EP2782949A1

EP2782949A1 - Synthesis of polyalkylene polyamines with low color index by homogeneously catalyzed alcohol amination in the presence of hydrogen

Info

Publication number: EP2782949A1
Application number: EP12787744.7A
Authority: EP
Inventors: Julia Strautmann; Thomas Schaub; Stephan Hüffer; Steffen Maas; Rocco Paciello
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2011-11-25
Filing date: 2012-11-20
Publication date: 2014-10-01
Also published as: CN103987757A; BR112014012440A2; WO2013076053A1; IN2014CN03935A; KR20140098204A; JP2014534249A

Abstract

The invention relates to a method for the production of polyalkylene polyamines by homogeneously catalyzed alcohol amination, wherein aliphatic alkanolamines are reacted with each other or aliphatic diamines or polyamines are reacted with aliphatic diols or polyols in the presence of a homogeneous catalyst while eliminating water and in the presence of hydrogen gas. The invention further relates to polyalkylene polyamines, which can be obtained by said methods, and to polyalkylene polyamines which contain hydroxyl groups, secondary amines or tertiary amines. The invention finally relates to uses of said polyalkylene polyamines as adhesion promoters in inks, adhesion promoters in composite films, cohesion promoters in adhesives, cross-linkers/hardeners for resins, primers for paints, wet adhesion promoters for dispersion paints, complexing agents and flocculants, penetration auxiliaries for use in wood preservation, corrosion inhibitors, and immobilization agents of proteins and enzymes.

Description

Synthesis of polyalkylenepolyamines having a low color number by homogeneously catalyzed alcohol amination in the presence of hydrogen

description

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.

Further embodiments of the present invention can be taken from the claims, the description and the examples. It is understood that the features mentioned above and those yet to be explained of the subject matter according to the invention can be used not only in the specific concretely specified combination but also in other combinations without departing from the scope of the invention. Preferred or very preferred are the embodiments of the present invention in which all features have the preferred or very preferred meaning.

Polyethyleneimines are valuable products with a variety of different uses. For example, 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 Hg, Pb, Cu, Ni and flocculants in water treatment / water treatment; h) as a penetration aid for active metal salt formulations in wood preservation; i) as corrosion inhibitors for iron and non-ferrous metals; j) for the immobilization of proteins and enzymes. Other 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).

In the β-chloroethylamine process, ethyleneimine is obtained by the reaction of β-chloroethylamine with NaOH. This can lead to the unwanted polymerization of ß-chloroethylamine by HCl cleavage, which must be carefully avoided. Another disadvantage is the use of two equivalents of NaOH and the formation of the by-product NaCl.

In the Dow process, 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.

In the Wencker process, in the first step, 2-aminoethanol is reacted with sulfuric acid to give 2-aminoethyl hydrogen sulfate. From this is then obtained in the second step by the addition of two equivalents of NaOH, the ethyleneamine. Again, the use of sulfuric acid and NaOH and the formation of the by-product sodium sulfate is disadvantageous.

In the catalytic dehydrogenation of 2-aminoethanol, 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.

In addition to the disadvantages mentioned in the processes for the production of ethyleneimine, the synthesis of polyethyleneimines starting from this starting compound is problematic since the highly reactive, toxic and corrosive ethyleneimine must be handled. It must also be ensured that no ethyleneimine remains in the products or wastewater streams obtained.

For the preparation of non-aziridine-derived polyalkylenepolyamines - [(CH ₂ ) _X N] - with alkylene groups> C ₂ (x> 2), there are no procedures analogous to the aziridino route, as a result of which there has hitherto been no cost-effective process for their preparation. The homogeneous-catalyzed amination of alcohols is known from the literature for the synthesis of primary, secondary and tertiary amines starting from alcohols and amines, monomeric products being obtained in all the embodiments described. US 3,708,539 describes the synthesis of primary, secondary and tertiary amines using a ruthenium-phosphine complex.

In 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 (PPh ₃ ) ₃ Cl ₂ ] as the catalyst.

EP 0 034 480 A2 discloses the preparation of N-alkyl or Ν, Ν-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.

A. Tillack, D. Hollmann, K. Mevius, D. Michalik, S. Bähn, M. Beller Eur. J. Org. Chem. 2008, 4745-4750, A. Tillack, D. Hollmann, D. Michalik , M. Beller Tetrahedron Lett. 2006, 47, 8881-8888, in D. Hollmann, S. Bähn, A. Tillack, M. Beller Angew. Chem. Int. Ed. 2007, 46, 8291-8294 and in M. Haniti, S.A. Hamid, C.L. Allen, G.W. Lamb, A.C. Maxwell, H.C. Maytum, A.J.A. Watson, J.M.J. Williams J. Am. Chem. Soc., 2009, 131, 1766-1774 describes syntheses of secondary and tertiary amines starting from alcohols and primary and secondary amines, respectively, using homogeneous ruthenium catalysts.

The synthesis of primary amines by the reaction of alcohols with ammonia using a homogeneous ruthenium catalyst is described in C. Gunanathan, D. Milstein Angew. Chem. Int. Ed. 2008, 47, 8661 -8664. In our unpublished application PCT / EP201 1/058758 general processes for the preparation of polyalkylenepolyamines by catalytic alcohol amination of alkanolamines or of di- or polyamines with di- or polyols are described. 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. Preferably, 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. In detail, 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, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 2- ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethyl-1 -methylpropyl, 1-ethyl-2-methylpropyl, or C ₇ -C ₀ -alkyl such as heptyl, octyl, 2-ethyl-hexyl, 2,4,4-trimethylpentyl, 1,1,3,3-tetramethylbutyl, nonyl or decyl and their isomers. 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.

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. In the context of the present invention, the symbol "*" denotes the valency for all chemical compounds via which one chemical group is attached to another chemical group.

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-aminoheptan-1-ol, aminooctanol, for example 2-aminooctan-1-ol or 8-aminooctan-1 - ol, aminononanol, for example 2-aminononan-1-ol or 9- Aminononan-1-ol, aminodecanol, for example 2-aminodecan-1-ol or 10-aminodecan-1-ol, aminoundecanol, for example 2-aminoundecan-1-ol or 1-aminoundecan-1-ol, amino-dodecanol, for example 2-aminodocedan-1-ol or 12-aminododecan-1-ol, aminotridecanol, for example 2-aminotridecan-1-ol, 1- (2-hydroxyethyl) piperazine, 2- (2-aminoethoxy) ethanol, alkylalkanolamines, for example butylethanolamine, Propylethanolamine, ethylethanolamine, methylethanolamine. Particularly preferred are monoethanolamine and monopropanolamine.

Aliphatic diamines which are suitable for a reaction under a hydrogen atmosphere 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-diaminooctane or 1, 2 -Diaminooctan, diaminononane, for example 1, 9-diaminononane or 1, 2-diaminononane, diaminodecane, for example, 1, 10-diaminodecane or 1, 2-diaminodecane, diaminoundecane, for example 1, 1 1 - diaminoundecane or 1, 2-diaminoundecane, diaminododecane , for example, 1, 12- diaminododecane, or 1, 2-diaminododecane, 3,3 ^{^{'-dimethyl-4,4'-diaminodicyclohexylmethane,}} ^{4,4'-diaminodicyclohexylmethane,} isophoronediamine, 2,2-dimethylpropane-1, 3-diamine, 4 , 7,10-trioxatridecane-1, 13-diamine, 4,9-dioxadodecane-1, 12-diamine, polyetheramine, piperazine, 3- (cyclohexylamino) propylamine, 3- (methylamino) propylamine, N, N-bis (3-aminopropyl) methylamine. Suitable aliphatic diols are linear branched or cyclic aliphatic diols.

Examples of 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-Butylgylkol, 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, nonanediols , for example 1, 9-nonanediol or 1, 2-nonanediol, decanediols, for example 1, 10-decanediol or 1, 2-decanediol, undecanediols, for example 1, 1 1 - undecanediol or 1, 2-undecanediol, dodecanediols, for example 1, 12-dodecanediol, 1,2-dodecanediol, tridecanediols, for example 1,13-tridecanediol or 1,2-tridecanediol, tetradecanols, for example 1,14-tetradecanediol or 1,2-tetradecanediol, pentadecanediols, for example 1,15-pentadecanediol or 1, 2-pentadecanediol, hexadecanediols, for example 1, 16-hexadecanediol or 1, 2-hexadecanediol, heptadecanediols, for example 1, 17-heptadecanediol or 1, 2-heptanedicarboxylic, octadecanediols, for example 1, 18-octadecanediol or 1, 2-octadecanediol, 3,4-dimethyl-2, 5-hexanediol, polyTHF, 1,4-bis (2-hydroxyethyl) piperazine, diethanolamines, for example butyldiethanolamine or methyldiethanolamine, dialcoholamines and trialcoholamines.

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 For example, 1, 12-dodecylene or 1, 2-dodecylene, tridecylene, for example, 1, 2-tridecylene, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, neopentylene. Also, cycloalkylene units are possible, for example, 1, 3 or 1, 4-cyclohexylene. The polyalkylenepolyamines particularly preferably have C ₂ -alkylene units.

It is also possible to use mixtures of aliphatic aminoalcohols or mixtures of alkanediols or mixtures of diaminoalkanes in the respective reactions under hydrogen pressure. The resulting polyalkylenepolyamines may contain alkylene units of different lengths.

Also, 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. Examples of 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. 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. Examples of 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.

In the synthesis, preference is given to at least (i) monoethanolamine (ii) monopropanolamine or (iii) ethylene glycol with ethylenediamine. Also preferred are at least (i) ethylenediamine or (ii) 1, 2-propylenediamine or (iii) 1, 3-propylenediamine and 1, 2-decanediol or 1, 2-dodecanediol.

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.

The preparation of the polyalkylenepolyamines is exemplified in Equations 2 and 2:

Alkanolamine Polyalkylenepolyamine

(R = H, alkyl)

Equation 1

polyalkylenepolyamines

Equation 2

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. The

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. In the case of two-phase reaction systems, the upper phase of a non-polar solvent containing most of the homogeneously dissolved catalyst, and the lower phase of the polar educts, the polyamines formed and water. Furthermore, 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.

In a preferred embodiment of the invention, (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. '2

polyethylene polyamine

H ₂

Catalyst _t r

'2 + HO ^ - ΓΝ

H ₂ 0 - | _ |

Polyethylene polyamine NH _{2 +}

(k = 1, 2) (R = C ₈ H ₁₇ , C ₁₀ H ₂₁ ) Polyalkylenepolyamine

(R = C ₈ H ₁₇ , C ₁₀ H ₂₁ ) polyalkylenepolyamine

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.

With preferred

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

integer from the range 1 to 50, preferably from 1 to 30,

more preferably from 1 to 20,

n, k are independent of each other, the same or different

integer from the range 0 to 50, preferably 0 to 30,

more preferably from 0 to 20,

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 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.

The 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 (linear, branched or cyclic) 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 . Examples of suitable 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-trimethyl-phenyl) -imidazole and 1-phenylindole. 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. Preferably, 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. In said unbranched or branched, acyclic or cyclic, aliphatic, aromatic or araliphatic radicals, individual carbon atoms may also be substituted by further phosphine groups. Thus, multidentate, for example bidentate or tridentate, phosphine ligands are also included whose phosphine groups are bridged by alkylene or arylene groups. The 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-methoxyphenyl) -1H-pyrrole, 2- (di-tert-butylphosphino) -1- (2-methoxyphenyl) -1H-pyrrole and 2- (di-tert-butyl-phosphino) -1-phenyl-1H-pyrrole. Very particularly preferred are 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. Particularly suitable multidentate phosphine ligands are 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 (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 2,3-

Bis (diphenylphosphino) butane, 1,3-bis (diphenylphosphino) propane 1,1,1-tris (diphenylphosphinomethyl) ethane, 1,1'-bis (diphenylphosphanyl) ferrocene and 4,5-bis (diphenylphosphino) -9 , 9-dimethylxanthene.

Furthermore, nitrogen-heterocyclic carbenes may be mentioned as particularly suitable ligands. Here, 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.

Cyclopentadienyl and its derivatives which are mono- to pentavalent-substituted with alkyl, aryl and / or hydroxy, such as, for example, methylcyclopentadienly, pentamethylcyclopentadienyl, tetraphenylhydroxycyclopentadienyl and pentaphenylcyclopentadienyl, may also be mentioned as particularly suitable ligands. Further particularly suitable ligands are indenyl and its substituted derivatives as described for cyclopentadienyl.

Also particularly suitable 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) (CO) ₂ CI], [Ru (cyclopentadienyl) (CO) ₂ H], [Ru (cyclopentadienyl) (CO) ₂ ] ₂ , [Ru (pentamethylcyclopentadienyl) (CO) ₂ Cl], [Ru (pentamethylcyclopentadienyl) (CO) ₂ H], [Ru (pentamethylcyclopentadienyl) (CO) ₂ ] ₂ , [Ru (indenyl) (CO ) ₂ Cl], [Ru (indenyl) (CO) ₂ H], [Ru (indenyl) (CO) ₂ ] ₂ , ruthenocene, [Ru (binap) Cl ₂ ], [Ru (bipyridine) ₂ Cl ₂ ^* 2H ₂ 0], [Ru (COD) Cl ₂ ] ₂ , [Ru (pentamethylcyclopentadienyl) (COD) Cl], [Ru ₃ (CO) i ₂ ], [Ru (tetraphenylhydroxycyclopentadienyl) (CO) ₂ H], [ Ru (PMe ₃ ) ₄ (H) ₂ ], [Ru (PEt ₃ ) ₄ (H) ₂ ], [Ru (PnPr ₃ ) ₄ (H) ₂ ], [Ru (PnBu ₃ ) ₄ (H) ₂ ], [Ru (PnOctyl ₃ ) ₄ (H) ₂ ], [IrCl ₃ ^* H ₂ O], ClrCl ₄ , K ₃ IrCl ₆ , [Ir (COD) Cl] ₂ , [Ir (cyclooctene) ₂ Cl] ₂ , [Ir (ethene) ₂ Cl] ₂ , [Ir (cyclopentadienyl) Cl ₂ ] ₂ , [Ir ( pentamethylcyclopentadienyl) CI ₂ ] ₂ , [Ir (cyclopentadienyl) (CO) ₂ ], [Ir (pentamethylcyclopentadienyl) (CO) ₂ ], [Ir (PPh ₃ ) ₂ (CO) (H)], [Ir (PPh ₃ ) ₂ (CO) (Cl)], [Ir (PPh ₃ ) ₃ (CI )] with the addition of the corresponding ligands, preferably the abovementioned mono- or polydentate phosphine ligands or the abovementioned nitrogen-heterocyclic carbenes, are produced only under the reaction conditions.

The amount of the metal component of the catalyst, preferably ruthenium or iridium, 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.

If the process is carried out in a solvent, the amount of solvent is frequently chosen so that the starting materials (i) and (ii) are just dissolved in the solvent. In general, 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. Preferably, 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.

The addition of 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.

In a preferred embodiment of the process according to the invention, 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. In a preferred embodiment of the process according to the invention, 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.

Another object of the invention are polyalkylenepolyamines, preferably polyethyleneamine or polypropyleneamine, 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 on a terminal carbon atom of an alkylene group and thus represent an end group. These polyalkylenepolyamines preferably contain hydroxyl groups.

For example, these polyalkylenepolyamines which contain hydroxy groups, secondary amines or tertiary amines are obtainable by means of the process according to the invention. In particular, 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 (primary, secondary, tertiary) is preferably from 10: 1 to 1:10, preferably from 5: 1 to 1: 5, particularly preferably from 2: 1 to 1: 2. In a further preferred embodiment, 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 invention is explained in more detail by the examples, without the examples limiting the subject matter of the invention. Examples

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. To measure the Hazen color number (according to APHA), 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.

In general, 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.

example 1

12.1 g (7.63 mmol) of [Ru (PnOctyl ₃ ) ₄ (H) ₂ ], 450 g (7.37 mol) of ethanolamine, 10.05, were added to a 250 mL autoclave with paddle stirrer under inert conditions to exclude oxygen weighed out g (89.56 mmol) of potassium tert-butoxide and 1620 ml of toluene. In the sealed autoclave hydrogen was pressed to 40 bar. Subsequently, the reaction mixture was heated to 140 ° C and stirred for 20 h. After completion of the reaction and cooling, two phases were formed. The upper phase containing the catalyst was separated from the lower phase containing the product. 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.

Example 2

In a 250 mL autoclave with paddle stirrer, 0.27 g (0.17 mmol) of [Ru (PnOctyl ₃ ) ₄ (H) ₂ ], 10.5 g of the effluent from Example 1, 230 mg (2.05 mmol ) Weighed in potassium tert-butoxide and 37 mL toluene. The reaction mixture is stirred in a sealed autoclave at 140 ° C under the autogenous pressure of the solvent for 10 h. After completion of the reaction and cooling, the product precipitated as a solid. The approach is done with 200 mL of water quenched, the product dissolves and forms two phases. The upper phase containing the catalyst was separated from the lower phase containing the product. 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.

Example 3

In a 250 mL autoclave with paddle stirrer, 0.27 g (0.17 mmol) of [Ru (PnOctyl ₃ ) 4 (H) ₂ ], 10.5 g of the product from Example 1, 230 mg (2.05 mmol ) Weighed in potassium tert-butoxide and 37 mL toluene. In the sealed autoclave hydrogen was pressed to 15 bar. Subsequently, the reaction mixture was heated to 140 ° C and stirred for 10 h. After completion of the reaction and cooling, the product precipitated as a solid. The batch is quenched with 200 mL of water, whereupon the product dissolves and forms two phases. 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.

Example 4

0.20 g (0.71 mmol) of [Ru (COD) Cl ₂ ], 0.50 g (2.9 mmol) of 1-butyl-3-methylimidazolium chloride, 12.1 g (in a 250 ml autoclave with paddle stirrer) were added under inert conditions. 0.06 mol) of 1,2-dodecanediol, 20.0 g (0.27 mol) of 1,3-propylenediamine, 0.50 g (4.46 mmol) of potassium tert-butoxide and 34 ml of toluene were weighed. The reaction mixture was stirred in the sealed autoclave at 150 ° C under the autogenous pressure of the solvent for 20 h. After completion of the reaction and cooling, 5 ml of water was added to the reaction mixture and shaken to obtain a solution (50.0 g) of the product in toluene and an aqueous solution (12.66 g) of the catalyst. The phases were separated. From the product phase, the unreacted starting material and volatile constituents were removed on a rotary evaporator at 20 mbar and 120 ° C., giving 14.13 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 74. Example 5

Under inert conditions, 0.20 g (0.71 mmol) of [Ru (COD) Cl ₂ ], 0.50 g (2.9 mmol) of 1-butyl-3-methylimidazolium chloride, 12.1 g, were used in a 250 mL autoclave with paddle stirrer g (0.06 mol) of 1, 2-dodecanediol, 20.0 g (0.27 mol) of 1, 3-propylenediamine, Ο., Ο g (4.46 mmol) of potassium tert-butoxide and weighed 34 ml of toluene , In the closed autoclave, hydrogen is pressed to 40 bar. Subsequently, the reaction mixture is heated to 150 ° C and stirred for 20 h. After completion of the reaction and cooling, 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.

Comparative Example 1

In an autoclave with paddle stirrer, 10 g (0.36 mmol) of [Ru (COD) (CI) ₂ ] ₂ , 0.22 g of triphos (0.36 mmol), 0.2 g of tri-n-octylphosphine ( 0.54 mmol), 10 g (0.16 mol) of ethanolamine, 0.15 g (1.3 mmol) of potassium tert-butoxide and weighed out 60 g of toluene. Subsequently, the reaction mixture was heated to 140 ° C and stirred for 20 h. After completion of the reaction and cooling, the mixture was mixed with 10 ml of water. The upper phase was separated from the lower phase containing the product. The water, unreacted starting materials and volatile constituents were then removed on a rotary evaporator at 12 mbar and 110 ° C., giving 6.5 g of the pure product. The color number was 871.

Claims

claims

1 . Process for the preparation of polyalkylenepolyamines by homogeneously catalyzed alcohol amination, in which

(i) aliphatic amino alcohols with each other or

(ii) reacting aliphatic diamines or polyamines with dehydrated aliphatic diols or polyols in the presence of a homogeneous catalyst and in the presence of hydrogen gas.

2. The method according to claim 1, characterized in that the reaction takes place at a partial pressure of the hydrogen gas of 0.1 to 25 MPa.

3. The method according to claim 1 or 2, characterized in that the hydrogen gas engages chemically in the catalyzed alcohol amination, whereby the formation of color bender components is reduced.

4. Process according to claims 1 to 3, characterized in that the catalyst is a transition metal complex catalyst.

5. Process according to claims 1 to 4, characterized in that the catalyst contains ruthenium or iridium.

6. Process according to claims 1 to 5, characterized in that the catalyst contains a nitrogen-heterocyclic carbene ligand.

7. The method according to claim 6, characterized in that the catalyst is a carbene ligand selected from the group consisting of 1-butyl-3-methylimidazolin-2-ylidene, 1-ethyl-3-methylimidazolin-2-ylidene, 1-methylimidazolin-2 yliden, dipropylimidazolin-2-ylidene contains.

8. Process according to claims 1 to 5, characterized in that the catalyst contains a monodentate or polydentate phosphine ligand. 9. The method according to claim 8, characterized in that the catalyst contains a monodentate phosphine ligand containing an unbranched, acyclic or cyclic aliphatic radical having from 1 to 12 carbon atoms or an aryliphatic radical.

10. The method according to claims 8 or 9, characterized in that the catalyst is a monodentate phosphine ligand selected from the group consisting of triphenylphosphine, tritolylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, trimethylphenyl phosphine, triethylphosphine, di (1-adamantyl) -n-butylphosphine, adamantyl) benzylphosphine, 2- (dicyclohexylphosphino) -1-phenyl-1H-pyrrole.

Process according to claim 8, characterized in that the catalyst contains a polydentate phosphine ligand consisting of at least one unbranched, acyclic or cyclic aliphatic radical having 1 to 12 carbon atoms or aryl-liphatic radical.

Process according to claims 8 or 11, characterized in that the catalyst is a polydentate phosphine ligand selected from the group consisting of 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 (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, 2,3-bis (diphenylphosphino) butane, 1,1,1-tris (diphenylphosphinomethyl) ethane, 1, 1 '-bis (diphenylphosphanyl) ferrocene and 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene.

13. The process according to claims 1 to 12, characterized in that the catalyst contains a ligand selected from the group consisting of cyclopentadienyl, substituted cyclopentadienyl, indenyl and substituted indenyl.

14. The method according to claims 1 to 13, characterized in that the catalyst contains a ligand selected from the group consisting of hydroxide, hydride, carbonyl and chloride.

15. Process according to claims 1 to 14, characterized in that the reaction is carried out in the presence of a solvent.

16. The method according to claim 15, characterized in that the solvent is selected from the group consisting of benzene, toluene, xylenes, alkanes, acyclic and cyclic ethers, alcohols having more than 3 carbon atoms.

17. The method according to claim 15, characterized in that the solvent is selected from the group consisting of water, ionic liquids, sulfoxides, formamide, acetonitrile.

18. Process according to claims 1 to 17, characterized in that 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, especially twelve or more, carbon atoms.

19. Process according to claims 1 to 17, characterized in that at least (i) monoethanolamine or (ii) ethylene glycol is reacted with ethylenediamine.

20. The method according to claims 1 to 17, characterized in that 3-amino-1 -ol is reacted.

21. Process according to claims 1 to 17, characterized in that at least ethylenediamine or 1, 2-propylenediamine or 1, 3-propylenediamine and 1, 2-decanediol or 1, 2-dodecanediol is selected.

22. The method according to claims 1 to 17, characterized in that at least one of the starting materials 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.

23. Process according to claims 1 to 17, characterized in that 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 20, preferably from 6 to 18, particularly preferably from Contains 7 to 16, in particular from 8 to 14 carbon atoms.

24. The method according to claims 1 to 18, 22 and 23, characterized in that the heteroatoms O or N of one of the starting materials aliphatic amino alcohols, aliphatic diamines or polyamines or aliphatic diols or polyols in alpha and beta position on the chain of C atoms and thus located on adjacent carbon atoms.

25. Process according to claims 1 to 18, 22 and 23, characterized in that the heteroatoms O of the N of one of the starting materials aliphatic amino alcohols, aliphatic diamines or polyamines or aliphatic diols or polyols in the alpha and omega position on the chain of C atoms and thus located at the opposite ends of the chain of carbon atoms.

26. Polyalkylenepolyamines obtainable by the process according to any one of claims 1 to 25.

27. Polyethyleneimine obtainable by the process according to claim 19.

28. Polypropylene amine obtainable by the process according to claim 20. 29. Polyalkylenepolyamines containing hydroxy groups, secondary amines or tertiary amines.

30. uses of the polyalkylenepolyamines according to claims 26 to 29 as a) adhesion promoter for printing inks,

b) adhesion promoter in composite films,

c) cohesive promoter for adhesives,

d) crosslinker / hardener for resins,

e) primers for paints,

f) wet adhesion promoter for emulsion paints,

g) complexing agents and flocculants,

h) penetration aids in wood preservation,

i) corrosion inhibitor,

j) Immobilizing agents of proteins and enzymes.