KR20140098204A - Synthesis of polyalkylene polyamines with low color index by homogeneously catalyzed alcohol amination in the presence of hydrogen - Google Patents

Abstract

The present invention relates to a process for the preparation of polyunsaturated alcohols by homogeneously catalyzed alcohol amination, in which 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, To a process for producing polyalkylene polyamines. The invention further relates to polyalkylene polyamines which can be obtained by the above process and to polyalkylene polyamines comprising hydroxyl groups, secondary amines or tertiary amines. Finally, the present invention relates to an adhesion promoter in ink, an adhesion promoter in a composite film, an adhesion promoter in an adhesive, a crosslinking agent / curing agent for a resin, a primer for a paint, a wet adhesion promoter for a disperse paint, To corrosion inhibitors, and to the use of said polyalkylene polyamines as immobilizing agents for proteins and enzymes.

Description

Synthesis of Polyalkylene Polyamines Having Low Color Index by Homogeneously Catalyzed Alcohol Amination in the Presence of Hydrogen {SYNTHESIS OF POLYALKYLENE POLYAMINES WITH LOW COLOR INDEX BY HOMOGENEOUSLY CATALYZED ALCOHOL AMINATION IN THE PRESENCE OF HYDROGEN}

The present invention relates to a process for preparing polyalkylene polyamines having a low color index by uniformly catalyzed alcohol amination of diols or polyols with alkanolamines or di- or polyamines in the presence of hydrogen. Furthermore, the present invention also relates to the use of polyalkylene polyamines and polyalkylene polyamines obtainable by these processes. The present invention further provides certain polyalkylene polyamines having a hydroxyl group, a secondary amine group or a tertiary amine group.

Further embodiments of the invention may be found in the claims, the description and the examples. It goes without saying that the characteristics of the object according to the present invention described above and still described in the following can be used in other combinations without departing from the scope of the present invention as well as combinations specifically mentioned in each case. Embodiments of the present invention in which all the features are preferred, or have highly desirable meanings, are each preferable or highly desirable.

Polyethyleneimine is an important product with a number of different uses. For example, the polyethyleneimine may be a) an adhesion promoter for ink printing for film lamination; b) as an adjuvant (adhesive) for the preparation of multiple composite films, when there is a metallic film, as well as different polymer layers of compatibility; c) as adhesion promoters for adhesives, for example with polyvinyl alcohol, butyrate and acetate and styrene copolymers, or as adhesion promoters for label adhesives; d) Further, low molecular weight polyethylene imines can be used as crosslinking / curing agents in epoxy resins and polyurethane adhesives; e) as a primer in coating applications for improving adhesion on substrates such as glass, wood, plastic and metal; f) to improve wet adhesion in standard emulsion paints and also to improve immediate rain resistance of paints, for example for road marking; g) as complexing agents with high binding capacity for heavy metals such as flocculants and Hg, Pb, Cu, Ni in water treatment / water processing; h) In wood preservation, as penetration aid for active metal salt formulations; i) as corrosion inhibitors for iron and non-ferrous metals; j) Used for immobilization of proteins and enzymes. For these applications, polyalkylene polyamines which are not derived from ethyleneimine can also be used.

Presently, polyethyleneimine is obtained by a single polymerization of ethyleneimine. Ethyleneimine is a highly reactive, caustic, and toxic intermediate that can be synthesized in different ways (aziridines, Ulrich Steuerle, Robert Feuerhake; in Ullmann's Encyclopedia of Industrial Chemistry, 2006, Wiley-VCH, Weinheim).

In the? -chloroethylamine process, ethyleneimine is obtained by reacting? -chloroethylamine with NaOH. This process can lead to the undesired polymerization of [beta] -chloroethylamine by HCl removal, which must be carefully avoided. In addition, the use of two equivalents of NaOH and the formation of co-product NaCl are disadvantageous.

In the Dow process, ethylene imine can be obtained by reacting 1,2-dichloroethane with 3 equivalents of ammonia. The use of large amounts of ammonia, the formation of co-product ammonium chloride, the corrosiveness of the reaction mixture and also the impurities in the product are disadvantageous.

In the Wencker process, in the first step, 2-aminoethanol is reacted with sulfuric acid to give 2-aminoethyl hydrogen sulphate. Ethyleneamine is then obtained from above by the addition of two equivalents of NaOH in the second step. Here too, the use of sulfuric acid and NaOH and also the formation of the co-product sodium sulfate is disadvantageous.

During catalytic dehydrogenation of 2-aminoethanol, ethyleneimine is obtained by catalytic dehydrogenation of 2-aminoethanol in the gas phase at 250-450 占 폚. A disadvantage of this process is the complex work-up by distillation, high energy requirements and also short catalyst life.

In addition to the mentioned disadvantages of the process for the preparation of ethyleneimine, the synthesis of polyethyleneimines starting from the abovementioned compounds is problematic because of the need to handle highly reactive, toxic and corrosive ethyleneimines. Likewise, ethylene imines should be ensured not to remain in the resulting product and / or wastewater stream.

For the preparation of polyalkylene polyamine - [(CH ₂ ) _x N] - (where alkylene group> C ₂ (x> 2)), which is not derived from aziridine, there is no process analogous to the aziridine route, So far, there has been no price-efficient process for its manufacture.

Homogeneous catalyzed amination of alcohols is known from the literature for the synthesis of primary, secondary and tertiary amines starting from alcohols and amines, and the monomeric products are obtained in all of the described embodiments.

US 3,708,539 describes the synthesis of primary, secondary and tertiary amines using ruthenium-phosphane complexes.

[Y. Watanabe, Y. Tsuji, Y. Ohsugi Tetrahedron Lett. 1981, 22, 2667-2670 reports the preparation of aryl amines by amination of anilines and alcohols using [Ru (PPh ₃ ) ₃ Cl ₂ ] as catalyst.

EP 0 034 480 A2 describes a process for the preparation of N-alkyl- or N, N-diols by reaction of primary or secondary alcohols with primary or secondary alcohols using iridium, rhodium, ruthenium, osmium, platinum, palladium or rhenium catalysts. - < / RTI > dialkylamines.

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 phosphane complexes.

[K.I. Fujita, R. Yamaguchi Synlett, 2005, 4, 560-571) discloses the synthesis of secondary amines by reaction of primary amines with alcohols, and also the synthesis of diols and primary amines by ring closure using iridium catalysts. The synthesis of cyclic amines by reaction of < RTI ID = 0.0 >

[A. Tillack, D. Hollmann, K. Mevius, D. Michalik, S. Bahn, M. Beller Eur. J. Org. Chem. 2008, 4745-4750], [A. Tillack, D. Hollmann, D. Michalik, M. Beller Tetrahedron Lett. 2006, 47, 8881-8885; Hollmann, S. Bahn, A. Tillack, M. Beller Angew. Chem. Int. Ed. 2007, 46, 8291-8294] and [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 the synthesis of secondary and tertiary amines starting from alcohols and primary or secondary amines, using homogeneous ruthenium catalysts.

The synthesis of primary amines by reaction of ammonia with alcohols using homogeneous ruthenium catalysts is described in [C. Gunanathan, D. Milstein Angew. Chem. Int. Ed. 2008, 47, 8661-8664.

Unpublished application PCT / EP2011 / 058758 describes a general method for the preparation of polyalkylene polyamines by catalytic alcohol amination of diols or polyols with alkanolamines, or diamines or polyamines.

It is an object of the present invention to find a process for producing polyalkylene polyamines in which aziridine is not used and an unwanted co-product is not formed, a product of the desired chain length is obtained and the color index of the product is as low as possible will be.

The object is to provide a process for the preparation of poly (amines) by homogeneously catalyzed alcohol amination which reacts with aliphatic diols or polyamines with aliphatic diols or polyols in the presence of (i) aliphatic amino alcohols, or (ii) Alkylene polyamines of the present invention. The reaction preferably occurs at a pressure of 0.1 to 25 MPa and at a temperature of 100 to 200 < 0 > C.

In the context of the present invention, the expression of the form C _a -C _b is referred to as a chemical compound or substituent having a certain number of carbon atoms. The number of carbon atoms may be selected from the entire range of a to b including a and b, a is at least 1, and b is usually greater than a. The chemical compound or substituent is further specified in the form of _a form C _a -C _b -V. Where V represents a chemical compound class or group of substituents, for example an alkyl compound or an alkyl substituent.

Specifically, the common terms mentioned for the various substituents have the following meanings:

C ₁ -C ₅₀ -alkyl: straight or branched hydrocarbon radicals having up to 50 carbon atoms, for example C ₁ -C ₁₀ -alkyl or C ₁ -C ₂₀ -alkyl, preferably C ₁ -C ₁₀ -alkyl, -Alkyl, for example C ₁ -C ₃ -alkyl, such as methyl, ethyl, propyl, isopropyl or C ₄ -C ₆ -alkyl, n-butyl, sec- Ethyl, pentyl, 2-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, Dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, or C ₇ -C ₁₀ - alkyl, such as heptyl, octyl, 2-ethylhexyl, 2 , 4,4-trimethylpentyl, 1,1,3,3-tetramethylbutyl, nonyl or decyl, and isomers thereof.

C ₃ -C ₁₅ -cycloalkyl: monocyclic, saturated hydrocarbon group having 3 to 15 carbon ring members, preferably C ₃ -C ₈ -cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclo Hexyl, cycloheptyl or cyclooctyl, and also saturated or unsaturated cyclic groups such as norbornyl or norbenyl.

Aryl: a 1 to 3 nuclear aromatic ring system comprising 6 to 14 carbon ring members such as phenyl, naphthyl or anthracenyl, preferably 1 to 2 nuclei, particularly preferably 1 nuclear aromatic ring system.

In the context of the present invention, the symbol "*" indicates the valency at which one chemical group is bonded to another chemical group for all chemical compounds.

The polyalkylene polyamines can be obtained by reacting (i) aliphatic aminoalcohols with each other, or (ii) aliphatic diamines or polyamines and aliphatic diols or polyols in each case in the presence of a catalyst. Surprisingly, it has been found that when the hydrogen is injected during the reaction, the color number of the product is reduced. The comparison used for this is the product synthesized in the same way except that in each case there is no hydrogen. Thus, according to the present invention, when hydrogen is injected before or during the synthesis of the polyalkylene polyamine, i. E. When the reaction occurs in the presence of hydrogen gas, a low number of polyalkylene polyamines are obtained. The injection of the hydrogen gas is preferably carried out at a pressure of 0.1 to 25 MPa, more preferably 1 to 10 MPa, more particularly 1 to 7 MPa (partial pressure of the hydrogen gas). The temperature is preferably set at 100 to 200 占 폚, more preferably 130 to 180 占 폚. As a result of hydrogen implantation, the number of colors is reduced to two or more factors, preferably from 10 to 100 factors.

Aliphatic aminoalcohols suitable for the reaction in a hydrogen atmosphere include 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, such as 3-aminopropane-1-ol or 2-aminopropane- Ol, 2-aminobutan-1-ol or 3-aminobutan-1-ol, aminopentanol, for example 5-aminopentan-1-ol or 1-aminopentane- For example, 5-amino-2,2-dimethyl pentanol, aminohexanol, such as 2-aminohexan-1-ol or 6-aminohexan-1-ol, aminoheptane For example, 2-aminoheptan-1-ol or 7-aminoheptan-1-ol, aminooctanols such as 2-aminooctan-1-ol or 8- Ol, such as 2-aminononan-1-ol or 9-aminonan-1-ol, aminodecanol, for example 2-aminodecan-1-ol or 10- Aminoundecanol, for example 2-aminonedo 1-ol or 11-amino undecan-1-ol, aminododecanol, for example 2-aminododecan-1-ol or 12-aminododecan- For example, 2-aminotridecan-1-ol, 1- (2-hydroxyethyl) piperazine, 2- (2-aminoethoxy) ethanol, alkylalkanolamines such as butylethanolamine, , Ethyl ethanol amine, and methyl ethanol amine. Particularly preferred are monoethanolamine and monopropanolamine.

Aliphatic diamines suitable for the reaction under hydrogen atmosphere include at least two primary or at least one primary and at least one secondary or two or more secondary amino groups, which preferably 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, Diaminopentane or 1,2-diaminopentane, 1,5-diamino-2-methylpentane, diaminohexane such as 1,6-diaminohexane or 1,2-diaminohexane, Minoheptane such as 1,7-diaminoheptane or 1,2-diaminoheptane, diaminooctane such as 1,8-diaminooctane or 1,2-diaminooctane, diaminononane, For example, 1,9-diaminononane or 1,2-diaminononane, diaminodecane such as 1,10-diamino-decane or 1,2-diaminodecane, diaminoundecane, For example, 1,11-diamino undecane or 1,2-diamino undecane, diaminododecane, for example 1,12-diaminododecane or 1,2-diamino-dodecane, 3'-dimethyl-4,4'-diamino dicyclohexyl methane, 4,4'-di Diaminocyclohexylmethane, isophoronediamine, 2,2-dimethylpropane-1,3-diamine, 4,7,10-trioxal tridecane-1,13-diamine, 4,9 dioxadodecane-1,12 3- (cyclohexylamino) propylamine, 3- (methylamino) propylamine and 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, butanediol, for example 1,4- 3-diol or 1,2-butylene glycol, pentanediol such as neopentyl glycol or 1,5-pentanediol or 1,2-pentanediol, hexanediol such as 1,6-hexanediol or 1 , 2-hexanediol, heptanediol such as 1,7-heptanediol or 1,2-heptanediol, octanediol such as 1,8-octanediol or 1,2-octanediol, For example 1,9-nonanediol or 1,2-nonanediol, decanediol such as 1,10-decanediol or 1,2-decanediol, undecanediol, for example 1,11-undecanediol Or 1,2-undecanediol, dodecanediol, for example 1,12-dodecanediol, 1,2-dodecanediol, tridecanediol, for example 1,13-tridecanediol or 1,2- - tridecanediol, tetradecanediol, such as 1,14-tetradecanediol Or 1,2-tetradecanediol, pentadecanediol such as 1,15-pentadecanediol or 1,2-pentadecanediol, hexadecanediol such as 1,16-hexadecanediol or 1,2 Hexadecanediol, heptadecanediol, such as 1,17-heptadecanediol or 1,2-heptadecanediol, octadecanediol, such as 1,18-octadecanediol or 1,2-octadecanediol , 3,4-dimethyl-2,5-hexanediol, poly THF, 1,4-bis (2-hydroxyethyl) piperazine, diethanolamine such as butyldiethanolamine or methyldiethanolamine, di Alcohol amines and tri-alcohol amines.

Preferred polyalkylene polyamines obtainable according to the invention under hydrogen atmosphere include C ₂ -C ₅₀ -alkylene units, particularly preferably C ₂ -C ₂₀ -alkylene units. They may be linear or branched and they are preferably 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- Such as 1,6-hexylene, octylene, such as 1,8-octylene or 1,2-octylene, nonylene, such as 1,9-nonylene or 1,2-nonylene, Decylenes such as 1,2-decylenes or 1,10-decylenes, undecylenes such as 1,2-undecylenes, dodecylenes such as 1,12-dodecylenes or 1,2- Dodecylene, tridecylene, for example, 1,2-tridecylene, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl and neopentylene. Cycloalkylene units, for example 1,3- or 1,4-cyclohexylene, are also possible. The polyalkylene polyamine particularly preferably has a C ₂ -alkylene unit.

It is also possible to use a mixture of diaminoalkanes or a mixture of alkanediols or a mixture of aliphatic amino alcohols in each reaction under hydrogen pressure. The resulting polyalkylene polyamines may contain alkylene units of different lengths.

Multifunctional amino alcohols having more than one OH group or more than one primary or secondary amino group can also be reacted together under hydrogen pressure. In this case, a highly branched product is obtained. Examples of the polyfunctional amino alcohols include diethanolamine, N- (2-aminoethyl) ethanolamine, diisopropanolamine, diisononanolamine, diisodecanolamine, diisododecanolamine, diisododecanolamine, Diisotridecanolamine.

A polyol or a mixture of diol and polyol can also be reacted with a diamine under hydrogen pressure. Mixtures of polyamines or diamines and polyamines can also be reacted with diols. Mixtures of polyols or diols and polyols can also be reacted with mixtures of polyamines or diamines and polyamines. In this case, a highly branched product is obtained. Examples of polyols are glycerol, trimethylol propane, sorbitol, triethanolamine, and triisopropanolamine. Examples of polyamines include diethylenetriamine, tris (aminoethyl) amine, triazine, 3- (2-aminoethylamino) propylamine, dipropylenetriamine, N, N'- to be.

Particularly suitable compounds are those in which one or more initiator aliphatic aminoalcohols, aliphatic diamines or polyamines, or aliphatic diols or polyols comprise alkyl or alkylene groups having 2 to 4 carbon atoms.

Likewise, compounds particularly suited for the reaction under hydrogen pressure include one or more initiator aliphatic aminoalcohols, aliphatic diamines or polyamines, or aliphatic diols or polyols having 5 or more, preferably 7 or more, particularly preferably 9 or more, in particular And alkyl or alkylene groups having 12 or more carbon atoms.

Particularly suitable compounds are those which comprise from 5 to 50, preferably from 5 to 20, particularly preferably from 6 to 18, aliphatic amino alcohols, aliphatic diamines or polyamines, or aliphatic diols or polyols, Preferably from 7 to 16, particularly preferably from 8 to 14, in particular from 9 to 12 carbon atoms.

For synthesis, it is preferred to select at least (i) monoethanolamine, (ii) monopropanolamine or (iii) ethylene glycol with ethylenediamine. Further preferably, at least (i) ethylenediamine or (ii) 1,2-propylenediamine or (iii) 1,3-propylenediamine and 1,2-decanediol or 1,2- Is selected.

The hydroxyl and amino groups in diols, polyols and diamines, polyamines are preferably used in a molar ratio of 20: 1 to 1:20, particularly preferably in a ratio of 8: 1 to 1: 8, especially 3: 1 to 1: 3 do.

The polyalkylene polyamine can also be reacted under hydrogen pressure. During the reaction, diamines or polyamines, or diols or polyols, or amino alcohols may be added.

Hydrogen may be injected while water in the reactant is continuously or discontinuously removed from the system.

The preparation of polyalkylene polyamines is illustrated by way of example in formulas 1 and 2:

Equation 1

Equation 2

A homogeneous catalyst is considered to mean a catalyst present in the reaction medium in a uniformly dissolved form during the reaction.

Homogeneous catalysts generally include one or more elements (transition metals) of the sub-families of the Periodic Table of Elements. Alcohol amination under hydrogen pressure can be carried out with or without additional solvent. The alcohol amination can be carried out in a multiphase, preferably a one- or two-phase liquid system, generally at a temperature of from 20 to 250 ° C. In the case of a two-phase reaction system, the upper phase may consist of a nonpolar solvent, which contains most of the homogeneously dissolved catalyst and the lower phase comprises the polar initiator material, the polyamine formed and also water. Further, the lower phase may consist of water and also a homogeneously dissolved catalyst, and the upper phase may consist of a non-polar solvent comprising most of the formed polyamine and the non-polar starting material.

In a preferred embodiment of the invention, the diamine selected from (i) monoethanolamine or (ii) monopropanolamine or (iii) ethylenediamine, 1,3-propylenediamine or 1,2-propylenediamine is reacted with ethylene glycol, , 2-decanediol or 1,2-dodecanediol in the presence of a homogeneous catalyst and with the removal of water formed under hydrogen pressure of 1 to 10 MPa and during the reaction.

The number n of alkylene units of the polyalkylene polyamine is generally from 3 to 50,000.

The polyalkylene polyamines thus obtained may have both NH ₂ and also OH groups as terminal groups at the chain ends.

[Wherein, preferably,

Alkyl, - R is independently the same or different, H, and C ₁ -C ₅₀ together

l and m are independently the same or different and are integers ranging from 1 to 50, preferably from 1 to 30, particularly preferably from 1 to 20,

n and k are independently the same or different and are integers ranging from 0 to 50, preferably from 0 to 30, particularly preferably from 0 to 20,

and i is an integer ranging from 3 to 50,000.

The number-average molecular weight Mn of the polyalkylene polyamines obtained is generally from 200 to 2,000,000, preferably from 400 to 750,000, particularly preferably from 400 to 50,000. The molar mass distribution Mw / Mn is generally in the range of 1.2 to 20, preferably in the range of 1.5 to 7.5. The cationic charge density (pH 4-5) is generally in the range of 4 to 22 mequ / g, preferably in the range of 6 to 18 mequ / g of dry matter.

The polyalkylene polyamines obtained by the process according to the invention can be present in linear or branched or multi-branched form and also have ring-shaped structural units.

In this context, the distribution of structural units (linear, branched or cyclic) is random. The polyalkylene polyamines thus obtained differ from the polyethylene imine prepared from ethylene imine by the OH end groups present and also optionally by different alkylene groups.

The homogeneous catalyst is preferably a transition metal complex catalyst comprising at least one different metal of the subgroups of the Periodic Table of the Elements, preferably at least one element of Groups 8, 9 and 10 of the Periodic Table of the Elements, particularly preferably ruthenium or iridium . The specified sub-group metals are present in complex compound form. A number of different ligands are considered.

Suitable ligands present in the transition metal complex compounds include, for example, phosphine substituted with alkyl or aryl, polydentate phosphine substituted with alkyl or aryl bridged through an arylene or alkylene group, nitrogen- An aryl, an olefinic ligand, a hydride, a halide, a carboxylate, an alkoxylate, a carbonyl, a hydroxide, a trialkylamine, a dialkylamine, a dialkylamine, a dialkylaminocarbonyl, a heterocyclic carbene, a cyclopentane dienyl and a pentamethylcyclopentadienyl, Monoalkylamines, nitrogen aromatics such as pyridine or pyrrolidine and polydentate amines. The organometallic complex may comprise one or more different specified ligands.

Preferred ligands comprise one or more non-branched or branched, non-cyclic or cyclic, aliphatic, aromatic or araliphatic radicals having from 1 to 20, preferably from 1 to 12 carbon atoms (Monodentate) phosphine or (polydentate) polyphosphine such as diphosphine. Examples of branched cycloaliphatic and aromatic aliphatic radicals are -CH ₂ -C ₆ H ₁₁ and -CH ₂ -C ₆ H ₅ . Suitable radicals which may be mentioned by way of example are: methyl, ethyl, 1 -propyl, 2-propyl, 1 -butyl, 2-butyl, 1- (2- 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, cyclopentenyl, cyclohexyl, cycloheptyl and cyclooctyl, , Methylcyclohexyl, 1- (2-methyl) pentyl, 1- (2-ethyl) hexyl, 1- (2-propylheptyl), adamantyl and norbornyl, phenyl, tolyl and xylyl, Phenylpyrrole, 1- (2-methoxyphenyl) pyrrole, 1- (2,4,6-trimethylphenyl) imidazole and 1-phenylindole. The phosphine group may comprise two or three of the specified unbranched or branched, bicyclic or cyclic, aliphatic, aromatic or aromatic aliphatic radicals. These may be the same or different.

Preferably, the homogeneous catalyst is a finely branched, bicyclic or cyclic aliphatic radical having from 1 to 12 carbon atoms, or an aromatic aliphatic radical, or a monodentate or polydiorganosiloxane comprising adamantyl or 1-phenylpyrrole as a radical, Dendritic phosphine ligand.

In the specified unbranched or branched, bicyclic or cyclic, aliphatic, aromatic or aromatic aliphatic radical, the individual carbon atoms may also be replaced by additional phosphine groups. Also included are polydentates, for example bi- or tridentate phosphine ligands (the phosphine group is bridged by an alkylene or arylene group). The phosphine group is preferably selected from the group consisting of 1,2-phenylene, methylene, 1,2-ethylene, 1,2-dimethyl-1,2-ethylene, 1,3-propylene, 1,4- It is bridged by a bridge.

Particularly suitable monodentate phosphine ligands include triphenylphosphine, tritolylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, trimethylphosphine and triethylphosphine, Adamantyl) -n-butylphosphine, di (1-adamantyl) benzylphosphine, 2- (dicyclohexylphosphino) (Dicyclohexylphosphino) -1-phenylindole, 2- (di-tert-butylphosphino) -1-phenylindole , 2- (dicyclohexylphosphino) -1- (2-methoxyphenyl) -1H-pyrrole, 2- And 2- (di-tert-butylphosphino) -1-phenyl-1H-pyrrole. Particularly preferred are triphenylphosphine, triphenylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, trimethylphosphine and triethylphosphine, and also di (1-adamantyl) (dicyclohexylphosphino) -1-phenyl-1H-pyrrole and 2- (di-tert-butylphosphino) -1-phenyl-1H-pyrrole.

Particularly suitable polydentate phosphine ligands include bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,2-dimethyl- 1,2-bis (diethylphosphino) ethane, 1,3-bis (diphenyl-phosphino) propane, 1,4-bis (diphenylphosphino) Bis (diphenylphosphino) propane, 1,1,1-tris (diphenylphosphinomethyl) ethane, 1,1 ' -Bis- (diphenylphosphanyl) ferrocene and 4,5-bis (diphenylphosphino) -9,9-dimethylzanthene.

Furthermore, nitrogen-heterocyclic carbenes may be mentioned as preferred, especially as suitable ligands. In this context, these ligands which form water-soluble complexes with Ru are highly preferred. Particularly preferred are 1-butyl-3-methylimidazolin-2-ylidene, 1-ethyl-3-methylimidazolin- Ylidene. ≪ / RTI >

Particularly suitable ligands which may be mentioned are also cyclopentadienyl and derivatives thereof, such as alkyl, aryl and / or hydroxy mono- to penta substituted, such as methylcyclopentadienyl, pentamethylcyclopentadienyl, tetraphenyl Hydroxycyclopentadienyl, and pentaphenylcyclopentadienyl. In addition, particularly suitable ligands are substituted indenyl and derivatives thereof as described for cyclopentadienyl.

Likewise, particularly suitable ligands are chloride, hydride and carbonyl.

Of course, the transition metal complex catalyst may comprise two or more of the above described or the same ligands.

If the homogeneous catalyst may be used directly in its active form, or, for example [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) Cl], [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]} , [Ru ( _{cyclopentadienyl) (CO) 2 Cl],} [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 ( inde carbonyl) (CO) ₂ Cl], [Ru (inde carbonyl) (CO) ₂ H], inde [Ru (Neal ) (CO) _{2] 2,} ruthenocene, [Ru (by-naphthyl) Cl _2], [Ru ^{_{(bipyridine) 2 Cl 2 * 2H 2 O}} ], [Ru (COD) Cl 2] 2, [Ru ( penta methylcyclopentadienyl) (COD) Cl], [ Ru 3 (CO) 12], [Ru ( tetraphenyl-hydroxy-bicyclo Other _{dienyl) (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 (Pn -octyl _{3) 4 (H) 2]} , [IrCl 3 * H 2 O], KIrCl 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) Cl _{2] 2,} [Ir _{(cyclopentadienyl) (CO) 2], [} Ir ( _{pentamethylcyclopentadienyl) (CO) 2], [} Ir (PPh 3) 2 (CO) (H)], [Ir ( (PPh ₃ ) ₂ (CO) (Cl)] and [Ir (PPh ₃ ) ₃ (Cl)] to form the corresponding ligand, preferably the mono- or polydentatephosphine A ligand, or an addition of the above-mentioned nitrogen-heterocyclic carbenes.

The amount of metal components in the catalyst, preferably ruthenium or iridium, is generally in each case 0.1 to 5000 ppm by weight, based on the total liquid reaction mixture.

The process according to the invention can be carried out in the presence of a solvent. Of course, the process according to the invention can also be carried out in a solvent mixture.

When the process is carried out in a solvent, the amount of solvent is often chosen such that the starting materials (i) and (ii) dissolve directly in the solvent. Generally, 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 generally takes place in a liquid phase at a temperature of from 20 to 250 ° C. Preferably, the temperature is 100 DEG C or higher, preferably 200 DEG C or lower. The reaction may be carried out at a total absolute pressure of 0.1 to 25 MPa, which may be a hydrogen pressure combined with the intrinsic pressure of the solvent at the reaction temperature, or a gas pressure such as nitrogen or argon combined with hydrogen. The average reaction time is generally from 15 minutes to 100 hours.

Addition of base can have a positive effect on product formation. Suitable bases which may be mentioned here are alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alcoholates, alkaline earth metal alcoholates, alkali metal carbonates and alkaline earth metal carbonates, 0.01 to 100 equivalents of which are used, Can be used as a reference.

In a preferred embodiment of the process according to the invention, the heteroatom O or N of one of the starting materials (i) an aliphatic amino alcohol, (ii) an aliphatic diamine or polyamine, or an aliphatic diol or polyol, , And thus are located at adjacent carbon atoms.

In a preferred embodiment of the process according to the invention, the heteroatom O or N of one of the starting materials (i) aliphatic amino alcohols, (ii) aliphatic diamines or polyamines, or aliphatic diols or polyols is replaced by the alpha and omega positions , And thus is located at the opposite end of the carbon atom chain.

The present invention further provides polyalkylene polyamines, preferably polyethyleneamines or polypropyleneamines, which are prepared by the described embodiments of the process according to the invention.

A further object of the present invention is a polyalkylene polyamine comprising a hydroxy group, a secondary amine or a tertiary amine. A hydroxy group, a secondary amine or a tertiary amine is preferably located at the terminal carbon atom of the alkylene group and thus constitutes a terminal group. These polyalkylene polyamines preferably include a hydroxy group.

These polyalkylene polyamines containing a hydroxy group, a secondary amine or a tertiary amine can be obtained, for example, by the process according to the present invention. More particularly, these polyalkylene polyamines are obtained by a process by polymerization of monomers in one step.

Preferably, the ratio of the number of hydroxy end groups to the number of amine end groups (primary, secondary and tertiary) is from 10: 1 to 1:10, preferably from 5: 1 to 1: 5, 2: 1 to 1: 2.

In another preferred embodiment, these polyalkylene polyamines comprising a hydroxyl group, a secondary amine or a tertiary amine have only a hydroxy end group or only an amine end group (primary, secondary, tertiary).

The invention also relates to a process for the production of a composite film comprising the steps of: a) as an adhesion promoter for ink printing, b) as an auxiliary agent (adhesive) for the preparation of a composite film, c) as an agglomeration accelerator for the adhesive, d) as a crosslinking agent / As a wetting and adhesion promoter in emulsion paints, g) as complexing agents and flocculants, h) as penetration aids in wood preservation, i) as corrosion inhibitors, j) as fixatives for proteins and enzymes, To the use of polyalkylene polyamines as topic.

The invention is illustrated in more detail by way of example, provided that the embodiments do not limit the subject matter of the present invention.

Example

The average molecular weight of the oligomers was measured by gel permeation chromatography according to the method of size exclusion chromatography. The eluent used was hexafluoro isopropanol containing 0.05% potassium trifluoroacetate. Measurements were carried out on a styrene-divinylbenzene copolymer column (8 mm * 30 cm) using a RI differential refractometer or UV photometer as a detector at a flow rate of 1 ml / min at 40 占 폚. Calibration is performed using a narrow-range PMMA standard.

For determination of hazen color numbers (according to APHA), the samples are diluted 1: 2500 with unabsorbed diluent in the 380-720 nm range. Thereafter, the Hazen color number is measured in the range of 380 to 720 nm in 10 nm steps.

Generally speaking, the number of polyethylenepolyamines produced by known prior art processes is greater than 100, in some cases greater than 200, and in some instances even greater than 600.

Example 1

To a 250 ml autoclave equipped with a paddle stirrer was added 12.1 g (7.63 mmol) of [Ru (Pn octyl ₃ ) ₄ (H) ₂ ], 450 g (7.37 mol) of ethanolamine, 10.05 g (89.56 mmol) -Butoxide and 1620 ml of toluene were charged under the exclusion of oxygen under inert conditions. In a closed autoclave, hydrogen was injected at 40 bar. The reaction mixture was then heated to 140 < 0 > C and stirred for 20 hours. After the completed reaction and cooling, two phases were formed. The top phase containing the catalyst was separated from the bottom phase containing the product. The product phase was extracted by shaking with toluene. The water, unreacted reactants and volatile components of the reactants were then removed in a rotary evaporator at 12 mbar and 116 DEG C to yield 115.66 g of pure product. The weight average (RI) of the obtained oligomer was 1470 g / mol, and the degree of dispersion (Mw / Mn) was 2.8. This corresponds to an average chain length n of the oligomer (CH ₂ CH ₂ NH) _n of 34. The number of colors was 20.

Example 2

To a 250 ml autoclave equipped with a paddle stirrer was added 0.27 g (0.17 mmol) of [Ru (Pn octyl ₃ ) ₄ (H) ₂ ], 10.5 g of the effluent from Example 1, 230 mg (2.05 mmol) -Butoxide and 37 ml of toluene were charged under inert conditions. In a sealed autoclave, the reaction mixture is stirred at 140 < 0 > C for 10 hours under the intrinsic pressure of the solvent. After the completed reaction and cooling, the product precipitated as a solid. The batch is quenched with 200 ml of water, the product is dissolved and two phases are formed. The top phase containing the catalyst was separated from the bottom phase containing the product. The water, unreacted reactants and volatile components of the reactants were removed in a rotary evaporator at 12 mbar and 116 캜 to yield 9.42 g of pure product. The weight average (RI) of the obtained oligomer was 1520 g / mol, and the dispersion degree (Mw / Mn) was 3.4. This corresponds to an average chain length n of the oligomer (CH ₂ CH ₂ NH) _n of 35. The number of colors was 71.

Example 3

To a 250 ml autoclave equipped with a paddle stirrer was added 0.27 g (0.17 mmol) of [Ru (Pn octyl ₃ ) ₄ (H) ₂ ], 10.5 g of the effluent from Example 1, 230 mg (2.05 mmol) -Butoxide and 37 ml of toluene were charged under inert conditions. In a closed autoclave, hydrogen was injected at 15 bar. The reaction mixture was then heated to 140 < 0 > C and stirred for 10 hours. After the completed reaction and cooling, the product precipitated as a solid. The batch is quenched with 200 ml of water, the product is dissolved and two phases are formed. The top phase containing the catalyst was separated from the bottom phase containing the product. The pure product was obtained by removing water, unreacted reactants and volatile components of the reactants in a rotary evaporator at 12 mbar and 116 < 0 > C. The weight average (RI) of the obtained oligomer was 1170 g / mol, and the dispersion degree (Mw / Mn) was 3.4. This corresponds to an average chain length n of the oligomer (CH ₂ CH ₂ NH) _n of 27. The number of colors was 54.

Example 4

To a 250 ml autoclave equipped with a paddle stirrer was added 0.20 g (0.71 mmol) [Ru (COD) Cl ₂ ], 0.50 g (2.9 mmol) 1-butyl- ) 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 under inert conditions. In a sealed autoclave, the reaction mixture was stirred at 150 < 0 > C under intrinsic pressure of the solvent for 20 hours. After the completion of the reaction and cooling, 5 ml of water was added to the reaction mixture, which was shaken to obtain a solution of the product (50.0 g) in toluene and an aqueous solution of the catalyst (12.66 g). The phases were separated. From the product phase, unreacted reactants and volatile components were removed in a rotary evaporator at 12 mbar and 120 ° C to yield 14.13 g of pure product. The weight average (RI) of the obtained oligomer was 1470 g / mol, and the degree of dispersion (Mw / Mn) was 3.9. This corresponds to an average chain length n of the oligomer (CH ₂ CH (C ₁₀ H ₂₁ ) NHCH ₂ CH ₂ NH) _n of 6. The number of colors was 74.

Example 5

To a 250 ml autoclave equipped with a paddle stirrer was added 0.20 g (0.71 mmol) [Ru (COD) Cl ₂ ], 0.50 g (2.9 mmol) 1-butyl- ) 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 under inert conditions. In a sealed autoclave, inject hydrogen at 40 bar. The reaction mixture is then heated to 150 < 0 > C and stirred for 20 hours. After the completed reaction and cooling, 20 ml of water was added to the reaction mixture, which was shaken to obtain a solution of the product in toluene and also an aqueous solution of the catalyst. The phases were separated. From the product phase, unreacted reactants and volatile components were removed at 20 mbar and 120 < 0 > C in a rotary evaporator to yield 11.97 g of pure product. The weight average (RI) of the obtained oligomer was 1470 g / mol, and the degree of dispersion (Mw / Mn) was 3.9. This corresponds to an average chain length n of the oligomer (CH ₂ CH (C ₁₀ H ₂₁ ) NHCH ₂ CH ₂ NH) _n of 6. The number of colors was 21.

Comparative Example 1

(0.36 mmol) of [Ru (COD) (Cl) ₂ ] ₂ , 0.22 g of Triphos (0.36 mmol) and 0.2 g of tri-n-octylphosphine (0.54 mmol) in an autoclave equipped with a paddle stirrer, , 10 g (0.16 mol) of ethanolamine, 0.15 g (1.3 mmol) of potassium tert-butoxide and 60 g of toluene were charged under inert conditions. The reaction mixture was then heated to 140 < 0 > C and stirred for 20 hours. After completion of the reaction and cooling, the batch was further mixed with 10 ml of water. The upper phase was separated from the lower phase containing the product. Subsequently, 6.5 g of pure product was obtained by removing water, unreacted reactants and volatile components in a rotary evaporator at 12 mbar and 110 < 0 > C. The number of colors was 871.

Claims (30)

(i) reacting an aliphatic amino alcohol with one another, or
(ii) reacting the aliphatic diamine or polyamine with an aliphatic diol or polyol in the presence of a homogeneous catalyst and in the presence of hydrogen gas, with removal of water, by homogeneously catalyzed alcohol amination. The process according to claim 1, wherein the reaction is carried out at a partial pressure of hydrogen gas of from 0.1 to 25 MPa. 3. The method of claim 1 or 2, wherein hydrogen gas is chemically participated in the catalyzed alcohol amination to reduce the formation of colored components. 4. The process according to any one of claims 1 to 3, wherein the catalyst is a transition metal complex catalyst. 5. The process according to any one of claims 1 to 4, wherein the catalyst comprises ruthenium or iridium. 6. The process according to any one of claims 1 to 5, wherein the catalyst comprises a nitrogen-heterocyclic carbene ligand. 7. The process of claim 6, wherein the catalyst is selected from the group consisting of 1-butyl-3-methylimidazolin-2-ylidene, 1-ethyl-3-methylimidazolin- Dibutyl, dipropylimidazolin-2-ylidene, and dipropylimidazolin-2-ylidene. 6. The process according to any one of claims 1 to 5, wherein the catalyst comprises a monodentate or polydentate phosphine ligand. The method of claim 8, wherein the catalyst comprises a monodentate phosphine ligand comprising a non-branched, non-cyclic or cyclic aliphatic radical having from 1 to 12 carbon atoms, or an aromatic aliphatic radical. 10. The method of claim 8 or 9, wherein the catalyst is selected from the group consisting of triphenylphosphine, tritolylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, trimethylphosphine, triethylphosphine, (1-adamantyl) benzylphosphine, 2- (dicyclohexylphosphino) -1-phenyl-1H-pyrrolo Lt; / RTI > ligand. The process of claim 8, wherein the catalyst comprises a polydentate phosphine ligand consisting of one or more non-branched, bicyclic or cyclic aliphatic radicals having from 1 to 12 carbon atoms, or an aromatic aliphatic radical. The process according to claim 8 or 11, wherein the catalyst is selected from the group consisting of bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,2- ) Ethane, 1,2-bis (dicyclohexylphosphino) ethane, 1,2-bis (diethylphosphino) Bis (diphenylphosphonyl) butane, 1,1,1-tris (diphenylphosphinomethyl) ethane, 1,1'-bis (diphenylphosphanyl) 4,5-bis (diphenylphosphino) -9,9-dimethylzanthene. ≪ / RTI > 13. The method according to any one of claims 1 to 12, wherein the catalyst comprises a ligand selected from the group consisting of cyclopentadienyl, substituted cyclopentadienyl, indenyl, and substituted indenyl. 14. The process according to any one of claims 1 to 13, wherein the catalyst comprises a ligand selected from the group consisting of hydroxides, hydrides, carbonyls and chlorides. 15. The process according to any one of claims 1 to 14, wherein the reaction is carried out in the presence of a solvent. 16. The process of claim 15, wherein the solvent is selected from the group consisting of benzene, toluene, xylene, alkane, bicyclic and cyclic ethers, alcohols having more than 3 carbon atoms. 16. The process of claim 15, wherein the solvent is selected from the group consisting of water, ionic liquids, sulfoxides, formamides, acetonitrile. 18. The process according to any one of claims 1 to 17, wherein at least one reactant-aliphatic amino alcohol, aliphatic diamine or polyamine, or aliphatic diol or polyol- is used in an amount of 5 or more, preferably 7 or more, more preferably 9 More particularly an alkyl or alkylene group having at least 12 carbon atoms. 18. The method according to any one of claims 1 to 17, wherein at least (i) the monoethanolamine or (ii) ethylene glycol is reacted with ethylenediamine. 18. The process according to any one of claims 1 to 17, wherein 3-aminopropane-1-ol is reacted. The method according to any one of claims 1 to 17, wherein at least ethylenediamine or 1,2-propylenediamine or 1,3-propylenediamine and 1,2-decanediol or 1,2-dodecanediol are selected . 18. The process according to any one of claims 1 to 17, wherein the at least one reactant-aliphatic amino alcohol, aliphatic diamine or polyamine, or aliphatic diol or polyol- comprises an alkyl or alkylene group having 2 to 4 carbon atoms . 18. The process according to any one of claims 1 to 17, wherein at least one of the reactant-aliphatic amino alcohols, aliphatic diamines or polyamines, or aliphatic diols or polyols is used in an amount of from 5 to 20, preferably from 6 to 18, Comprises an alkyl or alkylene group having 7 to 16, more particularly 8 to 14 carbon atoms. 24. A process according to any one of claims 1 to 18, 22 and 23, wherein the starting material is an aliphatic amino alcohol, an aliphatic diamine or a polyamine, or an aliphatic diol or polyol, Lt; RTI ID = 0.0 > and / or < / RTI > adjacent carbon atoms. 24. A process according to any one of claims 1 to 18, 22 and 23, wherein the starting material is an aliphatic amino alcohol, an aliphatic diamine or a polyamine, or an aliphatic diol or polyol, Wherein the alpha and omega positions of the carbon atom chain are located at opposite ends of the carbon atom chain. 25. A polyalkylene polyamine obtainable by a process according to any one of claims 1 to 25. 20. A polyethyleneimine obtainable by a process according to claim 19. A polypropyleneamine obtainable by the process according to claim 20. A polyalkylene polyamine comprising a hydroxyl group, a secondary amine or a tertiary amine. (a) an adhesion promoter for ink printing,
(b) an adhesion promoter in the composite film,
(c) a flocculant for the adhesive,
(d) a crosslinking agent / curing agent for the resin,
(e) a primer for paint,
(f) wet-adhesion promoters for emulsion paints,
(g) complexing agents and flocculants,
(h) Penetration auxiliaries in wood preservation,
(i) corrosion inhibitors,
(j) the use of the polyalkylene polyamines according to any one of claims 26 to 29 as immobilizing agents for proteins and enzymes.