where R has the meaning given above;
  • R9 N (R10) (R11), P (R10) (R11), N (R10) (R11) (R12) X, P (R10) (R11) (R12) X,
  • X is carboxylate, alcoholate, hydrogen carbonate, or carbene and M is ammonium, phosphonium, an alkali or alkaline earth metal cation.
  • An educt oligomerization takes place in the process according to the invention.
  • This is preferably a dimerization of isocyanates, particularly preferably uretdione formation, or trimerization of isocyanates, particularly preferably isocyanurate or iminooxadiazinedione formation.
  • starting material is understood to mean a polyisocyanate and in particular a low molecular weight mono-, di- or triisocyanate (mixture). Monomolecular monoisocyanates, diisocyanates and / or triisocyanates are particularly preferred.
  • the catalysts of the invention are particularly suitable for use in two-phase systems in which the catalyst and oligomeric polyisocyanate are separated from one another by extraction of a non-polar catalyst phase with a polar solvent.
  • the choice of the catalyst in the process according to the invention is based on the knowledge that its solubility or its distribution coefficient in a two-phase system can be influenced 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. It is preferably in the case of the exocyclic Si-substituted substituents R2 to R8 which are not substituted by catalytically active substructures, both in the ionic and in the nonionic 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).
  • 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-diisocyanatodicyclohexylmethane, 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 di- and triisocyanates mentioned above can also be used.
  • 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 CC multiple bonds.
  • Alkyl is preferably selected from the group consisting of methyl, ethyl, propyl, 2-propyl, n-rutyl, iso-butyl, .ver.-butyl, ieri.-butyl, n-pentyl, ao-pentyl, «eo-pentyl, nI icxyl, nI ieptyl, n-octyl, n-nonyl and / or n- Decyl includes.
  • 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 C-C 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 and possible 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 and possible 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, quinolanyl, dibenzyluryl, dibenzyluryl, dibenzyluryl , Imidazothiazolyl, indazolyl, Indolizinyl, indolyl, isoquinolinyl, isoxazoyl, isothiazolyl, indolyl, naphthyridinyl, oxazolyl, oxadiazolyl, phenazinyl, phenothiazinyl, phthalazinyl, pyrazolyl, pyridyl (2-pyridyl, 3-pyridyl, 4-pyrazolyl
  • heterocyclyl radicals from the group comprising azetidinyl, aziridinyl, azepanyl, diazepanyl, dithiolanyl, dihydroquinolinyl, dihydropyrrolyl, dioxanyl, dihydroindolol, dihydrofurylol, oxetanyl, pyrrolidinyl, piperazinyl, 4-methylpiperazinyl, piperidinyl, pyrazolidinyl, pyranyl, tetrahydropyrrolyl, tetrahydropyranyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, Tetrahydroindolinyl, tetrahydrofuranyl, tetrahydropyridinyl, tetrahydro- thiophenyl, tetrahydro-pyridoindolyl, tetrahydrona
  • Perfluoroaryl aryl radicals as defined above, where all aromatically bound hydrogen atoms have been replaced by fluorine atoms.
  • 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.
  • X is selected from the group comprising
  • R14-0 with R14 phenyl or 2,6-bis (l, l-dimethylethyl) -4-methylphenyl.
  • the starting material comprises hexamethylene diisocyanate.
  • oligomeric polyisocyanates can be used for a wide range of applications, particularly in the production of polyurethane coatings.
  • the isocyanate used preferably contains no other polyisocyanates besides those of the hexamethylene diisocyanate as a monomer unit.
  • the reaction takes place in a two-phase solvent pair, comprising a first solvent system and a second solvent system.
  • the solvent pair forms two phases if a phase boundary between the two liquid phases can be seen with the naked eye.
  • the first and the second solvent system can each contain solvents which show a miscibility gap within a certain temperature range.
  • the first and second solvent systems can each be present as mixtures of solvents with a corresponding mixture gap.
  • the first and second solvents originally present in pure Lorm partially mix with each other, whereby a first solvent system with the first solvent as the main component and the second solvent as a secondary component and a second solvent system with the second solvent as the main component. and the first solvent as Minor component is obtained.
  • liquid-liquid extraction is carried out on the reaction mixture obtained and a two-phase solvent pair comprising a first solvent system and a second solvent system is used in the liquid-liquid extraction.
  • the liquid-liquid extraction is a fractional extraction.
  • the first solvent system preferably comprises a linear, branched or cyclic, optionally partially or perfluorinated alkane (preferably all isomeric pentanes, hexanes, heptanes, octanes, decanes, undecanes, dodecanes, tridecanes, tetradecanes, pentadecanes, hexadecanes, cyclohexane, tetralin and any mixtures with one another ), Chloroaromatic and / or bromoaromatic (such as p-dibromobenzene) and the second solvent system comprises a solvent which is selected from the group comprising nitriles (preferably acetonitrile, propionitrile, phthalonitrile, dimethylmalonitrile, malononitrile, 3-butenenitrile, particularly preferably acetonitrile), cyclic carbonates (preferably propylene and ethylene carbonate), cyclic ether
  • solvent separation (avoidance of azeotropes, low specific heat, low evaporation heat), settling times in the extractor (large difference in relative density, low viscosity, high interfacial tension) and the mass transfer between the two phases ( low viscosity, low molecular weight).
  • the first solvent system comprises linear, branched or cyclic alkanes selected from the group comprising (all isomeric) pentanes, hexanes, heptanes, octanes, decanes, undecanes, tetradecanes and / or hexadecanes and the second solvent system comprises acetonitrile.
  • the solvent combinations mixture gaps were verified experimentally or are known from the literature (for example from J. Phys. Chem. Ref. Data 2007, 36 (3), pages 733-1131 and McLure et al, Fluid Phase Equilibria 1982, 8, pages 271 -284).
  • the described two-phase procedure allows an extractive workup of the reaction mixture without catalyst deactivation or a reaction procedure based on the principle of reactive extraction.
  • the catalysts to be used according to the invention are particularly suitable for this. Both possibilities are based on a different solution behavior of the starting material, for example HDI, and the oligomers, preferably the isocyanurate, in the mixture of two at least partially immiscible solvents.
  • the catalyst can be designed so that it has a high solubility in the same (non-polar) phase in which the starting material, for example HDI, dissolves better.
  • 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 «-heptane / x acetom rii of HDI is 0.189 and that of the isocyanurate A 3 (ideal structure) is 0.038.
  • the catalyst should then have a distribution coefficient greater than 0.038, preferably greater than 0.189.
  • a high solubility of the catalyst in the non-polar phase facilitates the separation of the catalyst from the product oligomers.
  • the monomer can be represented in both phases.
  • the concentration of HDI in the polar phase is not negligible.
  • a particularly favorable compromise with regard to the partition coefficient of the catalyst is generally present if the partition coefficient of the catalyst between the first solvent system and the second solvent system is> 0.19 to ⁇ 9 and thus the catalyst in the first solvent system is in> 0.19 times to ⁇ 9 times the amount compared to the second solvent system is present.
  • the distribution coefficient is preferably> 0.50 to ⁇ 4.
  • the present invention further relates to the use of a catalyst of the general formula (I) for the production of oligomeric polyisocyanates from starting materials.
  • 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):
  • R9 N (R10) (R11), P (R10) (R11), N (R10) (R11) (R12) X, P (R10) (R11) (R12) X,
  • RIO, RI 1 and RI 2 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.
  • X is selected from the group comprising
  • R14-0 with R14 phenyl or 2,6-bis (l, l-dimethylethyl) -4-methylphenyl.
  • the catalysts which can be used according to the invention have not yet been described in the prior art.
  • the present invention therefore further relates to polyhedral oligomeric silsesquioxanes of the general formula (I): wherein 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): (Ia): alkyl, cycloalkyl, aryl, heteroaryl, heterocyclyl, alkenyl, alkynyl, perfluoroaryl,
  • A ortho-, meta- or para-C ö R t , 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.
  • M is ammonium, phosphonium, an alkali or alkaline earth metal cation.
  • the reagents used were: 1,6-diisocyanatohexane (1,6-HDI), the corresponding isocyanurate of 1,6-HDI (1,3,5-tris (6-isocyanatohexyl) -1,3,5-triazinane-2 , 4,6-trione, "symmetrical trimer”) and the iminooxadiazinedione of 1,6-HDI ("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.
  • 1- (2-Methoxyphenyl) piperazine (MPP) was used as the internal standard for HPLC chromatography.
  • the catalysts obtained were characterized by high-resolution mass spectroscopy (HR-MS), infrared spectroscopy and NMR spectroscopy.
  • the mass spectra were measured by electrospray ionization on a Thermo Fisher Scientific Orbitrap XL.
  • the samples were dissolved in CHCE, 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 shock 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-IR spectrometer, the samples 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 CDCI3 on a Bruker AV400 Ultrashield.
  • the 1 11 ⁇ NMR spectra were measured at 376.5 MHz in CDCI3 on a Bruker AV400 Ultrashield.
  • the 11 NMR spectra were measured at 400 MHz in CDCI3 on a Bruker AV400.
  • the 3 C ⁇ 1 11 ⁇ NMR spectra were at 100.6 MHz measured in CDCI3 on a Bruker AV400 Ultrashield.
  • APT Attached Proton Test
  • signals with positive polarity were assigned to quaternary C atoms or CEL groups, signals with negative polarity to CH or CH3 groups.
  • the type of splitting is specified as a singlet (s), two singlets (2xs), three singlets (3xs), doublet (d), triplet (t), multiplet (m) or broad signal (b).
  • 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 aceto nitrile. From this solution, 0.5 ml was diluted to a volume of 5 ml with acetonitrile.
  • 0.1 ml of this solution was mixed with 0.4 ml of a solution of 250 mg of 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. 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.
  • Sales were compared by comparing the amount no of 1,6-HDI in a sample taken from the reaction mixture 10 seconds after catalyst addition and the amount n t of 1,6-HDI present in a sample at the time t was removed from the reaction mixture, calculated according to formula (III).
  • the selectivity given below relates to the amount of 1,6-HDI trimer divided by the sum of the amount of all oligomers formed (1.6-HDI trimer, 1,6-HDI pentamer, 1, 6-HDI heptamer, 1,6-HDI nonamer).
  • the initial reaction rate of trimerization of HDI was calculated according to a second order rate law for the consumption of HDI.
  • the second-order rate constant k was first determined for the part of the reaction in which the conversion from 1,6-HDI to 1,6-HDI trimer predominates. This part of the reaction corresponds to a decrease in the isocyanate content defined according to DIN 53185 from an initial 49.9% for the 1,6-HDI used to not less than 37.0% in the product mixture obtained.
  • the rate constant k was determined as the slope in a plot of the reversal of the amount of substance of 1,6-HDI (obtained by multiplying the amount of substance XA / XA ° by the amount of substance PA ° of 1,6-HDI) against the time.
  • the initial reaction rate is calculated from the rate constant (t—> 0) in moli ⁇ - HDi molc at 1 s 1 ) for the conversion of 1,6-HDI per mol catalyst (n catalyst 0 ) and time unit according to formula (IV).
  • the characteristic selectivity for the formation of 1,6-HDI trimer determined as the amount of the slope in a plot of the selectivity for the A3 isocyanurate type against the conversion of 1,6-HDI, describes the decrease in selectivity with increasing conversion .
  • this plot shows a linear curve for the initial area of the reaction, corresponding to a decrease in the isocyanate content defined according to DIN 53185 from 49.9% initially for the 1,6-HDI used to not less than 35.8% in the product mixture obtained Course.
  • Catalysts in which the formation of higher oligomers is slow compared to the formation of the 1,6-HDI trimer (corresponding to a high selectivity to 1,6-HDI trimer) have small values for the characteristic selectivity.
  • Example group 1 catalyst synthesis
  • Silver carboxylate or silver alcoholate used was obtained according to the following procedure: A mixture of the corresponding carboxylic acid R-COOH (10 mmol) or the corresponding phenol R-OH (10 mmol) and KOH (0.561 g, 10 mmol) in 10 mL water was added Room temperature stirred until a complete dissolution was observed. A solution of silver nitrate (1.699 g, 10 mmol) in 10 mL water was added to this solution. The solvent obtained was filtered off, washed with 25 ml of water and dried in vacuo.
  • 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 + R-COO or silver alcoholate Ag + RO (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 final product SQ + R-COO or SQ + RO was obtained after removing the solvent in a partial vacuum and characterized by means of high-resolution mass spectroscopy, infrared spectroscopy and multi-core NMR spectroscopy, with the respective proton and carbon spectra marked with letters in the figures Groups were clearly assigned based on displacement and integral by comparison with literature data.
  • the following silsesquioxanes were obtained with the silver carboxylates and silver alcoholates used:
  • Table 1-la Chemical shift and assignment of the characteristic signals for catalyst 1 (SQ + CHs-COO) in the ⁇ NMR spectra.
  • Table 1-lb Chemical shift and assignment of the characteristic signals for catalyst 1 (SQ + CHs-COO) in the 3 C f 1 11 ⁇ NMR spectra.
  • Catalyst 2 SQ + ieri.-butyl-COO
  • Table l-2a Chemical shift and assignment of the characteristic signals for catalyst 2 (SQ + tert-butyl-COO) in the 11 NMR spectra.
  • Table 1-2b Chemical shift and assignment of the characteristic signals for catalyst 2 (SQ + tert-butyl-COO) in the 3 C ⁇ 1 11 ⁇ NMR spectra.
  • Table l-3a Chemical shift and assignment of the characteristic signals for catalyst 3 (SQ + CH (CH) -COO) in the 11 NMR spectra.
  • 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.
  • Table 1-5b Chemical shift and assignment of the characteristic signals for catalyst 5 (SQ + 4-methoxyphenyl-COO) in the 3 C ⁇ 1 11 ⁇ NMR spectra.
  • Table 1-6a Chemical shift and assignment of the characteristic signals for catalyst 6 (SQ + 3,4,5-trimethoxyphenyl-COO) in the 11 NMR spectra.
  • Table 1 -6b Chemical shift and assignment of the characteristic signals for catalyst 6 (SQ + 3,4,5-trimethoxyphenyl-COO) in the 3 C ⁇ 1 11 ⁇ NMR spectra.
  • Table 1-7a Chemical shift and assignment of the characteristic signals for catalyst 7 (SQ + phenyl-O) in the 11 NMR spectra.
  • Table l-7b Chemical shift and assignment of the characteristic signals for catalyst 7 (SQ + phenyl-O) in the 3 C ⁇ 'II ⁇ NMR spectra.
  • Catalyst 8 SQ + 2,6-bis (l, l-dimethylethyl) -4-methylphenyl-0
  • Table l-8a Chemical shift and assignment of the characteristic signals for catalyst 8 (SQ + 2,6-bis (l, l-dimethylethyl) -4-methylphenyl-0) in the 11 NMR spectra.
  • Table 1-9a Chemical shift and assignment of the characteristic signals for catalyst 9 (SQ + CH 3 -CH (OH) -COC> -) in the II NMR spectra.
  • Table 1 -9b Chemical shift and assignment of the characteristic signals for catalyst 9 (SQ + CH 3 -CH (OH) -COC> -) in the 3 C f 1 11 ⁇ NMR spectra.
  • Example group 2 Catalyst tests
  • the catalyst 1 (SQ + CH3-COO) obtained as described above was tested for its suitability for the trimerization of hexamethylene diisocyanate (HDI).
  • HDI hexamethylene diisocyanate
  • HDI was heated to 60 ° C. without stirring in an argon atmosphere with stirring, and 5 min after reaching this temperature, 0.1426 g (1 mol%) of SQ + CH3-COO was added.
  • the isocyanate content of the mixture determined after 60 minutes by means of NCO titration in accordance with DIN 53185 was 38.4%, which results in 0.0032 s 1 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 (0.992 mol 1 min 1 ), the initial reaction rate is calculated to be 73.5 mol HDi mol Kataiysato Ü S 1 .
  • the characteristic selectivity for the formation of 1,6-HDI trimer is 0.828.
  • Table 2-1 Mass fractions of 1,6-HDI (A), trimer (A3) and higher oligomers (A5, A7 and A9) determined by HPLC chromatography in the reaction of HDI with catalyst 1 (SQ + CH 3 -COO- ).
  • the catalyst 2 (SQ + tert-butyl-COO) obtained as described above was examined with regard to its suitability for the trimerization of hexamethylene diisocyanate (HDI).
  • HDI hexamethylene diisocyanate
  • Samples were taken from the reaction mixture and analyzed by HPLC chromatography. The results are shown in Table 2-2.
  • the oligomerization of HDI started after an initial period of 2.6 min.
  • the characteristic selectivity for the formation of 1,6-HDI trimer is 0.861.
  • Table 2-2 Mass fractions of 1,6-HDI (A), trimer (A3) and higher oligomers (A5, A7 and A9) determined by HPLC chromatography in the reaction of HDI with catalyst 2
  • the catalyst 3 (SQ + CH (CH) -COO) obtained as described above was tested for its suitability for the trimerization of hexamethylene diisocyanate (HDI).
  • HDI hexamethylene diisocyanate
  • Samples were taken from the reaction mixture and analyzed by HPLC chromatography. The results are shown in Table 2-3. After a reaction time of 90 minutes, a conversion for the monomeric HDI of 52.0% with a 64.5% selectivity (based on the total amount of the reaction products) for the trimer of the isocyanurate type A was determined.
  • the remaining reaction products were identified as higher oligomers of the HDI.
  • the isocyanate content of the mixture determined after 60 minutes by means of NCO titration according to DIN 53185 was 37.1%, from which 0.0036 s 1 results 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 (1.278 mol 1 min 1 ), the initial reaction rate is calculated to be 111.9 mol HDi mol Kataiysato Ü s 1 .
  • the characteristic selectivity for the formation of 1,6-HDI trimer is 0.769.
  • the catalyst 4 (SQ + phenyl-COO) obtained as described above was tested for its suitability for the trimerization of hexamethylene diisocyanate (HDI).
  • HDI hexamethylene diisocyanate
  • Samples were taken from the reaction mixture and analyzed by HPLC chromatography. The results are shown in Table 2-4.
  • the oligomerization of HDI started after an initial period of 9.6 min.
  • the characteristic selectivity for the formation of 1,6-HDI trimer is 0.689.
  • Table 2-1 Mass fractions of 1,6-HDI (A), trimer (A3) and higher oligomers (A5, A7 and A9) determined by HPLC chromatography in the reaction of HDI with catalyst 4 (SQ + phenyl-COO).
  • the catalyst 5 (SQ + 4-methoxyphenyl-COO) obtained as described above was tested for its suitability for the trimerization of hexamethylene diisocyanate (HDI).
  • HDI hexamethylene diisocyanate
  • Samples were taken from the reaction mixture and analyzed by HPLC chromatography. The oligomerization of HDI started after an initial period of 0.1 min. The results are shown in Table 2-5.
  • the characteristic selectivity for the formation of 1,6-HDI trimer is 0.763.
  • the catalyst 6 (SQ + 3,4,5-trimethoxyphenyl-COO) obtained as described above was examined for its suitability for the trimerization of hexamethylene diisocyanate (HDI).
  • HDI hexamethylene diisocyanate
  • samples were taken from the reaction mixture and analyzed by HPLC chromatography. The oligomerization of HDI started after an initial period of 3.0 min. The results are shown in Table 2-6.
  • the isocyanate content of the mixture determined after 60 minutes by means of NCO titration in accordance with DIN 53185 was 37.4%, which results in 0.0035 s 1 as the value for the turnover frequency (TOF) (average number of moles of NCO groups converted per mole of catalyst used) , From the second-order rate constant (1.265 mol 1 min 1 ), the initial reaction rate is calculated to be 100.8 mol HDi mol Kataiysato Ü s 1 .
  • the characteristic selectivity for the formation of 1,6-HDI trimer is 0.795.
  • the catalyst 7 (SQ + phenyl-COO) obtained as described above was tested for its suitability for the trimerization of hexamethylene diisocyanate (HDI).
  • HDI hexamethylene diisocyanate
  • Samples were taken from the reaction mixture and analyzed by HPLC chromatography. The results are shown in Table 2-7. After a reaction time of 120 minutes, a conversion for the monomeric HDI of 49.7% with a 64.7% selectivity (based on the total amount of the reaction products) for the trimer of the isocyanurate type A 3 was determined.
  • the remaining reaction products were identified as higher oligomers of the HDI.
  • the isocyanate content of the mixture determined after 60 minutes by means of NCO titration in accordance with DIN 53185 was 39.0%, which results in 0.0030 s 1 as the value for the turnover frequency (TOF) (average number of moles of NCO groups converted per mole of catalyst used) , From the second-order rate constant (0.878 mol 1 min 1 ), the initial reaction rate is calculated to be 149.0 mol HDi mol Kataiysato Ü s 1 .
  • the characteristic selectivity for the formation of 1,6-HDI trimer is 0.839.
  • Table 2-7 Mass fractions of 1,6-HDI (A), trimer (A3) and higher oligomers (A5, A7 and A9) determined by HPLC chromatography in the reaction of HDI with catalyst 7 (SQ + phenyl-COO).
  • the catalyst 8 (SQ + 2,6-bis (l, l-dimethylethyl) -4-methylphenyl-O) obtained as described above was examined for its suitability for the trimerization of hexamethylene diisocyanate (HDI).
  • HDI hexamethylene diisocyanate
  • Samples were taken from the reaction mixture and analyzed by HPLC chromatography. The results are shown in Table 2-8.
  • the characteristic selectivity for the formation of 1,6-HDI trimer is 0.740.
  • Table 2-8 Mass fractions of 1,6-HDI (A), trimer (A3) and higher oligomers (A5, A7 and A9) determined by HPLC chromatography in the reaction of HDI with catalyst 8 (SQ + 2,6-bis (1,1-dimethylethyl) -4-methylphenyl-0).
  • the catalyst 9 (SQ + CH3-CH (OH) -COO) obtained as described above was tested for its suitability for the trimerization of hexamethylene diisocyanate (HDI).
  • HDI hexamethylene diisocyanate
  • Samples were taken from the reaction mixture and analyzed by HPLC chromatography. The results are shown in Table 2-9. After a reaction time of 120 minutes, a conversion for the monomeric HDI of 48.6% with a 63.3% selectivity (based on the total amount of the reaction products) for the trimer of the isocyanurate type A3 was determined.
  • the remaining reaction products were identified as higher oligomers of the HDI.
  • the isocyanate content of the mixture determined after 60 minutes by means of NCO titration in accordance with DIN 53185 was 37.8%, from which 0.0034 s 1 resulted as the value for the turnover frequency (TOF) (average NCO groups converted per mole of catalyst used per second) , From the second-order rate constant (1.023 mol 1 min 1 ), the initial reaction rate is calculated to be 90.7 mol HDi mol Kataiysato Ü S 1 .
  • the characteristic selectivity for the formation of 1,6-HDI trimer is 0.890.
  • the partition coefficient K x «-HePtan / x Acetomt rii is calculated as the ratio of the measured amount of the catalyst, which was dissolved in the nI Ieptane phase, and the measured amount of the catalyst, which was and is dissolved in the acetonitrile phase given in Table 10 below.
  • the partition coefficient K x «-HePtan / x Acetomtni calculated as the ratio of the measured amount of the catalyst dissolved in the nI ieptane phase and the measured amount of the catalyst dissolved in the acetonitrile phase became 0 , 74 determined.

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Abstract

La présente invention concerne un procédé d'oligomérisation de polyisocyanates, comprenant l'étape de la réaction d'un polyisocyanate, qui permet de former un polyisocyanate oligomère, en présence d'un catalyseur de silsesquioxane oligomère polyèdre. L'invention concerne en outre l'utilisation de tels silsesquioxanes pour produire des polyisocyanates ainsi que lesdits silsesquioxanes choisis. Le catalyseur comporte une structure selon la formule générale (I), dans laquelle en particulier R2 à R8 sont des groupes iso-butyle et R1 représente un −(CH2)n1−P(iso-butyle)2 ou un −(CH2)n1−P(iso-butyle)3X (avec n1 = 2, 3, 4 ou 5), et X étant choisi dans le groupe comprenant un R13−COO− (avec R13 = CF3, CH3, tert.-butyle, CH3(CH2)n2 (avec n2 = 1, 2, 3, 4, 5, 6, 7 ou 8), CH3CH(OH), phényle, 4-méthoxyphényle ou 3,4,5-triméthoxyphényle), R14−O− (avec R14 = phényle ou 2,6-bis(1,1-diméthyléthyl)-4-méthylphényle).
PCT/EP2019/068783 2018-07-16 2019-07-12 Procédé d'oligomérisation d'isocyanates à l'aide de catalyseurs de silsesquioxane polyèdres WO2020016119A1 (fr)

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Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3806276A1 (de) 1988-02-27 1989-09-07 Bayer Ag Verfahren zur herstellung von isocyanuratgruppen aufweisenden polyisocyanaten und ihre verwendung
EP0351873A2 (fr) 1988-07-22 1990-01-24 Dainippon Ink And Chemicals, Inc. Procédé de préparation d'un polyisocyanate
US5258482A (en) 1992-06-12 1993-11-02 Miles Inc. Polyisocyanates containing allophanate and isocyanurate groups, a process for their production from a mixture of diisocyanates and their use in two-component coating compositions
EP0668271A1 (fr) 1994-02-17 1995-08-23 BASF Aktiengesellschaft Procédé pour la préparation de polyisocyanates contenant des groupes isocyanurates
EP0896009A1 (fr) 1997-08-06 1999-02-10 Bayer Ag Procédé pour la préparation de polyisocyanates, les polyisocyanates ainsi préparés et leur utilisation
WO1999023128A1 (fr) 1997-11-04 1999-05-14 Rhodia Chimie Catalyseur et procede de trimerisation d'isocyanates
US5905151A (en) 1993-02-18 1999-05-18 Bayer Corporation Trimer catalyst for aliphatic and aromatic isocyanates
DE19824490A1 (de) 1998-06-02 1999-12-09 Bayer Ag Verfahren zur Herstellung Imidooxadiazindiongruppen enthaltender Polyisocyanate, die so hergestellte Verfahrensprodukte und deren Verwendung
DE10065176A1 (de) 2000-12-23 2002-06-27 Degussa Katalysator und Verfahren zur Herstellung von niedrigviskosen und farbreduzierten isocyanuratgruppenhaltigen Polyisocyanaten
WO2005087828A1 (fr) 2004-03-12 2005-09-22 Basf Aktiengesellschaft Procede de preparation de polyisocyanates contenant des groupes isocyanurate et utilisation desdits composes
DE102004060131A1 (de) 2004-12-13 2006-06-14 Basf Ag Verfahren zur Herstellung von Polyisocyanaten
US20090082502A1 (en) * 2003-12-18 2009-03-26 Lichtenhan Joseph D Metallized polyhedral oligomeric silsesquioxanes as catalysts for polyurethanes
EP2100885A1 (fr) 2008-03-14 2009-09-16 Bayer MaterialScience AG Fabrication de polyisocyanates de type trimère
US20160168308A1 (en) * 2013-07-25 2016-06-16 Covestro Deutschland Ag Method for producing polyisocyanates and use of said polyisocyanates

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3806276A1 (de) 1988-02-27 1989-09-07 Bayer Ag Verfahren zur herstellung von isocyanuratgruppen aufweisenden polyisocyanaten und ihre verwendung
EP0351873A2 (fr) 1988-07-22 1990-01-24 Dainippon Ink And Chemicals, Inc. Procédé de préparation d'un polyisocyanate
US5258482A (en) 1992-06-12 1993-11-02 Miles Inc. Polyisocyanates containing allophanate and isocyanurate groups, a process for their production from a mixture of diisocyanates and their use in two-component coating compositions
US5905151A (en) 1993-02-18 1999-05-18 Bayer Corporation Trimer catalyst for aliphatic and aromatic isocyanates
EP0668271A1 (fr) 1994-02-17 1995-08-23 BASF Aktiengesellschaft Procédé pour la préparation de polyisocyanates contenant des groupes isocyanurates
EP0896009A1 (fr) 1997-08-06 1999-02-10 Bayer Ag Procédé pour la préparation de polyisocyanates, les polyisocyanates ainsi préparés et leur utilisation
WO1999023128A1 (fr) 1997-11-04 1999-05-14 Rhodia Chimie Catalyseur et procede de trimerisation d'isocyanates
DE19824490A1 (de) 1998-06-02 1999-12-09 Bayer Ag Verfahren zur Herstellung Imidooxadiazindiongruppen enthaltender Polyisocyanate, die so hergestellte Verfahrensprodukte und deren Verwendung
DE10065176A1 (de) 2000-12-23 2002-06-27 Degussa Katalysator und Verfahren zur Herstellung von niedrigviskosen und farbreduzierten isocyanuratgruppenhaltigen Polyisocyanaten
US20090082502A1 (en) * 2003-12-18 2009-03-26 Lichtenhan Joseph D Metallized polyhedral oligomeric silsesquioxanes as catalysts for polyurethanes
WO2005087828A1 (fr) 2004-03-12 2005-09-22 Basf Aktiengesellschaft Procede de preparation de polyisocyanates contenant des groupes isocyanurate et utilisation desdits composes
DE102004060131A1 (de) 2004-12-13 2006-06-14 Basf Ag Verfahren zur Herstellung von Polyisocyanaten
EP2100885A1 (fr) 2008-03-14 2009-09-16 Bayer MaterialScience AG Fabrication de polyisocyanates de type trimère
US20160168308A1 (en) * 2013-07-25 2016-06-16 Covestro Deutschland Ag Method for producing polyisocyanates and use of said polyisocyanates

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
I. T. HORVÄTHF. U. RICHTER ET AL., ANGEW. CHEM. INT. ED., vol. 45, 2005, pages 107 - 110
J. PHYS. CHEM. REF. DATA, vol. 36, no. 3, 2007, pages 733 - 1131
J. PRAKT. CHEM./CHEM. ZTG., vol. 336, 1994, pages 185 - 200
JANSSEN, MICHELEMÜLLER, CHRISTIANVOGT, DIETERWILTING, JOS: "Angewandte Chemie, International Edition", vol. 49, 2010, pages: 7738 - 7741
LIU, HONGZHIKONDO, SHIN-ICHITAKEDA, NOBUHIROUNNO, MASAFUMI, EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, vol. 10, 2009, pages 1317 - 1319
MCLURE ET AL., FLUID PHASE EQUILIBRIA, vol. 8, 1982, pages 271 - 284

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