Classifications

• • 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
  • C08G73/0206—Polyalkylene(poly)amines
  • C08G73/0213—Preparatory process
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
  • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
  • C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
  • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton

Definitions

• the present invention relates to processes for increasing the molecular weight of polyalkylene polyamines by homogeneously catalyzed alcohol amination. Furthermore, the invention also relates to polyalkylenepolyamines, obtainable by these processes and the use of polyalkylenepolyamines. Another object of the invention are specific polyalkylenepolyamines having hydroxyl groups, secondary amine groups or tertiary amine groups.
• 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 a complexing agent with high binding capacity for heavy metals such as
• polyalkylene polyamines which are not derived from ethyleneimine.
• Polyethyleneimines are currently obtained by the homopolymerization of ethyleneimine.
• Ethyleneimine is a highly reactive, corrosive and toxic intermediate that can be prepared in a variety of ways (Aziridine, Ulrich Steuerle, Robert Feuerhake, in Ullmann 's Encyclopedia of Industrial Chemistry, 2006, Wiley-VCH, Weinheim).
• No. 3,708,539 describes the synthesis of primary, secondary and tertiary amines using a ruthenium-phosphine complex.
• Y. Watanabe Y. Tsuji, Y. Ohsugi Tetrahedron Lett. 1981, 22, 2667-2670 reports the preparation of arylamines by the amination of alcohols with aniline using [Ru (PPh3) 3C] as a catalyst.
• 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 catalyst.
• 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 was to find a process for increasing the molecular weight of polyalkylenepolyamines, in which no aziridine is used, no undesired by-products are formed and products of a desired chain length are obtained.
• a further object was to provide processes which make it possible, starting from already existing polyalkylenepolyamine starting materials, to obtain higher molecular weight polyalkylenepolyamines in comparison with these polyalkylenepolyamine starting materials.
• Water of reaction is understood as meaning the water formed during the elimination of water during the reaction of hydroxyl and amino groups of the monomers.
• Room temperature is understood to mean 21 ° C.
• 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 with 3 up to
• Aryl a mono- to trinuclear aromatic ring system containing 6 to 14 carbon ring members, e.g. As phenyl, naphthyl or anthracenyl, preferably a mono- to binuclear, more preferably a mononuclear aromatic ring system.
• Polyalkylenepolyamines can be obtained, for example, by reacting (i) aliphatic amino alcohols with elimination of water or of (ii) aliphatic diamines or polyamines with aliphatic diols or polyols with elimination of water, in each case in the presence of a catalyst.
• aliphatic amino alcohols with elimination of water
• aliphatic diamines or polyamines with aliphatic diols or polyols with elimination of water
• polyalkylene polyamines of lower molecular weight are used which have been prepared by any desired method, for example the abovementioned methods.
• These polyalkylenepolyamines of lower molecular weight can be used directly after their preparation or, if appropriate, after isolation and / or purification, preferably after the removal of water present, as starting materials for the preparation of polyalkylenepolyamines of higher molecular weight.
• the molar mass of the polyalkylenepolyamines of lower molecular weight is increased within the scope of a postcrosslinking of the first type by reacting the polyalkylenepolyamines of lower molecular weight in the presence of a homogeneous catalyst with dehydration and removing the water of reaction from the system.
• the polyalkylene polyamines of lower molecular weight preferably contain free hydroxyl and amino groups in order to enable post-crosslinking of the first type by alcohol amination. It is furthermore preferred to remove water present after preparation of the higher molecular weight polyalkylenepolyamines.
• sequence of a) reaction of the polyalkylenepolyamine lower molecular weight in the presence of a catalyst, b) separation of the water of reaction is repeated up to 30 times, wherein the molecular weight of the polyalkylenepolyamine higher molecular weight increases in each step sequence.
• first and the second preferred embodiment of the inventive method can be combined to ensure a further structure of the molecular weight.
• a so-called post-crosslinking of the second type is carried out to increase the molar mass.
• polyalkylenepolyamines of lower molecular weight are prepared which can be used in any desired manner.
• the methods described above were prepared.
• These lower molecular weight polyalkylene polyamines can be used as starting materials directly after their preparation or, if appropriate, after isolation and / or purification, preferably after removal of water present.
• the post-crosslinking of the second type is carried out, in which a polyalkylenepolyamine of lower molecular weight and (i) aliphatic amino alcohols or (ii) aliphatic diamines or polyamines with aliphatic diols or polyols are added.
• the polyalkylenepolyamine lower molecular weight and (i) aliphatic amino alcohols or (ii) aliphatic diamines or polyamines with aliphatic diols or polyols are used as starting materials and reacted with elimination of water and separation of the water of reaction from the reaction system in the presence of a homogeneous catalyst to a polyalkylenepolyamine higher molecular weight.
• An additional separation of the water of reaction can also take place after the preparation of the polyalkylenepolyamines.
• the sequence a) reaction of the polyalkylenepolyamine in the presence of a homogeneous catalyst and i) aliphatic amino alcohols or (ii) aliphatic diamines or polyamines with aliphatic diols or polyols, b) separation of the water of reaction is repeated up to 30 times, the molecular weight of the higher molecular weight polyalkylenepolyamine increases in each step.
• ethylene diamine is preferably used as the aliphatic diamine (ii).
• first, second and third preferred embodiment of the inventive method can be combined to ensure a further structure of the molecular weight.
• the second and third preferred embodiment of the method according to the invention one or more times following or alternately combine to ensure a further structure of the molecular weight.
• Aliphatic amino alcohols suitable for crosslinking of the second type contain at least one primary or secondary amino group and at least one OH group.
• 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-aminobutane-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-aminohexane 1 -ol or 6-aminohexan-1-ol, aminoheptanol, for example 2-aminoheptan-1-ol or 7-aminoheptan-1-ol, aminooctanol, for example 2-aminooctan-1-ol or 8-a
• Aliphatic diamines suitable for crosslinking of the second type contain at least two primary or at least one primary and one secondary or at least two secondary amino groups, preferably they contain two primary amino groups.
• Examples are linear branched or cyclic aliphatic diamines. 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-diamin
• Suitable aliphatic diols are linear branched or cyclic aliphatic diols.
• suitable aliphatic diols are 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 1, 2-Butylengylkol, pentanediols, for example, neopentyl glycol or 1, 5-pentanediol or 1, 2-pentanediol, hexanediols, for example, 1, 6-hexanediol or 1, 2-hexanediol, heptanediols, for example, 1, 7-heptanediol or 1 , 2-heptanediol, octanediols, for example 1, 8-octanediol or 1, 2-octanediol, nonan
• Preferred polyalkylenepolyamines obtainable according to the invention contain C 2 -C 50 -alkylene units, more preferably C 2 -C 20 -alkylene units. These may be linear or branched, preferably they are linear. Examples are ethylene, 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 1, 2-pentylene and 1, 6-hexylene, 1, 9-nonylene, 1, 10-decylene, 1, 12- Dodecylene, 1,2-octylene, 1,2-nonylene, 1,2-decylene, 1,2-undecylene, 1,2-dodecylene, 1,2-tridecylene, 1,8-ocytylene, nonylene, decylene, undecylene, Dodecylene, tridecylene, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, neopentylene. Also, cycloalkylene
• Compounds particularly suitable for crosslinking of the second type are those in which at least one of the aliphatic amino alcohols, aliphatic diamines or polyamines or aliphatic diols or polyols contains an alkyl or alkylene group having from 2 to 4 carbon atoms.
• Also particularly suitable for crosslinking of the second kind are those in which at least one of the aliphatic amino alcohols, aliphatic diamines or polyamines or aliphatic diols or polyols is an alkyl or alkylene group having five or more, preferably seven or more, more preferably nine or more, in particular contains twelve or more, carbon atoms.
• Also particularly suitable compounds for the second type of crosslinking are those in which at least one of the starting materials comprises 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.
• at least (i) monoethanolamine or (ii) ethylene glycol with ethylenediamine are preferably selected.
• preference is given here to at least ethylenediamine or 1,2-propylenediamine or 1,3-propylenediamine and 1,2-decanediol or 1,2-dodecanediol.
• 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. This highly branched products are obtained.
• polyfunctional amino alcohols are diethanolamine, N- (2-aminoethyl) ethanolamine, diisopropanolamine, diisononanolamine, diisodecanolamine, diisoundecanolamine, diisododecanolamine, diisotridecanolamine.
• polyols or mixtures of diols and polyols with diamines. It is also possible to react polyamines or mixtures of diamines and polyamines with diols. It is also possible to react polyols or mixtures of diols and polyols with polyamines or mixtures of diamines and polyamines. This highly branched products are obtained. Examples of polyols are glycerol, trimethylolpropane, sorbitol, triethanolamine, triisopropanolamine.
• polyamines examples include diethylenetriamine, tris (aminoethyl) amine, triazine, 3- (2-aminoethylamino) propylamine, dipropylenetriamine, N, N '-bis (3- minopropyl) -ethylenediamine.
• Hydroxy and amino groups in diols, polyols and diamines, polyamines are used, especially in postcrosslinking of the second kind, preferably in molar ratios of from 20: 1 to 1:20, more preferably in ratios of from 8: 1 to 1: 8, in particular of 3 : 1 to 1: 3.
• the separation of the water of reaction is carried out using a suitable water separator.
• the reaction water is separated off by means of a distillation in which the water, with or without the addition of a suitable solvent (tractor), is added to the reaction system. is withdrawn.
• the distillation is preferably carried out continuously.
• water in the distillation may be the lowest boiling component in the reaction mixture, and therefore can be removed from the system continuously or discontinuously.
• the water can be removed by distillation as an azeotrope with the addition of a suitable solvent (tractor).
• the separation of the reaction water is carried out using a device for phase separation.
• a portion of the reaction mixture is continuously passed from the reactor, optionally cooled and run in one or sequentially in several devices for phase separation, in which separate the water of reaction and the rest of the reaction mixture, and the reaction water is removed from the system , Particularly preferably, both phases are removed separately from the device for phase separation. Most preferably, the remainder of the reaction mixture is recycled to the reactor.
• the separation of the water is carried out using a membrane.
• the reaction water is separated off using a suitable absorber, for example polyacrylic acid and its salts, sulfonated polystyrenes and their salts, activated carbons, montmorillonites, bentonites and zeolites.
• a suitable absorber for example polyacrylic acid and its salts, sulfonated polystyrenes and their salts, activated carbons, montmorillonites, bentonites and zeolites.
• a suitable absorber for example polyacrylic acid and its salts, sulfonated polystyrenes and their salts, activated carbons, montmorillonites, bentonites and zeolites.
• the various measures for removing the water of reaction can also be used several times and also in combination.
• a homogeneous catalyst is understood as meaning a catalyst which is homogeneously dissolved in the reaction medium during the reaction.
• the homogeneous catalyst used in the process according to the invention for increasing the molar mass generally contains at least one element of the subgroups of the Periodic Table (transition metal).
• the alcohol amination can be carried out in the presence or absence of an additional solvent.
• the alcohol amination can be carried out in a multiphase, preferably single-phase or two-phase, liquid system at temperatures generally from 20 to 250 ° C.
• the lower phase can consist of water and most of the homogeneously dissolved catalyst and the upper phase of a nonpolar solvent which contains the majority of the polyamines formed and the non-polar starting materials.
• 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 catalyst and with removal of the reacted in the reaction of water by using a Wasserausnikers, a device for distillative separation of water, one or more devices for phase separation or an absorbent.
• a lower molecular weight polyalkylenepolyamine is reacted in the presence of a catalyst to form a higher molecular weight polyalkylenepolyamine, the lower molecular weight polyalkylenepolyamine being prepared in a preceding step from monoethanolamine or by reacting ethylenediamine, 1,3-propylenediamine or 1, 2-propylenediamine with ethylene glycol, 1, 2-decanediol or 1, 2-dodecanediol as described above was prepared and separated from the reaction water.
• the number of alkylene units in the polyalkylenepolyamines is generally in the range of 3 to 50,000.
• the Polyalkylenpolyamine thus obtained can carry as end groups at the chain ends both NH2 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
• i integer from the range of 3 to 50,000.
• 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 100,000.
• the molecular weight distribution Mw / Mn is generally in the range of 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.
• polyethylenimines obtained by the process according to the invention can be present both in linear form and 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 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 pentamethylcyclopentadienyl, aryl, olefin ligands , Hydride, halide, carboxylate, alkoxylate, carbonyl, hydroxide, trialkylamine, dialkylamine, monoalkylamine, nitrogen aromatics such as pyridine or pyrrolidine and multi-toothed amines.
• 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 cycloaliphatic and araliphatic radicals are - CH 2 -C 6 H 11 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-octyl, 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-trimethyl-
• 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-1H-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 preference is given to nitrogen-heterocyclic carbenes, in particular if, as described below, a polar solvent is added after the reaction, as particularly suitable ligands.
• ligands which form water-soluble complexes with Ru.
• Particularly preferred are 1-butyl-3-methylimidazolin-2-ylidene, 1-ethyl-3-methylimidazolin-2-ylidene, 1-methylimidazolin-2-ylidene and dipropylimidazolin-2-ylidene.
• Suitable ligands are cyclopentadienyl and its derivatives which are mono- to pentavalent-substituted with alkyl, aryl and / or hydroxy, for example methylcyclopentadienyl, pentamethylcyclopentadienyl, tetraphenylhydroxycyclopentadienyl and pentaphenylcyclopentadienyl.
• Suitable ligands are indenyl and its substituted derivatives as described for cyclopentadienyl.
• ligands are hydroxide, 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 customary 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 O], [Ru (acetylacetonate) 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) Cl 2], [Ru (PPh 3) 3 (CO) (H) 2], [Ru (PPh 3 ) 3 Cl 2 ], [Ru (cyclopentadienyl) (PPh 3 ) 2 Cl],
• customary standard complexes such as [Ru (p-cymene) Cl 2] 2, [Ru (benzene) Cl
• 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 polyalkylenepolyamines are just dissolved in the solvent.
• the weight ratio of the amount of solvent to the amount of polyalkylenepolyamines is from 100: 1 to 0.1: 1, preferably from 10: 1 to 0.1: 1.
• Separation of the water of reaction during the reaction can both by means of the measures already described, for example by means of a water separator, by means of a device for phase separation, by means of a device for distillation or medium of a suitable absorber, take place when the reaction is carried out with solvent, as well as in carrying out the reaction without solvent.
• a separation of the water of reaction during the post-crosslinking of the first or second type can also be carried out by means of the measures already described, for example by means of a water separator, by means of a device for phase separation, by means of a device for distillation or medium of a suitable absorber, if the reaction with solvent is carried out as well as in carrying out the reaction without solvent.
• the reaction or postcrosslinking is carried out without a solvent, after the reaction or postcrosslinking there is generally a phase which contains the product and the catalyst.
• Suitable solvents are, for example, toluene or mesitylene. If a solvent is used during the reaction and one or more phase separation devices are used to separate the water, the boiling point of the solvent may be below or above the boiling point of the water.
• Postcrosslinking of the first or second type of polyalkylenepolyamine can be carried out either with or without a solvent. If the reaction is carried out without solvent, the homogeneous catalyst is usually dissolved in the product after the reaction.
• the catalyst may remain in the product or be separated therefrom by a suitable method. Ways of separating off the catalyst are, for example, washing out with a solvent which is not miscible with the product, in which the catalyst dissolves better by suitable choice of the ligands than in the product.
• the catalyst is depleted of the product by multi-stage extraction.
• the extraction medium used is preferably a solvent which is also suitable for the target reaction and which, after concentration together with the extracted catalyst, can be used again for the reaction.
• non-polar solvents such as toluene, benzene, xylenes, mesitylene, alkanes such as hexanes, heptanes and octanes, and acyclic or cyclic ethers such as diethyl ether and tetrahydrofuran are suitable.
• the product is lipophilic, polar solvents such as acetonitrile, sulfoxides such as dimethylsulfoxide, formamides such as dimethylforamide, ionic liquids, e.g. 1-ethyl-3-methylimidazolium hydrogensulfate, 1-butyl-3-methylimidazolium methanesulfonate. It is also possible to remove the catalyst with a suitable absorber material.
• Separation of the catalyst from a hydrophilic product after postcrosslinking or after a reaction in which water has been separated continuously can also be effected by adding water or an ionic liquid to the product phase, if the reaction takes place in water or water ionic liquid immiscible solvent is performed.
• the catalyst preferably dissolves in the reaction mixture used for the reaction. th solvent, it can be separated with the solvent from the hydrophilic product phase and optionally used again. This can be effected by choosing suitable ligands.
• the resulting aqueous polyalkylenepolyamines can be used directly as technical polyalkylenepolyamine solutions.
• Separation of the catalyst from a lipophilic product after postcrosslinking or after a reaction in which water has been continuously separated may also be accomplished by adding a nonpolar solvent to the product phase if the reaction is in a solvent immiscible with the nonpolar solvent, eg ionic liquid, is carried out. If the catalyst preferably dissolves in the polar solvent, it can be separated off from the non-polar product phase with the solvent and optionally reused. This can be effected by choosing suitable ligands.
• the post-crosslinking or reaction in which water is continuously separated is carried out in a solvent, this may be miscible with the product and separated by distillation after the reaction. It is also possible to use solvents which have a miscibility gap with the product or the educts.
• solvents for this purpose in the case of hydrophilic products are toluene, benzene, xylenes, mesitylene, alkanes, such as hexanes, heptanes and octanes, and acyclic or cyclic ethers, such as diethyl ether, tetrahydrofuran (THF) and dioxane or alcohols more than three carbon atoms, in which the OH group is bonded to a tertiary carbon atom, called.
• THF tetrahydrofuran
• tert-amyl alcohol Preference is given to toluene, mesitylene and tetrahydrofuran (THF) and tert-amyl alcohol.
• the product is lipophilic, polar solvents such as acetonitrile, sulfoxides such as dimethylsulfoxide, formamides such as dimethylformamide, ionic liquids such as e.g. 1-ethyl-3-methylimidazolium hydrogensulfate, 1-butyl-3-methylimidazolium methanesulfonate.
• polar solvents such as acetonitrile, sulfoxides such as dimethylsulfoxide, formamides such as dimethylformamide, ionic liquids such as e.g. 1-ethyl-3-methylimidazolium hydrogensulfate, 1-butyl-3-methylimidazolium methanesulfonate.
• the solvent may also be miscible with the starting materials and the product under the reaction conditions and only after cooling, for example to room temperature, form a second liquid phase which contains the major part of the catalyst.
• solvents exhibiting this property in the case of polar starting materials and products, mention may be made, for example, of toluene, benzene, xylenes, mesitylene, alkanes, such as hexanes, heptanes and octanes.
• ionic liquids exhibit these properties.
• the catalyst can then be separated together with the solvent and reused.
• the product phase can also be mixed in this variant with water or another solvent.
• the portion of the catalyst contained in the product can then be replaced by suitable absorber materials such as, for example, polyacrylic acid and its salts, sulfonated polystyrenes and their salts, activated carbons, montmorillonites, bentonites and zeolites are separated or left in the product.
• suitable absorber materials such as, for example, polyacrylic acid and its salts, sulfonated polystyrenes and their salts, activated carbons, montmorillonites, bentonites and zeolites are separated or left in the product.
• the nonpolar solvents which are particularly suitable are toluene, benzene, xylenes, mesitylene, alkanes, such as hexanes, heptanes and octanes, in combination with lipophilic phosphine ligands on the transition metal catalyst such as triphenylphosphine, tritolylphosphine, tri-n-butylphosphine, tri -n-octylphosphine, trimethylphosphine, triethylphosphine, bis (diphenylphosphino) methane, 1, 2-bis (diphenylphosphino) ethane, 1, 2-dimethyl-1, 2-bis (diphenylphosphino) ethane, 1, 2-bis (dicyclohexylphosphino ) ethane, 1, 2-bis (diethylphosphino) ethane, 1, 3-bis (diphenylphosphine, trito
• Suitable polar solvents are ionic liquids, dimethylsulfoxide and dimethylformamide, in combination with hydrophilic ligands on the transition metal catalyst, e.g. nitrogen-heterocyclic carbenes, thereby enriching the transition metal catalyst in the polar phase.
• the majority of the catalyst can be separated from the product phase by simple phase separation and reused.
• 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 autogenous pressure of the solvent at the reaction temperature and the pressure of a gas such as nitrogen, argon or hydrogen.
• the average reaction time is generally 15 minutes to 100 hours.
• bases can have a positive effect on product formation.
• Suitable bases are alkali metal hydroxides, alkaline earth hydroxides, alkali metal alkoxides, alkaline earth metal alkoxides, alkali metal Li carbonates and alkaline earth carbonates, of which 0.01 to 100 equivalents can be used with respect to the metal catalyst used.
• Another object of the invention are polyalkylenepolyamines, in particular polyethylene enimines, which are prepared according to the described embodiments of the method according to the invention.
• Another object of the invention are polyalkylenepolyamines containing hydroxy groups, secondary amines or tertiary amines.
• the hydroxy groups, secondary amines or tertiary amines are preferably located at 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: second
• such Polyalkylenpolyamine containing the hydroxy groups, secondary amines or tertiary amines only Hyroxy-end groups or only amine-end groups (primary, secondary, tertiary).
• These polyalkylenepolyamines are preferably obtained by the process according to the invention with the aid of a secondary crosslinking of the second type.
• the invention further relates to the uses of these 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 primers in paints, f) as a wet adhesion promoter in emulsion paints, 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, k) as a hardener for epoxy resins.
• these 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 resin
• the present invention provides processes for increasing the molecular weight of polyalkylene polyamines, in which no aziridine is used, no unwanted by-products are formed and products of a desired chain length are obtained.
• the invention is explained in more detail by the examples without the examples restricting the subject matter of the invention.
• 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 performed at 40 ° C with a flow rate of 1 ml / min on a styrene-divinylbenzene copolymer column (8 mm * 30 cm) with a differential refractometer RI and 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 weight average (RI) of the obtained oligomer was 1740 g / mol with a dispersity (Mw / Mn) of 3.7. This corresponds to an average chain length of the oligomer n (CH 2 CH (CioH2i) NHCH2CH 2 NH) n of 7.3.
• Mw / Mn dispersity
• the reaction water, unreacted starting materials 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 upper phase containing the catalyst was separated from the lower phase containing the product.
• 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 upper phase containing the catalyst was separated from the lower phase containing the product.
• the reaction water, unreacted starting materials and volatiles were removed on a rotary evaporator at 12 mbar and 1 16 ° C, to give 8.14 g of the pure product.
• the weight average (RI) of the obtained oligomer was 1550 g / mol with a dispersity (Mw / Mn) of 3.3. This corresponds to an average chain length n of the oligomer (CH 2 CH 2 NH) n of 36.
• the color number was 1 12.
• the upper phase containing the catalyst was separated from the lower phase containing the product.
• the water of reaction, unreacted starting materials and volatile constituents were removed on a rotary evaporator at 12 mbar and 166 ° C., giving 8.73 g of the pure product.
• the weight average (RI) of the obtained oligomer was 1460 g / mol with a dispersity (Mw / Mn) of 3.3. This corresponds to an average chain length n of the oligomer (CH 2 CH 2 NH) n of 34.
• the color number was 91.

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• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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• 2012
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