EP2049675A1 - Procédé de fabrication de pentaméthylèn-1,5-diisocyanate - Google Patents

Procédé de fabrication de pentaméthylèn-1,5-diisocyanate

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Publication number
EP2049675A1
EP2049675A1 EP07787876A EP07787876A EP2049675A1 EP 2049675 A1 EP2049675 A1 EP 2049675A1 EP 07787876 A EP07787876 A EP 07787876A EP 07787876 A EP07787876 A EP 07787876A EP 2049675 A1 EP2049675 A1 EP 2049675A1
Authority
EP
European Patent Office
Prior art keywords
pentamethylene
diisocyanate
reaction
decarboxylase
lysine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP07787876A
Other languages
German (de)
English (en)
Inventor
Martin Fiene
Eckhard Stroefer
Wolfgang Siegel
Stephan Freyer
Oskar Zelder
Gerhard Schulz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP07787876A priority Critical patent/EP2049675A1/fr
Priority to EP11172650A priority patent/EP2418198A1/fr
Publication of EP2049675A1 publication Critical patent/EP2049675A1/fr
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P13/00—Preparation of nitrogen-containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
    • C07B59/001—Acyclic or carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C265/00—Derivatives of isocyanic acid
    • C07C265/14—Derivatives of isocyanic acid containing at least two isocyanate groups bound to the same carbon skeleton
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P13/00—Preparation of nitrogen-containing organic compounds
    • C12P13/001—Amines; Imines
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P13/00—Preparation of nitrogen-containing organic compounds
    • C12P13/02—Amides, e.g. chloramphenicol or polyamides; Imides or polyimides; Urethanes, i.e. compounds comprising N-C=O structural element or polyurethanes
    • 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
    • C08G2101/00—Manufacture of cellular products

Definitions

  • the present invention relates to a process for the preparation of pentamethylene-1, 5-diisocyanate, thus prepared pentamethylene-1, 5-diisocyanate and its use.
  • pentamethylene diisocyanate from 1,5-pentanediamine is known per se and can be phosgene-free (T. Lesiak, K. Seyda, Journal of Practical Chemistry (Leipzig), 1979, 321 (1), 161-163) or by reaction with phosgene (eg DE 2625075).
  • DE 1900514 (corresponding to GB 1225450) describes the two-stage preparation of pentamethylene-1,5-diisocyanate from caprolactam by conversion into the hydroxyamic acids and their subsequent phosgenation.
  • Caprolactam is produced on a large scale either from benzene by hydrogenation of the nucleus to cyclohexane, oxidation to cyclohexanone and Beckmann rearrangement with hydroxylamine or from 1,4-butadiene by hydrocyanation and selective hydrogenation and subsequent cyclization to caprolactam.
  • the base is a hydrocarbon from petroleum chemistry.
  • 1, 5-pentanediamine is known by enzymatic decarboxylation of lysine with, for example, lysine decarboxylase (EP 1482055 A1 or JP 2004-222569 A) in a cell-free system or by thermal or catalytic decarboxylation (G. Gautret de Ia Moriciere, G. Chatelus, Bull. Soc. Chim. France (1969, 12, 4421-4425) or by hydrogenation of the corresponding nitriles (for example EP 161419 or WO 2003/99768).
  • lysine decarboxylase EP 1482055 A1 or JP 2004-222569 A
  • thermal or catalytic decarboxylation G. Gautret de Ia Moriciere, G. Chatelus, Bull. Soc. Chim. France (1969, 12, 4421-4425) or by hydrogenation of the corresponding nitriles (for example EP 161419 or WO 2003/99768).
  • WO 2006/005603 describes a biochemical process for the preparation of 1, 4-butanediamine from ornithine using ornithine decarboxylase and its use as starting compound for the polyamide production.
  • Object of the present invention was to produce pentamethylene-1, 5-diisocyanate, which can be prepared from renewable resources.
  • the object has been achieved by a process for the preparation of pentamethylene-1,5-diisocyanate in which b) lysine is converted into 1,5-pentanediamine and c) the 1,5-pentanediamine thus obtained is converted into pentamethylene-1,5-diisocyanate transferred.
  • the advantage of the process according to the invention is that, in the preparation of the pentamethylene-1,5-diisocyanate, it is independent of crude oil as a raw material base.
  • the pentamethylene-1, 5-diisocyanate prepared in this way has a lower color than conventionally produced because it is thermally less stressed.
  • the pentamethylene-1,5-diisocyanate prepared according to the invention has a fraction of the branched pentamethylene diisocyanates of isomers of less than 100 ppm in each case.
  • the pentamethylene-1, 5-diisocyanate prepared according to the invention has almost exclusively two primary isocyanate groups and therefore exhibits a more uniform reactivity in reactions of the isocyanate groups, for example in the preparation of polyurethanes.
  • Branched pentamethylene diisocyanate isomers in contrast, have a primary and a secondary isocyanate group, which are different reactive.
  • the inventive step b) consists of a conversion of lysine in 1, 5-pentanediamine.
  • the lysine (2,6-diaminohexanoic acid) used for the process according to the invention is derived preferably from biological material and can be used as D-enantiomer, as
  • Enantiomer or as any desired mixture of these enantiomers, for example as racemate, preferably in the form of the L-enantiomer ([(S) -2,6-diaminohexanoic acid).
  • It can be used in free form or as an internal salt, in the form of its anion as carboxylate or mono- or di-protonated in the form of its mono- or di-ammonium salt, for example as chloride.
  • the lysine can be used in the form of its ester, for example as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl or iso-butyl ester.
  • Step b) is preferably a decarboxylation.
  • decarboxylation is lysine, optionally dissolved in a solvent or suspended at a temperature above 80 0 C, preferably above 100 0 C, particularly preferably above 120 0 C, most preferably above 150 0 C. and especially heated above 180 0 C (thermal decarboxylation).
  • the temperature may be up to 250 0 C, preferably up to 230 0 C, particularly preferably up to 210 0 C and most preferably up to 200 0 C.
  • pressure can be applied to keep any solvent present in the reaction mixture.
  • solvents are aromatic and / or (cyclo) aliphatic hydrocarbons and mixtures thereof, halogenated hydrocarbons, esters, ethers and alcohols.
  • aromatic hydrocarbons (cyclo) aliphatic hydrocarbons, alkanoic acid alkyl esters, alkoxylated alkanoic acid alkyl esters and mixtures thereof.
  • Particularly preferred are mono- or polyalkylated benzenes and naphthalenes, Alkanklarealkylester and alkoxylated Alkanklarealkylester and mixtures thereof.
  • aromatic hydrocarbon mixtures preferred are those which comprise predominantly aromatic C7- to Cu-hydrocarbons and may comprise a boiling range from 1 10 to 300 0 C, more preferably toluene, o-, m- or p-xylose lol, trimethylbenzene isomers, tetramethylbenzene , Ethylbenzene, cumene, tetrahydronaphthalene and mixtures containing such.
  • Solvesso® brands of ExxonMobil Chemical especially Solvesso® 100 (CAS No. 64742-95-6, predominantly C 9 and Cio-aromatics, boiling range about 154-178 0 C), 150 (boiling range about 182 - 207 0 C) and 200 (CAS No. 64742-94-5), as well as the Shellsol® brands of Shell.
  • Hydrocarbon mixtures of paraffins, cycloparaffins and aromatics are also available under the designations crystal oil (for example, crystal oil 30, boiling range about 158-198 0 C or crystal oil. 60: CAS No. 64742-82-1), petroleum spirit (for example likewise CAS No. 64742-.
  • hydrocarbon mixtures are generally more than 90% by weight, preferably more than 95, more preferably more than 98% and very particularly preferably more than 99% by weight. It may be useful to use hydrocarbon mixtures with a particularly reduced content of naphthalene.
  • Halogenated hydrocarbons are, for example, chlorobenzene and dichlorobenzene or isomeric mixtures thereof.
  • esters are n-butyl acetate, ethyl acetate, 1-methoxypropyl acetate-2 and 2-methoxyethyl acetate, and the mono- and diacetyl esters of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol, for example butyl glycol acetate.
  • Further examples are also carbonates, such as preferably 1, 2-ethylene carbonate, 1, 2-propylene carbonate or 1, 3-propylene carbonate.
  • Ethers are, for example, tetrahydrofuran (THF), dioxane and the dimethyl, ethyl or n-butyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol.
  • THF tetrahydrofuran
  • dioxane dioxane
  • dimethyl, ethyl or n-butyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol.
  • Examples of (cyclo) aliphatic hydrocarbons include decalin, alkylated decalin and isomer mixtures of straight-chain or branched alkanes and / or cycloalkanes.
  • Alcohols are, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, pentanol isomer mixtures, hexanol isomer mixtures, 2-ethylhexanol or octanol.
  • Particularly suitable is water.
  • a base for example an organic base, preferably an amine, more preferably a secondary or tertiary amine, or an inorganic base, such as alkali or alkaline earth metal oxides, hydroxides, carbonates or bicarbonates, preferably sodium hydroxide , Potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate, calcium hydroxide, milk of lime or potassium carbonate (catalytic decarboxylation).
  • a base for example an organic base, preferably an amine, more preferably a secondary or tertiary amine, or an inorganic base, such as alkali or alkaline earth metal oxides, hydroxides, carbonates or bicarbonates, preferably sodium hydroxide , Potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate, calcium hydroxide, milk of lime or potassium carbonate (catalytic decarboxylation).
  • lysine when used in the form of an ester, preferably of the methyl ester, carrying out the reaction as Desalkoxycarbonylierung under so-called "Krapcho" conditions is preferred, wherein the reaction mixture, a nucleophile, preferably a iodide or bromide, more preferably an iodide is added and is heated under these reaction conditions.
  • a nucleophile preferably a iodide or bromide, more preferably an iodide is added and is heated under these reaction conditions.
  • the microorganisms are particularly preferably Corynebacteria and particularly preferably Corynebacterium glutamicum.
  • lysine it does not matter whether lysine is isolated in pure form, is contained in a mixture obtained as an intermediate or is formed only intermediately, for example intracellularly, in the course of step a). Moreover, in the latter variant, it does not matter whether lysine is actually formed as an intermediate or whether the intermediate has only one lysine basic structure and, for example, the carboxyl group is esterified or the amino groups are substituted.
  • Phosphorus sources that can be used are phosphoric acid, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, or the corresponding sodium compounds.
  • the culture medium may further contain metal salts, for example magnesium sulfate or iron sulfate, which are necessary for growth. Further, essential growth-promoting compounds such as amino acids or vitamins may be used in addition to the above-mentioned compounds. Corresponding precursors may also be added to the culture medium.
  • the enzymatic decarboxylation is generally carried out at 0 to 100 0 C, preferably 20 to 80 0 C, more preferably 20 to 70 0 C, most preferably 20 to 60 ° C.
  • aqueous solvents can be added to the organic solvents, so that - depending on the organic solvent - single- or multi-phase reaction solutions.
  • aqueous solvents are water as well aqueous, dilute (eg 10 to 10 mM) buffer, for example having a pH in the range of about 6 to 8, such as potassium phosphate or TRIS-HCl buffer.
  • the substrates are either dissolved, suspended as solids or in emulsion in the reaction medium before.
  • the initial concentration of the reactants is in the range of about 0.1 to 20 mol / l, more preferably 0.15 to 10 mol / l or 0.2 to 5 mol / l.
  • the reaction can be carried out in all reactors suitable for such a reaction. Such reactors are known to the person skilled in the art.
  • the reaction preferably takes place in a stirred tank reactor or a fixed bed reactor.
  • the fixed bed reactor is preferably equipped with immobilized enzymes, the reaction mixture being pumped through a column filled with the enzyme. It is also possible to carry out the reaction in a fluidized bed, wherein the enzyme is used immobilized on a support.
  • the reaction mixture can be pumped continuously through the column, with the flow rate, the residence time and thus the desired conversion is controllable. It is also possible to pump the reaction mixture through a column in the circulation.
  • the reaction mixture obtained from the preceding reaction step generally contains in addition to 1, 5-pentanediamine and water still unreacted substrate, metabolites of the Subtsrats used and optionally organic solvents, and further possibly enzyme, intact or lysed microorganisms. As a rule, only the enzyme used is separated off from the reaction mixture and the reaction product is separated from any organic solvent used.
  • a separation from the enzyme is usually carried out by crystallization, precipitation, chromatography, reverse osmosis, electrophoresis, electrodialysis, extraction, distillation, filtration, absorption, centrifugation or decantation.
  • the separated enzyme can then be used for further reactions.
  • a separation from the microorganism or lysate is usually carried out by extraction, distillation, filtration, absorption, discontinuous or continuous centrifugation, Querstromzentrifugation or decantation. Separated intact microorganisms can then be used for further reactions.
  • microorganisms may still be digested, if desired, e.g. by shear.
  • the separation from the organic solvent is usually carried out by distillation, rectification.
  • a distillation column having 1 to 20 theoretical plates can be placed on the reaction vessel, in which the return can be adapted to the separation requirements.
  • the separation of the low boilers from the reaction mixture may be carried out by passing a stream of gas substantially inert under the reaction conditions (stripping), e.g. an oxygen-depleted. mixture of air and nitrogen (lean air) or preferably nitrogen or carbon dioxide are supported.
  • a stream of gas substantially inert under the reaction conditions (stripping), e.g. an oxygen-depleted. mixture of air and nitrogen (lean air) or preferably nitrogen or carbon dioxide are supported.
  • the removal of the water is then preferably carried out continuously or stepwise in a manner known per se, e.g. by vacuum, azeotropic removal, absorption, pervaporation and diffusion across membranes.
  • 1,5-pentanediamine into a salt, preferably into the hydrochloride, and to precipitate with water-soluble organic solvents, for example alcohols or acetone.
  • the precipitate can be purified by washing and / or crystallization, and the 5,5-diamine is subsequently released again by addition of a base.
  • a base for absorption are preferably molecular sieves or zeolites (pore size, for example in the range of about 3-10 Angstrom), alternatively a separation by distillation or with the aid of suitable semipermeable membranes.
  • the step c) can be phosgene-free or in the presence of phosgene, in the latter variant, the phosgenation can be carried out in the liquid phase or in the gas phase.
  • Phosgene-free processes for the preparation of isocyanates are known, for example, from EP 18588 A1, EP 28338 A2, EP 27952, EP 126299 and in particular EP 566925 A2.
  • the amine is reacted with urea and at least one, preferably exactly one, alcohol in a molar ratio of amine, urea and alcohol such as 1: 2 to 20: 5 to 40 at temperatures of 50-300 ° C. and in particular 180 ° C. 220 0 C under a pressure of 0.1 to 30 bar, preferably 5 - 20 bar reacted. Under these reaction conditions, the process has average reaction times of fractions of seconds to minutes.
  • the reaction can conveniently be carried out in the presence of dialkyl carbonates, advantageously in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, or carbamic acid alkyl esters in an amount of 1 to 20 mol%, preferably of 5 to 15 mol%, based on the diamine.
  • dialkyl carbonates advantageously in an amount of 0.1 to 30 mol%, preferably 1 to 10 mol%, or carbamic acid alkyl esters in an amount of 1 to 20 mol%, preferably of 5 to 15 mol%, based on the diamine.
  • dialkyl carbonates and / or carbamic acid esters are those whose alkyl radicals correspond to the alkyl radical of the alcohol used.
  • the reaction can also be carried out in the presence of catalysts.
  • catalysts are expediently used in amounts of from 0.001 to 20% by weight, preferably from 0.001 to 5% by weight, in particular from 0.01 to 0.1% by weight, based on the weight of the amine.
  • Suitable catalysts are inorganic or organic compounds containing one or more cations, preferably a cation of metals of group IA, IB, IIA, IIB, HIB, IVA, IVB, VA, VB, VIB, VIIB, VIIIB of the Periodic Table of the Elements as defined in Handbook of Chemistry and Physics 14th Edition, published by Chemical Rubber Publishing Co., 23 Superior Ave. NE, Cleveland, Ohio.
  • the cations of the following metals may be mentioned by way of example: lithium, sodium, potassium, magnesium, calcium, aluminum, gallium, tin, lead, bismuth, antimony, copper, silver, gold, zinc, mercury, cerium, titanium, vanadium, chromium, molybdenum, Manganese, iron and cobalt.
  • the catalyst may further contain at least one anion, for example halides, such as chlorides and bromides, sulfates, phosphates, nitrates, borates, alcoholates, phenates, sulfonates, oxides, oxide hydrates, hydroxides, carboxylates, chelates, carbonates and thio- or dithiocarbamates.
  • halides such as chlorides and bromides, sulfates, phosphates, nitrates, borates, alcoholates, phenates, sulfonates, oxides, oxide hydrates, hydroxides, carboxylates, chelates, carbonates and thio- or dithiocarbamates.
  • the catalysts can also be used in the form of their hydrates or ammoniaates without noticeable significant disadvantages.
  • Examples of typical catalysts are: lithium methoxide, lithium ethanolate, lithium propoxide, lithium butanolate, sodium methoxide, potassium tert-butoxide, magnesium methoxide, calcium methoxide, tin (II) chloride, tin (IV) chloride, Lead acetate, lead phosphate, antimony (III) chloride, antimony (V) chloride, aluminum acetylacetonate, aluminum isobutoxide, aluminum trichloride, bismuth (III) chloride, copper (II) acetate, copper (II) sulfate, copper (II) nitrate, bis (triphenylphosphine oxido) copper (II) chloride, copper molybdate, silver acetate, gold acetate, zinc oxide, zinc chloride, zinc acetate, zinc acetonyl acetate, zinc octoate, zinc oxalate, zinc hexy-lat, Zinc benzoate,
  • Examples of preferred catalysts are the following compounds: lithium butanolate, aluminum acetylacetonate, zinc acetylacetonate, titanium tetrabutoxide and zirconium tetrabutoxide.
  • the mixing of the educt streams can preferably be carried out in a suitable special mixing device, which is characterized by short mixing times.
  • the mixed educt stream is then passed to a reaction device which may be backmixed or designed as a tubular reactor or a combination thereof.
  • the reaction mixture is reacted in the reactor at an average of 10 seconds to 5 hours, preferably 20 seconds to 20 minutes, more preferably 30 seconds to 10 minutes.
  • the temperature is generally between 50 0 C and 300 0 C, preferably between 180 0 C and 220 0 C.
  • the pressure is generally between 0.1 bar abs and 30 bar abs and preferably between 5 and 20 bar abs.
  • the residence time is chosen so that the conversion, based on amino groups in the amine used to urethane groups, after leaving the reactor is at least 95%, preferably at least 98, more preferably at least 99 and most preferably at least 99.5%.
  • the conversion based on amino groups in the amine used to form urethane groups, is not complete after leaving the reactor and is, for example, less than 95%, then the discharge can be further reacted.
  • ammonia is separated by distillation. This succeeds in a good
  • the separation takes place in a pressure range of 0.01 to 20 bar, preferably 0.04 to 15 bar.
  • the necessary temperatures depend on the alcohol or alcohol mixture used.
  • the temperature is for example at 60-150 0 C, preferably at 80 to 140 0 C.
  • This distillation unit is of a known type and has the usual installations.
  • all standard installations are suitable as column internals, for example trays, packings and / or fillings.
  • trays bubble-cap trays, sieve trays, valve trays, Thormann trays and / or dual-flow trays are preferred; of the trays are those with rings, coils, calipers, Raschig, Intos or Pall rings, Barrel or Intalox saddles, Top-Pak etc. or braids preferred.
  • Floors are preferably used, more preferably bubble trays.
  • the distillation column preferably has 10 to 20 theoretical plates. Alcohol, dialkyl carbonates, if they are formed or present in the reaction mixture, or alkyl carbamates or mixtures of at least two of these components are then removed from the resulting ammonia-depleted reaction mixture and preferably recycled to the reaction stage.
  • the reaction mixture is advantageously expanded from the pressure level of the reaction stage to a pressure in the range from 1 to 500 mbar, preferably from 10 to 100 mbar.
  • the resulting vapors are separated in subsequent expedient purification stages, preferably by rectification, and the isolated products of value alcohol and Carbamidklarealkylester, individually or as a mixture, preferably recycled to the reaction stage to form the monomeric urethanes.
  • This apparatus may be a container or a combination of container and column, preferably a column, wherein in the head of the alcohol or the alcohol mixture and in the bottom, the urethane can be withdrawn. In the top of the column, in addition to the alcohol, more easily than the urethane boiling substances may be included.
  • the separation takes place in a pressure range of 0.001 to 1 bar, preferably 0.02 to 0.5 bar.
  • the liquid mixture containing the monomeric diurethanes, and optionally oligourea-polyurethanes and high-boiling oligomers obtained after removal of the vapors in the rule as sump discharge can either be performed completely in the subsequent stage or is preferably divided into two partial streams, wherein the weight ratio of the subsets 5 to 50:95 to 50 parts by weight, preferably 10 to 30:90 to 70 parts by weight.
  • the equal or preferably smaller subset is separated by distillation by means of a conventional distillation unit, preferably a thin film evaporator, at a temperature of 170 to 240 0 C, preferably from 180 to 230 0 C and under a pressure of 0.001 - 1 bar, preferably 0.002 - , 01 bar, into a desired product which contains the diurethanes and the lower-boiling by-products, and non-distillable by-products which are separated from the preparation process and are usually discarded as non-recyclable residue.
  • the desired product (distillate) is combined with the same or preferably larger other subset and fed the combined diurethane containing reaction mixture of the thermal cleavage.
  • Thin-film evaporators or short-path evaporators can be used as distillation devices.
  • the urethane is distilled at pressures of 0.001-1 bar, preferably in the range of 0.002-0.01 bar.
  • the distillate is fed to the cleavage.
  • the resulting diurethane-containing reaction mixture is in a suitable apparatus, preferably solvent-free in the liquid phase in the presence of catalysts at temperatures of 200 to 300 0 C, preferably 220 to 280 0 C and under reduced pressure of 0.01 - 0.6 bar , preferably continuously thermally split in the range of 0.02-0.1 bar.
  • the conversion of diurethane to diisocyanate in the apparatus for thermal cleavage can be chosen largely freely and is expediently in a range of 10 to 98 wt.%, Preferably 40 to 90 wt.% Of the amount supplied.
  • the uncleaved portion of the reaction mixture which contains unreacted diurethanes, oligourea-polyurethanes, high-boiling oligomers and other recyclable and unreachable by-products, is separated, continuously discharged from the cleavage apparatus and recycled directly or optionally after reaction with alcohol in the reurethanization in the reaction stage.
  • Particularly useful and therefore preferably used are dibutyltin dilaurate, iron (III) acetylacetonate, cobalt (II) acetylacetonate, zinc acetylacetonate, zirconium tetra-n-butoxide and tin (II) dioctoate.
  • cleavage devices are, for example, cylindrical cleavage reactors, such as tube ovens or preferably evaporator, for example, thin-film or Bulk evaporators, such as Robert evaporator, Herbert evaporator, caddle-type evaporator, Plattenspalter and preferably Schukerzenverdampfer.
  • cylindrical cleavage reactors such as tube ovens or preferably evaporator
  • thin-film or Bulk evaporators such as Robert evaporator, Herbert evaporator, caddle-type evaporator, Plattenspalter and preferably Schukerzenverdampfer.
  • the separation of the cleavage products takes place in a column, in which usually the isocyanate in the side and the alcohol are taken off at the top.
  • the crude isocyanate mixture is freed in a subsequent distillation of recombination products, by-products and, if present, the solvent.
  • the by-products are preferably recycled to the thermal cleavage. A part can also be removed.
  • the crude isocyanate mixture preferably obtained by rectification, is purified by distillation at a temperature of from 100 to 180 ° C. and under a pressure of from 1 to 50 mbar, the individual fractions being recycled or isolated as a pure product.
  • the top fraction which is preferably composed of diisocyanate
  • the side fraction consisting of pure diisocyanate, preferably with a purity of at least 98 % By weight, in particular more than 99% by weight, is discharged and fed to the storage and the bottoms fraction, which contains as essential components the partially split diurethanes and diisocyanates, is preferably recycled to the cleavage device for thermal cleavage.
  • reaction of the reaction effluent and / or distillation residues are preferably recirculated to the process.
  • the isocyanate groups contained in this mixture and / or allophanates and / or ureas or other reactive constituents are converted to urethanes with alcohol. It is possible, these reactions in separate reactors such.
  • For the alcoholysis of the residues are
  • the streams can be combined with alcohol, wherein the molar ratio of NCO groups or their equivalents, ie for example urethane groups, to hydroxy groups up to 1: 100, preferably up to 1: 20, particularly preferably up to 1: 10.
  • This reaction mixture is in the presence or absence of catalysts within 1 to 150 minutes, preferably 3 to 60 minutes at a temperature of 20 to 200 0 C, preferably 50 to 170 0 C at a pressure of 0.5 to 20 bar, preferably 1 to 15 bar implemented.
  • the reaction can be carried out in a continuous boiler cascade or in a tubular reactor.
  • catalysts in principle, all compounds in question, which promote the reaction of NCO- with OH groups. Examples which may be mentioned are tin octoate, dibutyltin dilaurate, tin chloride, zinc dichloride, tin (II) dioctoate and triethylamine.
  • the 1, 5-pentanediamine obtained from step b) is optionally pre-dissolved in free form or optionally as a hydrochloride in a solvent.
  • the water content of the used in the step c) 1, 5-pentanediamine depends on the nature of the reaction in step c) and should in the case of a phosgenation preferably below 200 ppm by weight, in the case of a phosgene-free implementation preferably below 10% by weight, particularly preferably below 1% by weight and very particularly preferably below 1000 ppm by weight.
  • chlorobenzene o- or p-dichlorobenzene, trichlorobenzene, chlorotoluenes, chlorol, chloroethylbenzene, chloronaphthalenes, chlorodiphenyls, methylene chloride, perchlorethylene, toluene, xylene, hexane, decahydronaphthalene, diethyl isophthalate (DEIP) and other carboxylic acid esters, such as No. 5,136,086, column 3, lines 3 to 18, tetrahydrofuran (THF), dimethylformamide (DMF), benzene and mixtures thereof are preferred. Particularly preferred is chlorobenzene and dichlorobenzene.
  • the content of amine in the amine / solvent mixture is usually between 1 and 50% by mass, preferably between 2 and 40% by mass, more preferably between 3 and 30% by mass.
  • the phosgene is used as a mixture with the same or another inert solvent, preferably the same, or pure. Particularly preferred as phosgene is at least partially a recycled stream from the workup used, which is supplemented according to the desired stoichiometry by fresh phosgene.
  • the phosgene can generally be used in the form of 10 to 100, preferably 30 to 95 and in particular 40 to 90% strength by weight, solutions in inert solvents, the phosgene preferably being used for this purpose same solvent as used for the amine.
  • the mixing of the educt streams is preferably carried out in a suitable special mixing device, which is characterized by low mixing times.
  • the temperature in the reaction is generally between 90 0 C and 250 0 C, preferably between 100 0 C and 240 0 C and particularly preferably between 1 10 and 230 0 C.
  • the generation of the gas phase in the bottom of the column is carried out by the operation of an evaporator which may be installed in the sump, for example a Robert evaporator, or in circulation with an external evaporator, for. B. tube or plate heat exchanger.
  • an evaporator which may be installed in the sump, for example a Robert evaporator, or in circulation with an external evaporator, for. B. tube or plate heat exchanger.
  • the compounds occurring in the course of the reaction ie starting materials (diamine and phosgene), intermediates (in particular the intermediately formed mono- and dicarbamoyl chlorides), end products (diisocyanate), and optionally metered inert compounds, among the Reaction conditions remain in the gas phase.
  • starting materials diamine and phosgene
  • intermediates in particular the intermediately formed mono- and dicarbamoyl chlorides
  • end products diisocyanate
  • optionally metered inert compounds among the Reaction conditions remain in the gas phase.
  • these or other components e.g. deposited on the reactor wall or other apparatus components, it can be changed by these deposits, the heat transfer or the flow through the affected components undesirable. This is especially true for occurring amine hydrochlorides, which are formed from free amino groups and hydrogen chloride (HCl), since the resulting amine hydrochlorides are easily precipitated and are difficult to re-evaporate.
  • the reaction generally starts with contact of the reactants immediately after mixing.
  • the reaction of phosgene with amine in the reaction space takes place at absolute pressures of more than 0.1 bar to less than 20 bar, preferably between 0.5 bar and 15 bar and particularly preferably between 0.7 and 10 bar.
  • the absolute pressure is very particularly preferably between 0.7 bar and 5 bar, in particular from 0.8 to 3 bar and especially 1 to 2 bar.
  • the pressure in the feed lines to the mixing device is higher than the above-mentioned pressure in the reactor. Depending on the choice of mixing device drops at this pressure.
  • the pressure in the supply lines is preferably 20 to 2000 mbar, particularly preferably 30 to 1000 mbar, higher than in the reaction space.
  • the gaseous reaction mixture passes through the reaction space at a flow rate of 10 to 300 meters / second, preferably from 25 to 250 meters / second, more preferably 40 to 230, most preferably 50 to 200, in particular more than 150 to 190 and especially 160 to 180 meters / second.
  • the pressure in the workup device is lower than in the reaction space.
  • the pressure is preferably 50 to 500 mbar, more preferably 80 to 150 mbar, lower than in the reaction space.
  • the laundry may be placed in a stirred tank or other conventional equipment, e.g. in a column or mixer-settler apparatus.
  • a suitable quench is known, for example, from EP-A1 1403248, Sp. 2, Z. 39 - Sp. 3, Z. 18, to which reference is expressly made in the scope of this disclosure.
  • chain extenders it is possible to use generally known compounds, for example diamines and / or alkanediols having 2 to 10 C atoms in the alkylene radical, in particular ethylene glycol and / or butanediol-1, 4, and / or hexanediol and / or di- and / or Tri-oxyalkylene glycols having 3 to 8 carbon atoms in the oxyalkylene radical, preferably corresponding oligo-polyoxypropylene glycols, it also being possible to use mixtures of the chain extenders.
  • diamines and / or alkanediols having 2 to 10 C atoms in the alkylene radical in particular ethylene glycol and / or butanediol-1, 4, and / or hexanediol and / or di- and / or Tri-oxyalkylene glycols having 3 to 8 carbon atoms in the oxyalkylene radical, preferably corresponding oligo-pol
  • chain extenders it is also possible to use 1,4-bis (hydroxymethyl) benzene (1,4-BHMB), 1,4-bis (hydroxyethyl) benzene (1,4-BHEB) or 1,4-bis (2 -hydroxyethoxy) -benzene (1, 4-HQEE) are used.
  • Preferred chain extenders are ethylene glycol and hexanediol, particularly preferably ethylene glycol.
  • the preparation of the TPU is usually carried out by conventional methods, such as by belt systems or reaction extruder.

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Abstract

L'invention concerne un procédé de fabrication de pentaméthylèn- 1,5-diisocyanate, le pentaméthylèn- 1,5-diisocyanate ainsi obtenu et son utilisation.
EP07787876A 2006-08-01 2007-07-25 Procédé de fabrication de pentaméthylèn-1,5-diisocyanate Ceased EP2049675A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP07787876A EP2049675A1 (fr) 2006-08-01 2007-07-25 Procédé de fabrication de pentaméthylèn-1,5-diisocyanate
EP11172650A EP2418198A1 (fr) 2006-08-01 2007-07-25 Pentaméthylène-1,5-diisocyanate

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP06118256 2006-08-01
PCT/EP2007/057646 WO2008015134A1 (fr) 2006-08-01 2007-07-25 Procédé de fabrication de pentaméthylèn-1,5-diisocyanate
EP07787876A EP2049675A1 (fr) 2006-08-01 2007-07-25 Procédé de fabrication de pentaméthylèn-1,5-diisocyanate

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EP11172650A Withdrawn EP2418198A1 (fr) 2006-08-01 2007-07-25 Pentaméthylène-1,5-diisocyanate

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Families Citing this family (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101981202B (zh) * 2008-01-23 2013-09-11 巴斯夫欧洲公司 发酵生产1,5-二氨基戊烷的方法
JP5254121B2 (ja) * 2009-04-22 2013-08-07 三井化学株式会社 ポリイソシアヌレート組成物およびその製造方法、および、ポリウレタン樹脂
JP5700575B2 (ja) * 2010-03-01 2015-04-15 三井化学株式会社 １，５−ペンタメチレンジイソシアネートの製造方法
JP2011201863A (ja) * 2010-03-01 2011-10-13 Mitsui Chemicals Inc ペンタメチレンジイソシアネート、ポリイソシアネート組成物、ペンタメチレンジイソシアネートの製造方法、および、ポリウレタン樹脂
JP5764336B2 (ja) * 2011-01-28 2015-08-19 三井化学株式会社 ペンタメチレンジイソシアネートの製造方法
KR101604961B1 (ko) 2011-03-09 2016-03-18 미쓰이 가가쿠 가부시키가이샤 펜타메틸렌 다이아이소사이아네이트, 펜타메틸렌 다이아이소사이아네이트의 제조 방법, 폴리아이소사이아네이트 조성물, 폴리우레탄 수지 및 폴리유레아 수지
CN104684881A (zh) * 2012-11-27 2015-06-03 株式会社吴羽 羰基化合物的制备方法
US20160289165A1 (en) * 2013-11-19 2016-10-06 Toray Industries, Inc. 1,5-pentamethylene diamine and production method therefor
WO2015095553A1 (fr) 2013-12-20 2015-06-25 Nephrogenesis, Llc Procédés et appareils de dialyse rénale
US10173970B2 (en) 2014-09-19 2019-01-08 Covestro Deutschland Ag Method for producing 1,5-pentanediisocyanate in the gas phase
CN107428904B (zh) 2015-03-16 2021-05-25 科思创德国股份有限公司 基于1,5-二异氰酸根合戊烷的亲水性多异氰酸酯
WO2016146474A1 (fr) 2015-03-17 2016-09-22 Covestro Deutschland Ag Polyisocyanates à base de 1,5-diisocyanatopentane, contenant des groupes silane
US10358576B2 (en) 2015-04-20 2019-07-23 Basf Se Two-component coating compounds
CN107438634A (zh) 2015-04-21 2017-12-05 科思创德国股份有限公司 基于1,5‑二异氰酸根合戊烷的多异氰酸酯混合物
CN106045882A (zh) * 2016-06-03 2016-10-26 山东崇舜化工有限公司 一种合成五亚甲基二异氰酸酯的方法
CN109476812B (zh) * 2016-07-28 2021-04-20 科思创德国股份有限公司 低硬度聚氨酯分散体
CN109415307B (zh) * 2016-10-26 2021-06-04 三井化学株式会社 五亚甲基二异氰酸酯的制造方法
WO2018092717A1 (fr) * 2016-11-16 2018-05-24 三井化学株式会社 Mousse de polyuréthanne, matière de vêtement, rembourrage de soutien-gorge, bonnet de soutien-gorge, et procédé de production de mousse de polyuréthanne
EP3580256B1 (fr) * 2017-02-08 2021-09-15 Covestro (Netherlands) B.V. Composition de revêtement aqueux
US20210107865A1 (en) * 2017-03-28 2021-04-15 Covestro Deutschland Ag Aliphatic amine and its preparation method and use
CN107602419B (zh) * 2017-10-23 2020-05-12 南京工业大学 一种基于二氧化碳耦合的1，5-戊二异氰酸酯制备方法
CN108689884A (zh) * 2018-08-01 2018-10-23 南京工业大学 一种1,5-戊二异氰酸酯的制备方法
JP2022068377A (ja) * 2019-03-04 2022-05-10 太陽ホールディングス株式会社 ジアミン化合物の精製方法
KR102364914B1 (ko) * 2019-12-06 2022-02-18 에스케이씨 주식회사 디이소시아네이트 조성물 및 광학 렌즈의 제조방법
KR102456419B1 (ko) * 2019-12-06 2022-10-19 에스케이씨 주식회사 디이소시아네이트 조성물 및 광학 렌즈의 제조방법
KR102456421B1 (ko) * 2019-12-06 2022-10-19 에스케이씨 주식회사 디이소시아네이트 조성물 및 광학 렌즈의 제조방법
KR102456416B1 (ko) * 2019-12-06 2022-10-19 에스케이씨 주식회사 디아민 조성물, 및 이를 이용한 디이소시아네이트 조성물 및 광학 재료의 제조방법
CN115702183A (zh) 2020-06-15 2023-02-14 巴斯夫欧洲公司 高机械性能、抗紫外线辐射良好和低起霜起雾的热塑性聚氨酯组合物
CN114105825A (zh) * 2020-08-27 2022-03-01 中国科学院过程工程研究所 一种1,5-戊二异氰酸酯的制备方法
WO2022043428A1 (fr) * 2020-08-28 2022-03-03 Basf Se Granulés expansés faits de polyuréthane thermoplastique
EP4225731A1 (fr) * 2020-10-10 2023-08-16 Mojia Biotech Ltd. Procédé amélioré pour produire du diisocyanate 1,5-pentaméthylène à partir de sel de cadavérine
US20220356150A1 (en) 2021-04-30 2022-11-10 Evoco Limited Biobased diisocyanates, and process for preparation of same
CN113461894A (zh) * 2021-08-25 2021-10-01 上海壳麦科技有限公司 一种由生物基异氰酸酯合成的海绵及由该海绵所制备的床垫
CN114149345B (zh) * 2021-12-09 2023-04-21 万华化学集团股份有限公司 一种制备异氰酸酯的方法
CN114407145B (zh) * 2022-02-24 2024-05-31 上海壳麦科技有限公司 一种生物基mdi粘合的欧松板的制备方法及其产品
WO2023193178A1 (fr) * 2022-04-07 2023-10-12 Mojia (Shanghai) Biotechnology Co., Ltd. Polyuréthanes thermoplastiques et élastomères produits à partir de diisocyanate de 1,5-pentaméthylène biosourcé

Family Cites Families (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3424780A (en) 1964-03-16 1969-01-28 Upjohn Co Process for manufacturing polyisocyanates
DE1900514B2 (de) 1969-01-07 1976-08-26 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von aliphatischen diisocyanaten
DE2625075A1 (de) 1976-06-04 1977-12-22 Basf Ag Verfahren zur herstellung von carbamidsaeurechloriden und isocyanaten
DE2917490A1 (de) 1979-04-30 1980-11-13 Basf Ag Verfahren zur herstellung von aliphatischen und cycloaliphatischen di- und polyurethanen
DE2942503A1 (de) 1979-10-20 1981-05-07 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von aromatischen di- und/oder polyisocyanaten
DE2943480A1 (de) 1979-10-27 1981-05-07 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von n,o-disubstituierten urethanen, sowie ihre verwendung als ausgangsmaterial zur herstellung von isocyanaten
DE3314788A1 (de) 1983-04-23 1984-10-25 Basf Ag, 6700 Ludwigshafen Mehrstufenverfahren zur herstellung von hexamethylendiisocyanat-1,6 und/oder isomeren aliphatischen diisocyanaten mit 6 kohlenstoffatomen im alkylenrest
US4601859A (en) 1984-05-04 1986-07-22 Allied Corporation Selective hydrogenation of aliphatic dinitriles to omega-aminonitriles in ammonia with supported, finely dispersed rhodium-containing catalyst
FR2603278B1 (fr) * 1986-09-03 1988-11-18 Rhone Poulenc Chimie Procede de preparation de polyisocyanate a groupement biuret
DE3714439A1 (de) 1987-04-30 1988-11-10 Bayer Ag Verfahren zur herstellung von (cyclo)aliphatischen diisocyanaten
JPH02311452A (ja) 1989-05-26 1990-12-27 Daicel Chem Ind Ltd ジイソシアネート化合物
DE4213099A1 (de) 1992-04-21 1993-10-28 Basf Ag Mehrstufiges Verfahren zur kontinuierlichen Herstellung von organischen Polyisocyanaten
IT1255763B (it) 1992-05-15 1995-11-15 Franco Rivetti Procedimento per la preparazione di isocianati alchilici
DE4217019A1 (de) 1992-05-22 1993-11-25 Bayer Ag Verfahren zur Herstellung von aromatischen Diisocyanaten
FR2697017B1 (fr) 1992-10-16 1995-01-06 Rhone Poulenc Chimie Procédé de préparation de composés du type isocyanates aromatiques en phase gazeuse.
JP2000044649A (ja) 1998-08-03 2000-02-15 Asahi Chem Ind Co Ltd 新規な水性（ブロック）ポリイソシアネート組成物及びそれを用いた水性塗料組成物
JP2002223771A (ja) 2001-02-01 2002-08-13 Toray Ind Inc カダベリンの製造方法
DE10133729A1 (de) 2001-07-11 2003-01-23 Bayer Ag Verfahren zur Herstellung von (cyclo)aliphatischen Diisocyanaten
DE10133728A1 (de) 2001-07-11 2003-01-23 Bayer Ag Verfahren zur Herstellung von (cyclo)aliphatischen Diisocyanaten
DE10158160A1 (de) 2001-11-28 2003-06-12 Basf Ag Herstellung von Isocyanaten in der Gasphase
DE10223827A1 (de) 2002-05-28 2003-12-11 Basf Ag Verfahren zur Reduzierung des Gehalts an einem ungesättigten Amin in einer Mischung enthaltend ein Aminonitril, ein Diamin, ein Dinitril oder deren Gemische
DE10238995A1 (de) 2002-08-20 2004-02-26 Basf Ag Gasphasenphosgenierung bei moderaten Drücken
DE10245704A1 (de) 2002-09-30 2004-04-01 Bayer Ag Verfahren zum Quenchen eines gasförmigen Reaktionsgemisches bei der Gasphasenphosgenierung von Diaminen
JP4201582B2 (ja) 2002-11-26 2008-12-24 旭化成ケミカルズ株式会社 イソシアヌレート基を含有するポリイソシアネート組成物
JP2004222569A (ja) 2003-01-22 2004-08-12 Toray Ind Inc コリネ型細菌、ならびにカダベリンもしくはその塩およびそれらの製造方法
DE10307141A1 (de) 2003-02-20 2004-09-02 Bayer Ag Verfahren zur Herstellung von (Poly)isocyanaten in der Gasphase
EP1482055B1 (fr) * 2003-05-26 2006-03-01 Ajinomoto Co., Inc. Méthode pour la préparation de carboxylate de cadaverine et son utilisation pour la production de nylon
DE10359627A1 (de) 2003-12-18 2005-07-21 Bayer Materialscience Ag Verfahren zur Herstellung von Diisocyanaten
DE102004026152A1 (de) 2004-05-28 2005-12-15 Basf Ag Fermentative Herstellung von Feinchemikalien
DE102004030164A1 (de) 2004-06-22 2006-01-19 Basf Ag Verfahren zur Herstellung von Isocyanaten
EP2949755B1 (fr) 2004-07-15 2018-03-28 DSM IP Assets B.V. Synthèse biochimique de 1,4-butanediamine
DE102005042392A1 (de) 2005-09-06 2007-03-08 Basf Ag Verfahren zur Herstellung von Isocyanaten

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PANKE S ET AL: "Advances in biocatalytic synthesis of pharmaceutical intermediates", CURRENT OPINION IN CHEMICAL BIOLOGY, CURRENT BIOLOGY LTD, LONDON, GB LNKD- DOI:10.1016/J.CBPA.2005.02.007, vol. 9, no. 2, 1 April 2005 (2005-04-01), pages 188 - 194, XP004848122, ISSN: 1367-5931 *
See also references of WO2008015134A1 *

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US8044166B2 (en) 2011-10-25
EP2418198A1 (fr) 2012-02-15
US20090292100A1 (en) 2009-11-26

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