WO2013076053A1 - Synthese von polyalkylenpolyaminen mit einer geringen farbzahl durch homogen-katalysierte alkohol-aminierung unter anwesenheit von wasserstoff - Google Patents

Synthese von polyalkylenpolyaminen mit einer geringen farbzahl durch homogen-katalysierte alkohol-aminierung unter anwesenheit von wasserstoff Download PDF

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WO2013076053A1
WO2013076053A1 PCT/EP2012/073051 EP2012073051W WO2013076053A1 WO 2013076053 A1 WO2013076053 A1 WO 2013076053A1 EP 2012073051 W EP2012073051 W EP 2012073051W WO 2013076053 A1 WO2013076053 A1 WO 2013076053A1
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aliphatic
process according
bis
catalyst
polyamines
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PCT/EP2012/073051
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German (de)
English (en)
French (fr)
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Julia Strautmann
Thomas Schaub
Stephan Hüffer
Steffen Maas
Rocco Paciello
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Basf Se
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Priority to CN201280057369.5A priority Critical patent/CN103987757A/zh
Priority to EP12787744.7A priority patent/EP2782949A1/de
Priority to BR112014012440A priority patent/BR112014012440A2/pt
Priority to JP2014542794A priority patent/JP2014534249A/ja
Priority to IN3935CHN2014 priority patent/IN2014CN03935A/en
Priority to KR1020147017514A priority patent/KR20140098204A/ko
Publication of WO2013076053A1 publication Critical patent/WO2013076053A1/de

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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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines

Definitions

  • the present invention relates to a process for the preparation of polyalkylenepolyamines having a low color number by homogeneously catalyzed alcohol amination of alkanolamines or of di- or polyamines with diols or polyols in the presence of hydrogen. Furthermore, the invention also relates to polyalkylenepolyamines obtainable by these processes and the use of polyalkylenepolyamines. Another object of the invention are specific Polyalkylenpolyamie with hydroxyl groups, secondary amine groups or tertiary Amingrup- pen.
  • Polyethyleneimines are valuable products with a variety of different uses.
  • polyethyleneimines are used: a) as adhesion promoter for printing inks for laminate films; b) as an aid (adhesion) for the production of multilayer composite films, whereby not only different polymer layers but also metal foils are made compatible; c) as a bonding agent for adhesives, for example in conjunction with Polyvi- nylalkohol, butyrate, and acetate and styrene copolymers, or as a cohesion promoter for label adhesives; d) low molecular weight polyethyleneimines can also be used as crosslinkers / hardeners in epoxy resins and polyurethane adhesives; e) as a primer in paint applications to improve adhesion to substrates such as glass, wood, plastic and metal; f) to improve the wet adhesion in standard emulsion paints and to improve the instantaneous rainfastness of paints, for example for road markings; g) as
  • polyalkylene polyamines which are not derived from ethyleneimine can also be used for these applications.
  • Polyethyleneimines are currently obtained by the homopolymerization of ethyleneimine.
  • Ethyleneimine is a highly reactive, corrosive and toxic intermediate which can be prepared in a variety of ways (Aziridine, Ulrich Steuerle, Robert Feuerhake, in Ullmann 's Encyclopedia of Industrial Chemistry, 2006, Wiley-VCH, Weinheim).
  • the ethyleneimine can be obtained by reacting 1, 2-dichloroethane with three equivalents of ammonia. Disadvantages are the use of large amounts of ammonia, the formation of the by-product ammonium chloride, the corrosivity of the reaction mixture and impurities of the product.
  • the ethyleneimine is obtained by the catalytic dehydrogenation of 2-aminoethanol in the gas phase at 250-450 ° C. Disadvantages of this process are the complicated product work-up by distillation, the high energy requirement and the low catalyst life.
  • EP 0 034 480 A2 discloses the preparation of N-alkyl or ⁇ , ⁇ -dialkylamines by the reaction of primary or secondary amines with a primary or secondary alcohol using an iridium, rhodium, ruthenium, osmium, platinum , Palladium or Rhenium ummatalysators disclosed.
  • EP 0 239 934 A1 describes the synthesis of mono- and diaminated products starting from diols such as ethylene glycol and 1,3-propanediol with secondary amines using ruthenium and iridium phosphine complexes.
  • Incl. Fujita, R. Yamaguchi Synlett, 2005, 4, 560-571 describes the synthesis of secondary amines by the reaction of alcohols with primary amines and the synthesis of cyclic amines by the reaction of primary amines with diols by ring closure using iridium catalysts.
  • the object of the present invention is to find a process for the preparation of polyalkylenepolyamines in which no aziridine is used, no undesired by-products are formed, products of a desired chain length are obtained and the color number of the product is as low as possible.
  • the object is achieved by a process for the preparation of polyalkylenepolyamines by homogeneously catalyzed alcohol amination in which (i) aliphatic amino alcohols with each other or (ii) aliphatic diamines or polyamines with aliphatic diols or polyols with elimination of water in the presence of a homogeneous catalyst and hydrogen gas.
  • this reaction takes place at pressures between 0.1 and 25 MPa and temperatures between 100 and 200 ° C.
  • Expressions of the form C a -C b designate in the context of this invention chemical compounds or substituents with a certain number of carbon atoms.
  • the number of carbon atoms can be selected from the entire range from a to b, including a and b, a is at least 1 and b is always greater than a.
  • Further specification of the chemical compounds or substituents is made by terms of the form C a -C b -V.
  • V here stands for a chemical compound class or substituent class, for example for alkyl compounds or alkyl substituents.
  • the collective terms given for the various substituents have the following meaning:
  • C 1 -C 50 -alkyl straight-chain or branched hydrocarbon radicals having up to 50 carbon atoms, for example C 1 -C 10 -alkyl or C 2 -C 20 -alkyl, preferably C 1 -C 10 -alkyl, for example C 1 -C 3 -alkyl, such as methyl, ethyl , Propyl, isopropyl, or C 4 -C 6 -alkyl, n-butyl, sec-butyl, tert-butyl, 1, 1-dimethylethyl, pentyl, 2-methylbutyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 2-methylpentyl, 3-methyl-pentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl
  • C 3 -C 5 -cycloalkyl monocyclic, saturated hydrocarbon groups having 3 to 15 carbon ring members, preferably C 3 -C 8 -cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl and a saturated or unsaturated cyclic system such as , B. norbornyl or norbenyl.
  • Polyalkylenepolyamines can be obtained by reacting (i) aliphatic aminoalcohols with one another or from (ii) aliphatic diamines or polyamines with aliphatic diols or polyols, each in the presence of a catalyst. Surprisingly, it was found that the color number of the product decreases when hydrogen is pressed on during the reaction. In each case the product is used as a comparison, which is synthesized analogously, but without hydrogen. Therefore, polyalkylene polyamines of lower color number are obtained in accordance with the invention when hydrogen is injected before or during the synthesis of the polyalkylenepolyamines, i. the reaction is carried out in the presence of hydrogen gas.
  • the pressurization of hydrogen gas is preferably carried out at pressures of from 0.1 to 25 MPa (partial pressure of hydrogen gas), particularly preferably from 1 to 10 MPa and in particular from 1 to 7 MPa. It is preferred to set a temperature between 100 and 200 ° C, more preferably 130 to 180 ° C.
  • the color number is reduced by the pressing of the hydrogen by at least a factor of 2, preferably by a factor of 10 to 100.
  • Aliphatic amino alcohols which are suitable for reaction under a hydrogen atmosphere contain at least one primary or secondary amino group and at least one OH group.
  • Examples are linear, branched or cyclic alkanolamines such as monoethanolamine, diethanolamine, aminopropanol, for example 3-aminopropan-1-ol or 2-aminopropan-1-ol, aminobutanol, for example 4-aminobutan-1-ol, 2-aminobutane-1 -ol or 3-aminobutan-1-ol, aminopentanol, for example 5-aminopentan-1-ol or 1-aminopentan-2-ol, aminodimethylpentanol, for example 5-amino-2,2-dimethylpentanol, aminohexanol, for example 2- Aminohexan-1-ol or 6-aminohexan-1-ol, aminoheptanol, for example 2-aminoheptan-1-ol or 7-aminoh
  • Examples are ethylenediamine, 1, 3-propylenediamine, 1, 2-propylenediamine, butylenediamine, for example 1, 4-butylenediamine or 1, 2-butylenediamine, diaminopentane, for example 1, 5-diaminopentane or 1, 2-diaminopentane, 1, 5-diamino-2-methylpentane, diaminohexane, for example 1, 6-diaminohexane or 1, 2-diaminohexane, diaminoheptane, for example 1, 7-diaminoheptane or 1, 2-diaminoheptane, diaminooctane, for example 1, 8-diaminooctane or 1, 2 -Diaminooctan, diaminononane, for example 1, 9-diaminononane or 1, 2-diaminononane, diaminodecane, for example, 1,
  • aliphatic diols examples include ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 2
  • Methyl-1, 3-propanediol, butanediols for example, 1, 4-butylene glycol or butane-2,3-diol or
  • Preferred polyalkylenepolyamines obtainable under hydrogen pressure according to the invention contain C 2 -C 5 0-alkylene units, more preferably C 2 -C 2 o-alkylene units. These may be linear or branched, preferably they are linear.
  • Examples are ethylene, propylene, for example 1, 3-propylene, butylene, for example 1, 4-butylene, pentylene, for example 1, 5-pentylene or 1, 2-pentylene, hexylene, for example 1, 6-hexylene, octylene, for example 1 , 8-octylene or 1, 2-octylene, nonylene, for example 1, 9-nonylene or 1, 2-nonylene, decylene, for example 1, 2-decylene or 1, 10-decylene, undecylene, for example 1, 2-undecylene, dodecylene
  • cycloalkylene units are possible, for example, 1, 3 or 1, 4-cyclo
  • polyalkylenepolyamines may contain alkylene units of different lengths.
  • polyfunctional amino alcohols having more than one OH group or more than one primary or secondary amino group can be reacted with each other under hydrogen pressure. This highly branched products are obtained.
  • polyfunctional amino alcohols are diethanolamine, N- (2-aminoethyl) ethanolamine, diisopropanolamine, diisononanolamine, diisodecanolamine, diisoundecanolamine, diisododecanolamine, diisotridecanolamine. It is also possible to react polyols or mixtures of diols and polyols with diamines under hydrogen pressure. It is also possible to react polyamines or mixtures of diamines and polyamines with diols.
  • polyols or mixtures of diols and polyols with polyamines or mixtures of diamines and polyamines.
  • polyamines or mixtures of diamines and polyamines are glycerol, trimethylolpropane, sorbitol, triethanolamine, triisopropanolamine.
  • polyamines are diethylenetriamine, tris (aminoethyl) amine, triazine, 3- (2-aminoethylamino) -propylamine, dipropylene triamine, N, N '-bis (3-aminopropyl) ethylenediamine.
  • Particularly suitable compounds are those in which at least one of the educts contains aliphatic amino alcohols, aliphatic diamines or polyamines or aliphatic diols or polyols an alkyl or alkylene group having from 2 to 4 carbon atoms.
  • Also particularly suitable compounds for the reaction under hydrogen pressure are those in which at least one of the educts aliphatic amino alcohols, aliphatic diamines or polyamines or aliphatic diols or polyols an alkyl or alkylene group with five or more, preferably seven or more, more preferably nine or more , in particular twelve or more, contains carbon atoms.
  • Particularly suitable compounds are those in which at least one of the educts aliphatic amino alcohols, aliphatic diamines or polyamines or aliphatic diols or polyols an alkyl or alkylene group having from 5 to 50, preferably from 5 to 20, particularly preferably from 6 to 18, very particularly preferably from 7 to 16, particularly preferably from 8 to 14 and in particular from 9 to 12 carbon atoms.
  • Hydroxy and amino groups in diols, polyols and diamines, polyamines are preferably used in molar ratios of from 20: 1 to 1:20, more preferably in ratios of from 8: 1 to 1: 8, in particular from 3: 1 to 1: 3.
  • Polyalkylenepolyamines can also be reacted under hydrogen pressure. During the reaction, diamines or polyamines or diols or polyols or amino alcohols may be added. Hydrogen can be injected while the water of reaction is continuously or discontinuously separated from the system.
  • a homogeneous catalyst is understood as meaning a catalyst which is homogeneously dissolved in the reaction medium during the reaction.
  • the homogeneous catalyst generally contains at least one element of the subgroups of the periodic table (transition metal).
  • the hydrogenation under hydrogen pressure can be carried out in the presence or absence of an additional solvent.
  • Alcohol amination can be carried out in a multi-phase, preferably single-phase or two-phase, liquid system at temperatures generally from 20 to 250 ° C.
  • the lower phase of water and the homogeneously dissolved catalyst and the upper phase of a non-polar solvent, which contains the majority of the polyamines formed and the non-polar starting materials consist.
  • (i) monoethanolamine or (ii) mono-propanolamine or (iii) diamines are selected from ethylenediamine, 1,3-propylenediamine or 1,2-propylenediamine with diols selected from ethylene glycol, 1,2-decanediol or 1, 2-Dodecanediol in the presence of a homogeneous catalyst and under a hydrogen pressure of 1 to 10 MPa and with removal of the water formed in the reaction.
  • the number of alkylene units n in the polyalkylenepolyamines is generally between 3 and 50,000.
  • the polyalkylenepolyamines thus obtained can carry as end groups at the chain ends both NH 2 and OH groups.
  • R independently of one another, identical or different, denote H, C 1 -C 50 -alkyl
  • I, m are independent of each other, the same or different
  • n, k are independent of each other, the same or different
  • the number average molecular weight Mn of the polyalkylenepolyamines obtained is generally from 200 to 2,000,000, preferably from 400 to 750,000 and more preferably from 400 to 50,000.
  • the molecular weight distribution Mw / Mn is generally in the range from 1.2 to 20, preferably from 1, 5-7.5.
  • the cationic charge density (at pH 4-5) is generally in the range of 4 to 22 mequ / g dry matter, preferably in the range of 6 to 18 mequ / g.
  • polyalkylenepolyamines obtained by the process according to the invention can be present both in linear form as well as in branched or multiply branched form, as well as ring-shaped structural units.
  • the distribution of the structural units is statistical.
  • the polyalkylenepolyamines thus obtained differ from the polyethyleneimines prepared from ethyleneimine by the OH groups present and, if appropriate, by different alkylene groups.
  • the homogeneous catalyst is preferably a transition metal complex catalyst containing one or more different metals of the subgroups of the Periodic Table, preferably at least one element of Groups 8, 9 and 10 of the Periodic Table, more preferably ruthenium or iridium.
  • the subgroup metals mentioned are in the form of complex compounds. There are many different ligands in question.
  • Suitable ligands present in the transition metal complex compounds are, for example, alkyl- or aryl-substituted phosphines, multidentate alkyl- or aryl-substituted phosphines bridged by arylene or alkylene groups, nitrogen-heterocyclic carbenes, cyclopentadienyl and pentamethylcylopentadienyl, aryl, olefin ligands , Hydride, halide, carboxylate, alkoxylate, carbonyl, hydroxide, trialkylamine, dialkylamine, monoalkylamine, nitrogen aromatics such as pyridine or pyrrolidine and polyamines.
  • the organometallic complex may contain one or more different of said ligands.
  • Preferred ligands are (monodentate) phosphines or (polydentate) polyphosphines, for example diphosphines, having at least one unbranched or branched, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having 1 to 20, preferably 1 to 12 C atoms.
  • Examples of branched cyloaliphatic and araliphatic radicals are - CH 2 -C 6 HH and -CH 2 -C 6 H 5 .
  • radicals are: methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 1- (2-methyl) propyl, 2- (2-methyl) propyl, 1-pentyl, 1 -Hexyl, 1-heptyl, 1-oytyl, 1 -nonyl, 1-decyl, 1-undecyl, 1-dodecyl, cyclopentenyl, cyclohexyl, cycloheptyl and cyclooctyl, methylcyclopentyl, methylcyclohexyl, 1- (2-methyl) -pentyl , 1- (2-ethyl) -hexyl, 1- (2-propylheptyl), adamantyl and norbornyl, phenyl, tolyl and xylyl and 1-phenylpyrrole, 1- (2-methoxyphenyl) -pyrrole, 1- (2,4, 6-tri
  • the phosphine group may contain one, two or three of said unbranched or branched acyclic or cyclic, aliphatic, aromatic or araliphatic radicals. These can be the same or different.
  • the homogeneous catalyst contains a monodentate or polydentate phosphine ligand containing an unbranched, acyclic or cyclic aliphatic radical having from 1 to 12 carbon atoms or an aliphatic radical or adamantyl or 1 - phenylpyrrole as the radical.
  • phosphine groups are preferably selected from 1,2-phenylene, methylene, 1,2-ethylene, 1,2-dimethyl-1,2-ethylene, 1,3-propylene, 1,4-butylene and bridged 1, 5-propylene bridges.
  • Particularly suitable monodentate phosphine ligands are triphenylphosphine, tritolylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, trimethylphosphine and triethylphosphine and di (1-adamantyl) -n-butylphosphine, di (1-adamantyl) benzylphosphine, 2- (dicyclohexylphosphino) - 1-phenyl-1H-pyrrole, 2- (dicyclohexylphosphino) -1- (2,4,6-trimethyl-phenyl) -1H-imidazole, 2- (dicyclohexylphosphino) -I-indylindole, 2- (di-tert -butylphosphino) -1-phenylindole, 2- (dicyclohexylphosphino) -1- (2-methoxy
  • triphenylphosphine Tritolylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, trimethylphosphine and triethylphosphine and di (1 -adamantyl) -n-butylphosphine, 2- (dicyclohexylphosphino) -1-phenyl-1 H-pyrrole and 2- (di-tert-butyl-phosphino) -1-phenyl-1H-pyrrole.
  • multidentate phosphine ligands are bis (diphenylphosphino) methane 1, 2-bis (diphenylphosphino) ethane, 1, 2-dimethyl-1,2-bis (diphenylphosphino) ethane, 1, 2
  • nitrogen-heterocyclic carbenes may be mentioned as particularly suitable ligands.
  • those ligands which form water-soluble complexes with Ru are quite preferred.
  • Particularly preferred are 1-butyl-3-methylimidazolin-2-ylidene, 1-ethyl-3-methylimidazolin-2-ylidene, 1-methylimidazolin-2-ylidene and dipropylimidazolin-2-ylidene.
  • ligands are chloride, hydride and carbonyl.
  • the transition metal complex catalyst may, of course, contain several different or the same of the ligands described above.
  • the homogeneous catalysts can be used both directly in their active form and starting from conventional standard complexes such as [Ru (p-cymene) Cl 2 ] 2 , [Ru (benzene) Cl 2 ] n , [Ru (CO) 2 Cl 2 ] n , [Ru (CO) 3 Cl 2 ] 2 , [Ru (COD) (allyl)], [RuCl 3 * H 2 0], [Ru (acteylacetonate) 3 ], [Ru (DMSO) 4 Cl 2 ] , [Ru (PPh 3) 3 (CO) (H) CI], [Ru (PPh 3) 3 (CO) Cl 2], [Ru (PPh 3) 3 (CO) (H) 2], [Ru ( PPh 3) 3 Cl 2], [Ru (cyclopentadienyl) (PPh 3) 2 CI], [Ru (cyclopentadienyl) (
  • the amount of the metal component of the catalyst is generally from 0.1 to 5000 ppm by weight, based in each case on the entire liquid reaction mixture.
  • the process according to the invention can be carried out both in a solvent and without solvent. Of course, the inventive method can also be carried out in a solvent mixture.
  • the amount of solvent is frequently chosen so that the starting materials (i) and (ii) are just dissolved in the solvent.
  • the weight ratio of the amount of solvent to the amount of starting materials (i) and (ii) is from 100: 1 to 0.1: 1, preferably from 10: 1 to 0.1: 1.
  • the reaction according to the invention takes place in the liquid phase at a temperature of generally from 20 to 250.degree.
  • the temperature is at least 100 ° C and preferably at most 200 ° C.
  • the reaction may be carried out at a total pressure of 0.1 to 25 MPa absolute, which may be both the pressure of hydrogen in combination with the autogenous pressure of the solvent at the reaction temperature, and the pressure of a gas such as nitrogen or argon in combination with hydrogen become.
  • the average reaction time is generally 15 minutes to 100 hours.
  • bases can have a positive effect on product formation.
  • Suitable bases include alkali metal hydroxides, alkaline earth hydroxides, alkali metal alkoxides, alkaline earth metal alkoxides, alkali metal carbonates and alkaline earth carbonates, of which 0.01 to 100 equivalents can be used with respect to the metal catalyst used.
  • the heteroatoms O or N of one of the educts are (i) aliphatic amino alcohols, (ii) aliphatic diamines or polyamines or aliphatic diols or polyols in the alpha and beta positions on the chain of C atoms and with neighboring C atoms.
  • the heteroatoms O of one of the starting materials are (i) aliphatic amino alcohols, (ii) aliphatic diamines or polyamines or aliphatic diols or polyols in the alpha and omega position on the chain of C atoms and thus at the opposite ends of the chain of carbon atoms.
  • polyalkylenepolyamines preferably polyethyleneamine or polypropyleneamine, which are prepared according to the described embodiments of the method according to the invention.
  • polyalkylenepolyamines containing hydroxy groups, secondary amines or tertiary amines are preferably located on a terminal carbon atom of an alkylene group and thus represent an end group.
  • These polyalkylenepolyamines preferably contain hydroxyl groups.
  • these polyalkylenepolyamines which contain hydroxy groups, secondary amines or tertiary amines are obtainable by means of the process according to the invention.
  • these polyalkylenepolyamines are obtained in one process by the polymerization of monomers in one step.
  • the ratio of the number of hydroxyl end groups to amine end groups is preferably from 10: 1 to 1:10, preferably from 5: 1 to 1: 5, particularly preferably from 2: 1 to 1: 2.
  • such Polyalkylenpolyamine containing the hydroxy groups, secondary amines or tertiary amines only Hyroxy-end groups or only amine-end groups (primary, secondary, tertiary).
  • the invention also relates to the uses of the polyalkylenepolyamines a) as adhesion promoters for printing inks, b) as auxiliaries (adhesion) for the production of composite films, c) as cohesion promoters for adhesives, d) as crosslinkers / hardeners for resins, e) as G) as a complexing agent and flocculant, h) as a penetration aid in wood preservation, i) as a corrosion inhibitor j) as immobilizing agent of proteins and enzymes.
  • the polyalkylenepolyamines a) as adhesion promoters for printing inks, b) as auxiliaries (adhesion) for the production of composite films, c) as cohesion promoters for adhesives, d) as crosslinkers / hardeners for resins, e) as G) as a complexing agent and flocculant, h) as a penetration aid in wood preservation, i) as a corrosion inhibitor j)
  • the average molecular weight of the oligomers was determined by gel permeation chromatography by size exclusion chromatography.
  • the eluant used was hexafluoroisopropanol with 0.05% trifluoroacetic acid potassium salt.
  • the measurement was carried out at 40 ° C at a flow rate of 1 ml / min on a styrene-divinylbenzene copolymer column (8 mm * 30 cm) with an RI differential refractometer or UV photometer as a detector. Calibration was carried out using narrowly distributed PMMA standards.
  • the sample is diluted 1: 2500 with a diluent which does not absorb in the range of 380 to 720 nm.
  • the Hazen color number is then determined in a range of 380 to 720 nm in 10 nm increments.
  • the color numbers of the polyethylenepolyamines prepared by the processes of the known art are more than 100, sometimes more than 200, and sometimes even more than 600.
  • the product phase was shaken out with toluene. Subsequently, the water of reaction, the unreacted starting material and volatile constituents were removed on a rotary evaporator at 12 mbar and 1 16 ° C, to give 15.65 g of the pure product.
  • the weight average (RI) of the obtained oligomer was 1470 g / mol with a dispersity (Mw / Mn) of 2.8. This corresponds to an average chain length n of the oligomer (CH 2 CH 2 NH) n of 34.
  • the color number was 20.
  • the reaction water, the unreacted educt and volatiles were removed on a rotary evaporator at 12 mbar and 1 16 ° C to give 9.42 g of the pure product.
  • the weight average (RI) of the obtained oligomer was 1520 g / mol with a dispersity (Mw / Mn) of 3.4. This corresponds to an average chain length n of the oligomer (CH 2 CH 2 NH) n of 35.
  • the color number was 71.
  • the water of reaction, the unreacted educt and volatiles were removed on a rotary evaporator at 12 mbar and 1 16 ° C, whereby the pure product was obtained.
  • the weight average (RI) of the obtained oligomer was 1,170 g / mol with a dispersity (Mw / Mn) of 3.4. This corresponds to an average chain length n of the oligomer (CH 2 CH 2 NH) n of 27.
  • the color number was 54.
  • the reaction mixture is heated to 150 ° C and stirred for 20 h.
  • 20 ml of water are added to the reaction mixture and shaken to obtain a solution of the product in toluene and an aqueous solution of the catalyst.
  • the phases were separated. From the product phase, the unreacted educt and volatile components were removed on a rotary evaporator at 20 mbar and 120 ° C, to give 1 1, 97 g of the pure product.
  • the weight average (RI) of the obtained oligomer was 1470 g / mol with a dispersity (Mw / Mn) of 3.9. This corresponds to an average chain length n of the oligomer (CH 2 CH (CioH 2 i) NHCH 2 CH 2 NH) n of 6.
  • the color number was 21.

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PCT/EP2012/073051 2011-11-25 2012-11-20 Synthese von polyalkylenpolyaminen mit einer geringen farbzahl durch homogen-katalysierte alkohol-aminierung unter anwesenheit von wasserstoff WO2013076053A1 (de)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CN201280057369.5A CN103987757A (zh) 2011-11-25 2012-11-20 通过在氢气存在下均相催化醇胺化合成低比色指数的聚亚烷基多胺
EP12787744.7A EP2782949A1 (de) 2011-11-25 2012-11-20 Synthese von polyalkylenpolyaminen mit einer geringen farbzahl durch homogen-katalysierte alkohol-aminierung unter anwesenheit von wasserstoff
BR112014012440A BR112014012440A2 (pt) 2011-11-25 2012-11-20 processo para a preparação de polialquileno poliminas, polialquileno poliamina, e, uso de polialquileno poliminas
JP2014542794A JP2014534249A (ja) 2011-11-25 2012-11-20 水素の存在下でのアルコールの均一系接触アミノ化による低い色数を有するポリアルキレンポリアミンの合成
IN3935CHN2014 IN2014CN03935A (en:Method) 2011-11-25 2012-11-20
KR1020147017514A KR20140098204A (ko) 2011-11-25 2012-11-20 수소 존재 하의 균일 촉매화 알코올 아민화에 의한 낮은 색 지수를 갖는 폴리알킬렌 폴리아민의 합성

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US9550725B2 (en) * 2011-11-25 2017-01-24 Basf Se Lipophilic polyalkylenepolyamines by homogeneously catalyzed alcohol amination
TWI768076B (zh) * 2017-07-10 2022-06-21 荷蘭商安科智諾貝爾化學國際公司 製造直鏈及非直鏈伸乙基胺混合物之方法
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EP2782949A1 (de) 2014-10-01
JP2014534249A (ja) 2014-12-18
KR20140098204A (ko) 2014-08-07
IN2014CN03935A (en:Method) 2015-09-04
CN103987757A (zh) 2014-08-13

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