EP2961787A1

EP2961787A1 - Polyamines and method for the production thereof

Info

Publication number: EP2961787A1
Application number: EP14705155.1A
Authority: EP
Inventors: Ansgar Gereon Altenhoff; Christoph Müller; Christian Müller; Andreas Kunst; Thomas Reissner; Kirsten Dahmen
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2013-02-28
Filing date: 2014-02-18
Publication date: 2016-01-06
Also published as: WO2014131649A1; JP2016514178A; CN105008431A

Abstract

The present invention relates to polyamines and a method for producing polyamines.

Description

Polyamines and process for their preparation

Description The present invention relates to polyamines and to a process for the preparation of polyamines.

Polyamines generally refer to polymers having in the chain aminic repeating units R-NH-R or R-NR-R. Such polyamines are typically prepared by polymerization of diamines, aminoalcohols, cyclic imines such as aziridines, and cyclic imino ethers such as 2-oxazolines.

Polyamines in whose main chains NH groups are present, which are separated from each other by two methylene groups

are commonly referred to as polyethyleneimines (PEI).

Polyethyleneimines are valuable products with a variety of different uses. For example, polyethyleneimines are used: a) as adhesion promoters, for example for printing inks for laminate films;

b) as an aid (adhesion), for example for the production of multilayer composite films, whereby not only different polymer layers, but also metal foils are compatibilized;

c) as a bonding agent for adhesives, for example in conjunction with polyvinyl alcohol, - butyrate, and acetate and styrene copolymers, or as cohesive promoter for label adhesives;

d) as a primer in paint applications to improve adhesion to substrates such as glass, wood, plastic and metal;

e) to improve the wet adhesion, for example in standard emulsion paints and to improve the instantaneous rainfastness of paints, for example for

Road markings;

f) as a complexing agent, in particular with high binding capacity for heavy metals such as Hg, Pb, Cu, Ni;

g) as a flocculant, for example in water treatment / water treatment; h) as a penetration aid, for example for active metal salt formulations in wood preservation;

i) as corrosion inhibitors, for example for iron and non-ferrous metals and in areas of gasoline production, the secondary oil production

j) for the immobilization of proteins and enzymes; Microorganisms or immobilizing the carrier of enzymes and microorganisms

k) for blocking and sealing, for example oil and gas industry;

I) as a fixing agent, for example in the textile industry, in particular as a formaldehyde-free co-fixer;

m) as an additive in the cosmetics sector, for example for hair fixatives and rinses;

n) as auxiliaries in the paper industry, for example for dewatering acceleration, impurity elimination, charge neutralization and paper coating as versatile; o) for the separation of oil and water, for example in the metalworking industry; p) as an additive for landfill gaskets;

q) as a flocculant;

r) as swimming pool gallbladder;

s) for the production of bitumen chemicals by conversion with fatty acids;

t) as an anti-swelling agent for delaying the absorption of water;

u) as an emulsifier or emulsion breaker;

v) as surfactant in industrial cleaning (IC);

w) as a wood preservative;

x) for the preparation of complexing agents (polycarboxylates);

(y) for the production of ore mining and mineral processing equipment;

z) as a dispersant for pigments, ceramics, carbon black, carbon, carbon fibers, metal powder; aa) for gas scrubbing as an absorbent of CO2, NOx, SOx, C and aldehydes and for the neutralization of acidic constituents;

bb) for water softening;

cc) as a crystallization inhibitor;

dd) as a rheology modifier (thickener);

(ee) as auxiliaries or building blocks of aids for the extraction and processing of oil, coal and natural gas;

ff) for the production of synthetic rubber and rubber chemicals;

gg) as an additive in coolants, lubricants and coolants;

hh) as auxiliaries in the field of construction chemistry;

ii) as part of electroplating baths; or

jj) for the production of non-viral gene vectors.

Other polyalkylene polyamines which are not derived from ethyleneimine can also be used for these applications. Polyethyleneimines are generally prepared by ring-opening polymerization of unsubstituted or substituted 2-oxazolines of the formula A.

(A)

or unsubstituted or N-substituted aziridines of the formula B

R N

A

(B) produced. The preparation of polyethyleneimines is described in detail in, for example, the review article by S. Kobayashi (Prog. Polym., Vol. 15, 751-823, 1990).

By cationic polymerization of 2-oxazolines and subsequent alkaline hydrolysis unbranched linear polyethyleneimines (LPEI) can be obtained as far as possible. Linear polyethyleneimines are usually crystalline (melting temperature at about 59 ° C) and generally dissolve only in hot water.

The ring-opening polymerization of aziridines generally leads to hyperbranched polyethylenimines (BPEI). In these polymers, the ratio of primary amines, secondary amines and tertiary amines is approximately 25:50:25 (Kobayashi, supra p. 758).

In addition to the ring opening of aziridine, the ring opening of other cyclic imines is known. Thus, it has been disclosed in DE-1 037 126 that hexamethyleneimine (hexahydro-1 H-azepine) can be polymerized using an acidic catalyst. The polymerization was carried out at high temperatures in the range of 200 to 300 ° C. However, the polymers thus obtained had only a low degree of polymerization.

The ring-opening polymerization requires the use of cyclic monomers as starting material. Only a few cyclic monomers suitable for the preparation of polyamines are commercially and inexpensively or in larger quantities available. Other cyclic imines, in particular ethyleneimine, require a complicated handling, since they have highly reactive, toxic or corrosive properties. It must also be ensured that no ethyleneimine remains in the products or wastewater streams obtained.

For the preparation of non-aziridine-derived polyalkylene polyamines

[(CH2) xN] - With alkylene groups> C2 (x> 2), there is no industrially practiced, the Aziridinroute analogous process, which there is no cost-effective process for their preparation.

An alternative route of preparation for obtaining polyamines is the polymerization of diamines and diols or aminoalcohols. The polymerization can be catalyzed homogeneously or heterogeneously.

The homogeneously catalyzed preparation of polyamines is described, for example, in DE-A 26 24 135 or WO 201 1/151268. DE-A 26 24 135 discloses the preparation of polyalkylenepolyamines by reacting alkylenediamines with diols in the presence of phosphoric acid, their anhydrides, metal salts and esters at temperatures of from 250 to 350 ° C. in the liquid phase.

In WO 201 1/151268 a process for the preparation of polyalkylenepolyamines by catalyzed alcohol amination is described in which aliphatic amino alcohols are reacted with each other or aliphatic diamines or polyamines with aliphatic diols or polyols with elimination of water in the presence of a catalyst. The catalysts used in the reaction medium are homogeneously dissolved ruthenium or iridium compounds which contain a monodentate or polydentate phosphine ligand.

In the homogeneous-catalyzed preparation of polyamines, the catalyst usually remains in the polymerization. The fate of catalytically active metals in the polymer can lead to a degradation reaction in the polymer or affect the processability of the polymer, especially when the polymer is reacted with crosslinkers or chain extenders. Furthermore, the fate of residual metal can lead to high manufacturing costs, if the catalyst contains a metal or precious metal, which has a high market value. Alternatively, the homogeneously dissolved catalyst can be separated. However, such separation processes are technically complicated and also contribute to an increase in the production costs. Because of side reactions, which can also be catalyzed by the catalyst remaining in the polymer, the homogeneously produced polyamines can often be discolored. Furthermore, polyamines with a low molecular weight are generally obtained by means of homogeneous catalysis. molecular weight and / or a high degree of branching. These properties may limit the uses of the polyamines so produced.

The heterogeneously catalyzed preparation of polyamines from alkylenediamines is described in several patents.

DE 2439275 and DE 254087 describe the reaction of ethylenediamine and 1,3-propylenediamine into oligomers having a low degree of oligomerization. From DE 2439275 it is known to implement ethylenediamine at 100 to 150 ° C in the presence of metals of the eighth to eleventh subgroup of the Periodic Table of the Elements as catalysts to diethylenetriamine (DETA) and triethylenetetramine (TETA). As catalysts, copper and nickel or copper, nickel and cobalt-containing catalysts are explicitly mentioned. The reaction takes place at 100 to 150 ° C, preferably in the presence of hydrogen. The hydrogen pressure can be varied within wide limits. It can be up to 250 bar. The reaction can be carried out discontinuously or continuously. The residence time in continuous driving is 5 to 10 hours. The conversion of ethylenediamine is less than 70%. DE 2540871 represents a further embodiment of DE 2439275. Instead of ethylenediamine, 1,3-propylenediamine is used and reacted under similar conditions as in DE 2439275 to dipropylenetriamine and tripropylenetetramine. Work is carried out at 50 to 250 ° C, pressures of 1 to 500 bar and residence times of 1 to 4 hours.

From a further embodiment of DE 2540871, namely DE 2605212 it is apparent that the reaction of 1, 2 or 1, 3-propylenediamine can lead to any desired conversion. It is described that waxy polypropylene polyamines are obtained at about 180 ° C

WO 92/17437 discloses polymers of hexamethylenediamine, their preparation and their use as lubricants. The polymerization is carried out in the range of 100-230 ° C at atmospheric pressure on nickel catalysts, such as Raney nickel. It is disclosed that preferably the ammonia formed during the polycondensation should be removed from the reactor. In the examples it is described that the polymerization products are brown discolored and have a mean degree of oligomerization of 2 to 5, with the dimer being formed as the main component.

JP 49102800 discloses the discontinuous polymerization of diamines of the type

R - HN - CH ₂ - (CH = CH) _n - CH ₂ NH R ₁

in which n = 0 or> 1 and R and Ri denote hydrogen or hydrocarbon radicals, in the presence of palladium, rhodium or their compounds. From ethylenediamine (n = 0, R and Ri = H), a viscous polymer was obtained at 200 ° C, 7 atm and a reaction time of 11 hours in the presence of palladium.

DE 2842264 describes a process for the preparation of oligo- and polyhexamethylene polyamines by reacting hexamethylenediamine in the presence of a palladium catalyst from the group of metallic palladium or palladium compounds. Apparently, the reaction is carried out at 50 to 300 ° C at atmospheric pressure or elevated pressures using ammonia or nitrogen. The process can be carried out continuously or batchwise. As soon as the pressure has risen due to the formation of ammonia in discontinuous mode of operation, it is kept at about below 5 to 8 bar by expansion (examples 2, 1 and 3). According to the description, the polyhexamethylene polyamines thus obtained have an average molecular weight of 500 to 20,000 g / mol and are largely linear since more than 70% of the monomers in the polymer are linked as secondary amines. In the examples, yellowish-white polymers having an average molecular weight in the range of slightly less than 500 to 3000 g / mol are obtained.

The object of the present invention was to provide a process for the preparation of polyamines that - allows the use of a variety of monomers, so that a wide variety of homo- and co-polyamines can be achieved (by the choice the monomers can be tailored to the properties of the polyamines prepared),

the use of monomers which are available commercially and / or inexpensively and / or which can be handled without high safety-related use or which are advantageous in terms of their toxicological properties,

enables the production of polyamines from bifunctional monomers which are substantially linear and less branched,

enables the production of polyamines which have a low metal content,

allows the preparation of polyamines which have a low phosphorus content, allows the preparation of polyamines which are essentially colorless or have only a slight degree of discoloration,

enables the production of polyamines having a high average degree of polymerization,

enables the production of polyamines which have a low OH number and, associated therewith, a high charge density,

- allows the production of polyamines with a low degree of deamination,

enables the production of polyamines which have a low chloride content,

- allows the production of polyamines having both a low degree of branching and a high average degree of polymerization. Furthermore, should

the process has comparatively short residence times or reaction times,

the catalyst used for the polymerization can easily be separated off from the polymer and reused for further polymerizations, the service life and activity of the catalyst in the process can be high, so that the frequency of costly catalyst changes can be reduced,

a high degree of polymerization or a high conversion of diamines are achieved in low residence times,

the recycling of unreacted diamine is made possible,

- The degree of side reactions are kept as low as possible, and / or

a method is provided which also operates continuously

can be.

The object was achieved by a process for the preparation of polyamines in a reactor, by reacting diamines, which are in the liquid phase, in the presence of a catalyst which is in the solid phase, characterized in that the reactor Gas feeds, wherein the amount of supplied gas is 1 to 1000 liters of gas per liter of free reactor volume per hour and the gas is introduced into the liquid phase and the gas together with ammonia, which is formed in the reaction, removed from the reactor.

reactants

The starting compounds used are preferably diamines (also referred to below as "monomers").

Particular preference is given to using aliphatic alkylenediamines having 2 or more C atoms in the alkylene chain.

Particularly preferred aliphatic alkylenediamines can be described by formula I.

(I) and the radicals have the following meaning: R 1 and R ₂ are simultaneously or independently hydrogen, linear or branched C ₁ - to C 12 -alkyl, C ₇ - to C 12 -aralkyl, C ₆ - to Cio-aryl, C ₃ - to C ₈ -cycloalkyl or C ₃ - to C ₈ - cycloalkyl in which a Ch group is replaced by O, NH or NR 10; R 3 _X and R 4 _X are simultaneously or independently hydrogen, linear or branched C ₁ - to C 12 -alkyl, C ₇ - to C ₂ -aralkyl, C ₆ - to Cio-aryl, C ₃ - to C ₈ -cycloalkyl or C ₃ - to C ₈ - cycloalkyl in which a Ch group is replaced by O, NH or NR 10;

R 10 is linear or branched C ₁ - to C 12 -alkyl, C ₇ - to C 12 -aralkyl, C ₆ - to C 10 -aryl or C ₃ - to C ₈ -cycloalkyl; z is a value of 2 to 20, preferably 3 to 20; and x is an index that can take all values from 1 to z.

R1, R2, R3 _X and R4 _X are preferably hydrogen and z is a value of 2 to 8, more preferably R1, R2, R3 _X and R4 _{X are} hydrogen and z is a value of 3 to 8.

Very particularly preferred aliphatic alkylenediamines are

Ethylenediamine, 1,3-propylenediamine, 1,2-propylenediamine, 1,4-butylenediamine, 1,2-butylenediamine, 1,5-diaminopentane, 1,2-diaminopentane, 1,5-diamino-2-methylpentane, 1, 6-diaminohexane, 1, 2-diaminohexane 1, 7-diaminoheptane, 1, 2-diaminoheptane, 1, 8-diaminooctane, 1, 2-diamino octane, 1, 9-nonamethylenediamine, 1, 10-decamethylenediamine, 1, 2-diaminodecane , 1,1,1-undcamethylendiamine, 1,2-diaminoundekane, 1,12-dodecamethylenediamine, 1,2-diaminododecane, 2,2-dimethylpropane-1,3-diamine, 4,7,10-trioxatridane-1-one, 13-diamine, 4,9-dioxadodecane-1, 12-diamine and 3- (methylamino) propylamine, or mixtures thereof.

Especially preferred is the process when ethylenediamine is used only in mixtures with the above aliphatic alkylenediamines. In particular, the process according to the invention is particularly particularly preferred when ethylenediamine is excluded as the sole diamine to be used.

Further preferred diamines are oligomeric polyalkyleneamines consisting of 2 to 5 amine units, or mixtures thereof.

Particularly preferred oligomeric polyalkyleneamines can be described by formula II

(Ii)

and the radicals have the following meaning:

R1, R2, R3 _y R4 _Y and R 5 are simultaneously or independently of one another are hydrogen, linear or branched d- to Ci2-alkyl, C7-Ci2-aralkyl, C6- to Cio-aryl, C3-Cs-cycloalkyl or C3 - to Cs-cycloalkyl, in which a Ch group is replaced by O, NH or NR10;

R10 has the meaning given above; a) is a value of 2 to 5;

b) is a value from 2 to 12; and y is an index that can take all values between 1 and b. Very particularly preferred polyalkyleneamines are N, N-bis (3-aminopropyl) methylamine, N, N'-bis- (3-aminopropyl) ethylenediamine, 3- (2-

Aminoethylamino) propylamine, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethyl-enpentamine (TEPA), di-1,3-propylenetriamine, tri-1,3-propylenetetramine and tetra-1,3-propylenepentamine, Di-1,2 -propylentriamine, tri-1, 2-propylenetetramine and tetra-1,2-propylenepentamine, dihexamethylenetriamine, trihexamethylenetetramine and tetrahexamethylenepentamine.

Other preferred diamines are cyclic diamines in which the amino groups are attached either directly or indirectly to one or more unsubstituted or substituted cycloaliphatic, heteroaliphatic, aromatic or heteroaromatic rings bonded together.

Particularly preferred cyclic diamines are alicyclic diamines.

Preferred alicyclic diamines are 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, isophoronediamine, 1,3-bis- (aminomethyl) -cyclohexane, bis- (4- amino-cyclohexyl) -methane, bis (4-amino-3,5-dimethyl-cyclohexyl) -methane or bis (4-amino-3-methylcyclohexyl) -methane, 3- (cyclohexylamino) propylamine, bis ( Aminoethyl) piperazine and bis (aminomethyl) piperazine. Particularly preferred aromatic cyclic diamines are aromatic diamines in which the amino group is not substituted directly on the aromatic nucleus.

Preferred aromatic diamines are the isomeric bis (aminomethyl) benzenes, especially meta-xylenediamine (MXDA), or isomers of aminobenzylamine (2-aminobenzylamine, 4-aminobenzylamine), 4- (2-aminoethyl) aniline, m-xylylenediamine, o- Xylylenediamine, or 2,2'-biphenyldiamines, or oxydianilines, such as 4,4'-oxydianiline, isomers of diaminofluorene, isomers of diaminophenanthrene and 4,4'-ethylenedianiline.

Further preferred diamines are polyetheramines of the formula III

(III)

and the radicals have the following meaning:

R 1 and R ₂ are simultaneously or independently hydrogen, linear or branched C ₁ - to C 12 -alkyl, C ₇ - to C 12 -aralkyl, C ₆ - to Cio-aryl, C ₃ - to C ₈ -cycloalkyl or C ₃ - to C ₈ - cycloalkyl in which a Ch group is replaced by O, NH or NR 10; R 3, R 4 and R 5 are simultaneously or independently hydrogen, linear or branched C 1 to C 12 alkyl, C 7 to C 12 aralkyl, C 6 to C 10 aryl, C 3 to C 8 cycloalkyl or C 3 to C 8 cycloalkyl, by a CH 2 group is replaced by O, NH or NR 10;

R 10 is linear or branched C 1 - to C 12 -alkyl, C 7 - to C 12 -aralkyl, C 6 - to C 10 -aryl or C 3 - to C 8 -cycloalkyl; u, v and w are independently a value from 0 to 100.

Preferably u and w take a value of 0 and v a value> 0 and the substituents R 1 to R 5 are preferably hydrogen (polyether amines based on ethylene glycol). Further preferably, v assumes a value of 0 and (u + w) a value of> 0 and the substituents R1 and R2 are preferably hydrogen and the substituents R3 to R5 are preferably methyl (polyether amines based on propylene glycol). With further preference v assumes a value of> 0 and (u + w) a value of> 0 and the substituents R1 to R2 are preferably hydrogen and the substituents 3 to R5 are preferably methyl (block polyetheramines having a middle block based on Polyethylene glycol and outer blocks based on propylene glycol). Very particular preference Polyether diamines are 4,7,10-Trioxatridekan-1, 13-diamine, 4,9-dioxadodecane-1, 12-diamine and so-called Jeffamine® the Fa. Huntsman, especially Jeffamin D230, Jeffamin D400, Jeffamin D2000, Jeffamine D4000, Jeffamin ED600, Jeffamin ED900, Jeffamine ED2003, Jeffamin EDR148 and Jeffamin EDR176

(Designations from the product brochure of the company Alfa Chemicals Ltd with the reference number "Hunt32").

80 mol% and more, more preferably 90 mol% and more, very particularly preferably 95 mol% and more and especially preferably 99 mol% and more of the abovementioned bifunctional monomers can preferably be used in the process.

In addition to diamines, no further monomers are very particularly preferably used in the process.

catalyst

As catalysts for the reaction of diamines to polyamines, in particular catalysts can be used which contain one or more elements of the 8th subgroup of the Periodic Table (Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt), preferably Co, Ni , Ru, Cu or Pd, more preferably Co, Ni and / or Cu (hereinafter also referred to as catalytically active metals).

The abovementioned catalysts can be doped in the customary manner with promoters, for example with chromium, iron, cobalt, manganese, molybdenum, titanium, tin, metals of the alkali metal group, metals of the alkaline earth metal group and / or phosphorus.

As catalysts, so-called skeletal catalysts (also referred to as Raney® type, hereinafter also referred to as: Raney catalyst) which are obtained by leaching (activation) of an alloy of catalyst, reactive metal and a further component (preferably Al) may preferably be used , Preference is given to using Raney nickel catalysts or Raney cobalt catalysts. As catalysts, preference is furthermore given to using Pd or Pt supported catalysts. Preferred support materials are activated carbon, Al2O3, ΤΊΟ2, ZrÜ2 and S1O2.

Very particular preference is given to using catalysts in the process according to the invention which are prepared by reduction of so-called catalyst precursors.

The catalyst precursor contains an active material which contains one or more catalytically active components, optionally promoters and optionally a carrier material. The catalytically active components are oxygen-containing compounds of the abovementioned catalytically active metals, for example, and their metal oxides or hydroxides, such as CoO, NiO, CuO and / or their mixed oxides.

In the context of this application, the term catalytically active components is used for the abovementioned oxygen-containing metal compounds, but is not intended to imply that these oxygen-containing compounds are already catalytically active per se. As a rule, the catalytically active components have a catalytic activity in the reaction according to the invention only after the reduction has taken place. Particular preference is given to catalyst precursors comprising one or more oxides of the elements Cu, Co and Ni, such as the oxide mixtures disclosed in EP-A-0636409 which, prior to reduction with hydrogen, have 55 to 98% by weight of Co, calculated as CoO, 0.2 to 15% by weight of phosphorus, calculated as H 3 PO 4, from 0.2 to 15% by weight of manganese, calculated as MnO ₂ , and from 0.2 to 15% by weight of alkali, calculated as M ₂ O (M = alkali) , or in EP-A-0742045 disclosed oxide mixtures, prior to reduction with hydrogen 55 to 98 wt .-% Co, calculated as CoO, 0.2 to 15 wt .-% phosphorus, calculated as H3PO4, 0.2 to 15% by weight of manganese, calculated as MnO ₂ , and 0.05 to 5% by weight of alkali, calculated as M ₂ O (M = alkali), or oxide mixtures disclosed in EP-A-696572, which have been prepared before Reduction with hydrogen 20 to

85% by weight of ZrO.sub.2, 1 to 30% by weight of oxygen-containing compounds of copper, calculated as CuO, 30 to 70% by weight of oxygen-containing compounds of nickel, calculated as NiO, 0.1 to 5% by weight of oxygen-containing compounds of molybdenum, calculated as M0O3, and 0 to 10 wt .-% of oxygen-containing compounds of aluminum and / or manganese, calculated as Al2O3 or MnÜ2 contains, for example, the in loc. Cit., page 8, disclosed catalyst having the composition 31, 5 wt .-% Zr0 ₂ , 50 wt .-% NiO, 17 wt .-% CuO and 1, 5 wt .-% M0O3, or contain in EP-A-963975 disclosed oxide mixtures, prior to reduction with hydrogen 22 to 45 wt .-% ZrÜ2, 1 to 30 wt .-% oxygen-containing compounds of copper, calculated as CuO, 15 to 50 wt .-% of oxygen-containing compounds of Nickel, calculated as NiO, where the molar Ni: Cu ratio is greater than 1, 15 to 50% by weight of oxygen-containing compounds of cobalt, calculated as CoO, 0 to 10% by weight of oxygen-containing compounds of aluminum and / or manganese, calculated as Al2O3 or MnÜ2, and contains no oxygen-containing compounds of molybdenum, for example, the in loc. cit., page 17, disclosed catalyst A having the composition 33 wt% Zr, calculated as ZrO2, 28 wt% Ni, calculated as NiO, 11 wt% Cu, calculated as CuO and 28 wt%. % Co calculated as CoO.

In a very particularly preferred embodiment, 50 to 100 mol%, particularly preferably 60 to 99 mol% and very particularly preferably 75 to 98 mol% of the catalytically active metals contained in the catalytically active composition one or more metals selected from the group consisting of Cu , Co and Ni.

The molar ratio of the atoms of the components of the active composition to one another can be measured by known methods of elemental analysis, for example atomic absorption spectrometry (AAS), atomic emission spectrometry (AES), X-ray fluorescence analysis (RFA) or ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometry) become. However, the molar ratio of the atoms of the components of the active mass to one another can also be determined mathematically, for example by determining the weights of the compounds used, which contain the components of the active composition, and the proportions of the atoms of the components of the active composition on the basis of known stoichiometry of the compounds used can be determined so that the atomic ratio of the weigh-in and the stoichiometric formula of the compound used can be calculated. Of course, the stoichiometric formula of the compounds used can also be determined experimentally, for example by one or more of the above methods. Depending on the process carried out (suspension polymerization, fluidized bed process, fixed-bed polymerization), the catalysts are used as powder, grit or shaped body (preferably extrudates or tablets).

The catalysts or catalyst precursors are preferably used in the form of shaped bodies in the process according to the invention.

As moldings are those with any geometry or shape. Preferred shapes are tablets, rings, cylinders, star strands, cartwheels or balls. Particularly preferred are tablets, rings, cylinders, spheres or star strands. Especially suitable is the strand shape. impregnation

In a preferred embodiment, the catalysts are used in the form of shaped bodies in the process according to the invention, which are produced by impregnation of carrier materials which have the abovementioned geometry or which after impregnation deforms into shaped bodies having the above-mentioned geometry become.

Examples of suitable carrier materials are carbon, such as graphite, carbon black, graphene, carbon nanotubes and / or activated carbon, aluminum oxide (gamma, delta, theta, alpha, kappa, chi or mixtures thereof), silicon dioxide, zirconium dioxide, zeolites, aluminosilicates or mixtures thereof consideration.

The impregnation of the abovementioned support materials can be carried out by the usual methods (A.B. Stiles, Catalyst Manufacture - Laboratory and Commercial Preparations, Marcel Dekker, New York, 1983), for example by applying a metal salt solution in one or more impregnation stages. Suitable metal salts are, as a rule, water-soluble metal salts, such as the nitrates, acetates or chlorides of the corresponding catalytically active components or doping elements, such as co-nitrate or co-chloride. Subsequently, the impregnated support material is usually dried and optionally calcined.

The calcination is generally carried out at temperatures between 300 and 800 ° C, preferably 350 to 600 ° C, especially at 450 to 550 ° C.

The impregnation can also be carried out by the so-called "incipient wetness method", in which the support material is moistened to the maximum saturation with the impregnation solution in accordance with its water absorption capacity. The impregnation can also be done in supernatant solution.

In the case of multistage impregnation methods, it is expedient to dry between individual impregnation steps and, if appropriate, to calcine. The multi-step impregnation is advantageous to apply when the carrier material is to be applied in a larger amount with metal salts.

For applying a plurality of metal components to the support material, the impregnation can take place simultaneously with all metal salts or in any order of the individual metal salts in succession.

Preferably, carrier materials are used which already have the preferred geometry of the shaped bodies described above.

However, it is also possible to use carrier materials which are present as powder or grit, and to subject impregnated carrier materials to a shaping. Thus, for example, the impregnated and dried or calcined carrier material can be conditioned.

The conditioning can be carried out, for example, by adjusting the impregnated carrier material by grinding to a specific particle size.

After grinding, the conditioned, impregnated carrier material can be mixed with molding aids, such as graphite, or stearic acid, and further processed into shaped bodies. Common methods of shaping are described, for example, in Ullmann [Ullmann's Encyclopedia Electronic Release 2000, Chapter: "Catalysis and Catalysts", pages 28-32] and by Ertl et al. [Ertl, Knözinger, Weitkamp, Handbook of Heterogeneous Catalysis, VCH Weinheim, 1997, pages 98 ff]. Common methods of molding include extrusion, tableting, i. mechanical pressing or pelleting, i. Compacting by circular and / or rotating movements.

By the process of shaping moldings can be obtained with the above geometry.

After conditioning or shaping is usually a tempering. The temperatures during the heat treatment usually correspond to the temperatures during the calcination. mixed precipitation

In a further preferred embodiment, molded articles are used in the process according to the invention, which are prepared by a co-precipitation (mixed precipitation) of all their components and the thus precipitated catalyst precursors are subjected to shaping.

For this purpose, as a rule, a soluble compound of the corresponding active component, the doping elements and optionally a soluble compound of a carrier material in a liquid in the heat and with stirring as long as mixed with a precipitating agent until the precipitation is complete.

The liquid used is usually water.

As a soluble compound of the active components are usually the corresponding metal salts, such as the nitrates, sulfates, acetates or chlorides, the above-mentioned metals into consideration. Water-soluble compounds of Ti, Al, Zr, Si, etc., for example the water-soluble nitrates, sulfates, acetates or chlorides of these elements, are generally used as the soluble compounds of a carrier material. Water-soluble compounds of the doping elements, for example the water-soluble nitrates, sulfates, acetates or chlorides of these elements, are generally used as the soluble compounds of the doping elements.

Usually, in the precipitation reactions, the soluble compounds are precipitated by addition of a precipitant as sparingly or insoluble, basic salts.

The precipitants used are preferably bases, in particular mineral bases, such as alkali metal bases. Examples of precipitants are sodium carbonate, sodium hydroxide, potassium carbonate or potassium hydroxide. As precipitating agent it is also possible to use ammonium salts, for example ammonium halides, ammonium carbonate, ammonium hydroxide or ammonium carboxylates.

The precipitation reactions may e.g. at temperatures of 20 to 100 ° C, especially 30 to 90 ° C, in particular at 50 to 70 ° C, are performed.

The precipitates obtained in the precipitation reactions are generally chemically nonuniform and generally contain mixtures of the oxides, oxide hydrates, hydroxides, carbonates and / or bicarbonates of the metals used. It may prove beneficial for the filterability of the precipitates when they are aged, i. if left for some time after precipitation, possibly in heat or by passing air through it.

The precipitates obtained by these precipitation processes are usually processed by washing, drying, calcining and conditioning.

After washing, the precipitates are generally dried at 80 to 200 ° C, preferably 100 to 150 ° C, and then calcined.

The calcination is generally carried out at temperatures between 300 and 800 ° C, preferably 350 to 600 ° C, in particular at 450 to 550 ° C.

After calcination, the powdery catalyst precursors obtained by precipitation reactions are usually conditioned. The conditioning can be carried out, for example, by adjusting the precipitation catalyst by grinding to a specific particle size. After milling, the catalyst precursor obtained by precipitation reactions can be mixed with molding aids, such as graphite, or stearic acid, and further processed to give moldings. Common methods of shaping are described, for example, in Ullmann [Ullmann's Encyclopedia Electronic Release 2000, Chapter: "Catalysis and Catalysts", pages 28-32] and by ErtI et al. [Ert I, Knoeginger, Weitkamp, Handbook of Heterogeneous Catalysis, VCH Weinheim, 1997, pages 98 ff]. Common methods of shaping are, for example, extrusion, tabletting, ie mechanical pressing or pelleting, ie compacting by circular and / or rotating movements.

By the process of shaping moldings can be obtained with the above geometry.

After conditioning or shaping is usually a tempering. The temperatures during the heat treatment usually correspond to the temperatures during the calcination.

precipitation

In a further preferred embodiment, the shaped bodies can be produced by precipitation.

Precipitation is understood as meaning a preparation method in which a sparingly soluble or insoluble carrier material is suspended in a liquid and subsequently soluble compounds, such as soluble metal salts, are added to the corresponding metal oxides, which are then precipitated onto the suspended carrier by addition of a precipitating agent (eg be in EP-A2-1 106 600, page 4, and AB Stiles, Catalyst Manufacture, Marcel Dekker, Inc., 1983, page 15).

As heavy or insoluble support materials are for example carbon compounds such as graphite, carbon black and / or activated carbon, alumina (gamma, delta, theta, alpha, kappa, chi or mixtures thereof), silica, zirconia, zeolites, aluminosilicates or mixtures thereof into consideration ,

The carrier material is usually present as a powder or grit.

As a liquid in which the carrier material is suspended, water is usually used.

Suitable soluble compounds are the abovementioned soluble compounds of the active components or of the doping elements. The precipitation reactions can be carried out, for example, at temperatures of from 20 to 100.degree. C., especially from 30 to 90.degree. C., in particular from 50 to 70.degree.

The precipitates obtained in the precipitation reactions are generally chemically ununiform and generally contain mixtures of the oxides, oxide hydrates, hydroxides, carbonates and / or bicarbonates of the metals used. It may prove beneficial for the filterability of the precipitates when they are aged, i. if left for some time after precipitation, possibly in heat or by passing air through it.

The calcination is generally carried out at temperatures between 300 and 800 ° C, preferably 350 to 600 ° C, especially at 450 to 550 ° C. After calcination, the powdery catalyst precursors obtained by precipitation reactions are usually conditioned.

The conditioning can be carried out, for example, by adjusting the precipitation catalyst by grinding to a specific particle size.

After milling, the catalyst precursor obtained by precipitation reactions can be mixed with molding aids, such as graphite, or stearic acid, and further processed to give moldings. Common methods of shaping are described, for example, in Ullmann [Ullmann's Encyclopedia Electronic Release 2000, Chapter: "Catalysis and Catalysts", pages 28-32] and by Ertl et al. [Ertl, Knözinger, Weitkamp, Handbook of Heterogeneous Catalysis, VCH Weinheim, 1997, pages 98 ff].

Common methods of molding include extrusion, tableting, i. mechanical pressing or pelleting, i. Compacting by circular and / or rotating movements.

By the process of shaping moldings can be obtained with the above geometry. After conditioning or shaping is usually a tempering. The temperatures during the heat treatment usually correspond to the temperatures during the calcination.

reduction

Formed bodies which have been produced by impregnation or precipitation (precipitation or mixed precipitation) generally contain the catalytically active components after calcination, generally in the form of their oxygen-containing compounds, for example their metal oxides or hydroxides, such as CoO, NiO, CuO and / or their mixed oxides (catalyst precursor).

The catalyst precursors prepared by impregnation or precipitation as described above are generally reduced after calcination. The reduction usually converts the catalyst precursor into its catalytically active form.

The reduction of the catalyst precursor can be carried out at elevated temperature in a moving or stationary reduction furnace.

The reducing agent used is usually hydrogen or a gas containing hydrogen.

The hydrogen is generally used technically pure. The hydrogen may also be in the form of a hydrogen-containing gas, i. in admixtures with other inert gases, such as nitrogen, helium, neon, argon or carbon dioxide are used. The hydrogen stream can also be recycled as recycle gas into the reduction, possibly mixed with fresh hydrogen and, if appropriate, after removal of water by condensation.

The reduction of the catalyst precursor is preferably carried out in a reactor in which the shaped bodies are arranged as a fixed bed. Particularly preferably, the reduction of the catalyst precursor takes place in the same reactor in which the subsequent reaction takes place.

Furthermore, the reduction of the catalyst precursor can take place in a fluidized bed reactor in the fluidized bed.

The reduction of the catalyst precursor is generally carried out at reduction temperatures of 50 to 600 ° C, in particular from 100 to 500 ° C, particularly preferably from 150 to 450 ° C. The hydrogen partial pressure is generally from 1 to 300 bar, in particular from 1 to 200 bar, more preferably from 1 to 100 bar, wherein the pressure data here and below relate to the absolute measured pressure. The duration of the reduction is preferably 1 to 20 hours, and more preferably 5 to 15 hours. During the reduction, a solvent can be supplied to dissipate any water of reaction formed and / or, for example, to heat the reactor faster and / or to be able to dissipate the heat better during the reduction. The solvent can also be supplied supercritically.

As suitable solvents, the solvents described above can be used. Preferred solvents are water; Ethers, such as methyl tert-butyl ether, ethyl tert-butyl ether, dioxane or tetrahydrofuran. Particularly preferred are water or tetrahydrofuran. Suitable suitable solvents are also suitable mixtures.

The resulting shaped article can be handled after reduction under inert conditions. Preferably, the molded article may be handled and stored under an inert gas such as nitrogen or under an inert liquid, for example, an alcohol, water or the product of the respective reaction, for which the catalyst is used. If necessary, the catalyst must then be freed from the inert liquid before the start of the actual reaction.

The storage of the catalyst under inert substances allows uncomplicated and safe handling and storage of the molding.

The molding can after reduction but also with an oxygen-containing

Gas stream such as air or a mixture of air with nitrogen are brought into contact.

As a result, a passivated molded body is obtained. The passivated molding generally has a protective oxide layer. Through this protective oxide layer, the handling and storage of the catalyst is simplified, so that, for example, the incorporation of the passivated molded body is simplified in the reactor. A passivated molding is preferably reduced prior to contacting with the reactants as described above by treatment of the passivated catalyst with hydrogen or a hydrogen-containing gas. The reduction conditions generally correspond to the reduction conditions used in the reduction of the catalyst precursors. Activation typically removes the protective passivation layer.

gas

In a particularly preferred embodiment, a gas is fed to the reactor in which the reaction of the diamines takes place.

Particularly preferably, the gas is supplied, in which it is introduced into the liquid phase of the reactor.

The supplied gas is particularly preferably an inert gas or hydrogen or a mixture of inert gas and hydrogen. Inert gases are gases which are predominantly inert under the present reaction conditions and essentially do not react with the diamines present in the reaction mixture or the polyamines formed. Nitrogen or noble gases, in particular helium, neon, argon or xenon, are preferably used as the inert gas. Most preferably, nitrogen is supplied. As inert gases and mixtures of the above-mentioned gases can be used.

Hydrogen In a particularly preferred embodiment, hydrogen is supplied as gas.

The hydrogen is generally used technically pure. The hydrogen may also be in the form of a gas containing hydrogen, i. with admixtures of other inert gases, such as nitrogen, helium, neon, argon or carbon dioxide are used. For example, reformer effluents, refinery gases, etc. can be used as the hydrogen-containing gases if and insofar as these gases do not contain any contact poisons for the catalysts used, for example CO. However, preference is given to using pure hydrogen or essentially pure hydrogen in the process, for example hydrogen having a content of more than 99% by weight of hydrogen, preferably more than 99.9% by weight of hydrogen, particularly preferably more than 99.99 Wt .-% hydrogen, in particular more than 99.999 wt .-% hydrogen.

If the reaction is carried out in the presence of hydrogen, high conversions and reaction rates and / or degrees of polymerization can be achieved. Furthermore, the polyamines obtained have a lower degree of discoloration.

In a particularly preferred embodiment, the gas supplied contains at least 50 mol% of hydrogen, more preferably at least 75 mol% of hydrogen and most preferably at least 99 mol% of hydrogen.

In a very particularly preferred embodiment, the supplied gas consists of hydrogen.

solvent

The reaction according to the invention can be carried out in bulk or in a liquid as solvent.

Suitable liquids are, for example, liquids which behave as far as possible inert under reaction conditions. Preferred liquids are C 4 - to C 12 -dialkyl ethers, such as diethyl ether, diisopropyl ether, di-butyl ether or tert-butyl methyl ether, or cyclic C 4 - to C 12 ethers, such as tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran or dioxane, dimethoxyethane, diethylene glycol dimethyl ethers or hydrocarbons, such as pentane, hexane, heptane, 2,2,4-trimethylpentane, octane, cyclohexane, cyclooctane, methylcyclohexane, xylene, toluene or ethylbenzene, or amides, such as formamide, dimethylformamide or N-methylpyrrolidone.

Suitable liquids may also be mixtures of the abovementioned liquids.

The reaction according to the invention is preferably carried out in the absence of solvent in the substance. When a solvent is used, the concentration of monomers used at the beginning of the reaction is generally in the range of 0.1 to 50% by weight, preferably 1 to 40% by weight, more preferably 2 to 30% by weight, and most preferably 5 to 25% by weight. reactor

The preparation of the polyamines in the presence of catalysts can preferably be carried out continuously, semicontinuously or discontinuously in customary reaction vessels suitable for catalysis in a fixed bed or suspension mode.

suspension

In a particularly preferred embodiment, the catalyst is suspended in the reaction mixture to be polymerized.

The polymerization in suspension mode can preferably be carried out in a stirred reactor, jet loop reactor, jet nozzle reactor, bubble column reactor, or in a cascade of such identical or different reactors.

The polymerization is particularly preferably carried out in suspension operation in a stirred reactor.

The settling rate of the catalyst in the liquid diamines or the chosen solvent should be low in order to keep the catalyst well in suspension.

The particle size of the catalysts used in the suspension procedure is therefore preferably between 0.1 and 500 μm, in particular 1 and 100 μm. fixed bed

In a particularly preferred embodiment, the polymerization is carried out in a reactor in which the catalyst is arranged as a fixed bed.

Suitable fixed bed reactors are described, for example, in the article "Catalytic Fixed Bed Reactors" (Ullmann's Encyclopedia of Industrial Chemistry, Published Online: 15 JUN 2000, DIO:

10.1002 / 14356007.b04_199).

The process is preferably carried out in a shaft reactor, shell-and-tube reactor or tubular reactor.

The process is particularly preferably carried out in a tubular reactor.

The reactors can each be used as a single reactor, as a series of individual reactors and / or in the form of two or more parallel reactors.

In a preferred embodiment, the fixed bed arrangement comprises a catalyst charge in the true sense, d. H. loose, supported or unsupported moldings, which are preferably in the geometry or shape described above. For this purpose, the moldings are introduced into the reactor.

So that the shaped bodies remain in the reactor and do not fall through it, a grid base or a gas- and liquid-permeable sheet is usually used, on which the shaped bodies rest. The shaped bodies can be surrounded by an inert material both at the inlet and at the outlet of the reactor. The inert material used is as a rule moldings which have a similar geometry to the catalyst moldings described above, but are inert in the reaction, e.g. Pall rings, balls of an inert material (e.g., ceramic, steatite, aluminum).

However, the shaped bodies can also be mixed with inert material and introduced as a mixture into the reactor.

The catalyst bed (molding + optionally inert material) preferably has a bulk density (according to EN ISO 6) in the range of 0.1 to 3 kg / l, preferably from 1, 5 to 2.5 kg / l and particularly preferably 1, 7 to 2.3 kg / l.

Process Parameters The catalyst loading in continuous operation is typically 0.1 to 1.5, preferably 0.3 to 1.2, more preferably 0.4 to 1.0 kg, of starting material per liter of catalyst per hour. The residence time in batchwise or semi-continuous mode is typically 0.5 to 3, preferably 0.5 to 2.5, more preferably 0.5 to 1.5 hours. The reaction is preferably carried out at temperatures in the range of 50 to 200 ° C, more preferably 90 to 190 ° C and most preferably 130 to 170 ° C.

In a preferred embodiment, the temperature in the reactor is 165 ° C or less, preferably 50 to 165 ° C, more preferably 90 to 165 ° C, and most preferably 130 to 165 ° C. In this temperature range, the selectivity is high (little deamination and other side reactions).

The reaction is preferably carried out at a pressure at which the monomers and dimers are largely in the liquid state at the reaction temperature. The reaction is preferably carried out at a pressure in the range from 1 to 400 bar, more preferably 1 to 200 bar and most preferably 1 to 70 bar.

If the reaction is carried out in the presence of hydrogen, the hydrogen partial pressure is preferably from 1 to 400 bar, in particular from 1 to 200 bar, particularly preferably from 1 to 70 bar.

Carrying out the reaction in the above-mentioned ranges of pressure and temperature makes it possible to produce polyamines having good space-time yields and high selectivity (e.g., little deamination) in the intended molecular range.

Feed of the monomers

In a batch process, the diamines are preferably initially charged in the reactor. For this purpose, the diamines can be treated with suitable conveying devices, e.g. Liquid pumps, vacuum conveyors or pneumatic conveyors are conveyed into the reactor. Suitable devices for filling a reactor, depending on the state of matter of the substance to be delivered are known in the art.

The diamines are preferably conveyed in the liquid state into the reactor. For this purpose it may be necessary to heat the diamines to a temperature above their melting or solidification point and / or to operate under a pressure at which the diamines are in the liquid state. Furthermore, it may be preferable to dissolve the diamines in one of the aforementioned solvents. In a continuous reactor, the diamines are preferably pumped in the liquid state into the reactor. The stream of feedstocks in the reactor can be from top to bottom (trickle) or from bottom to top (sumping).

Gas supply

The amount of gas supplied is preferably in the range of 1 to 1000 liters of gas per hour per liter of free reactor volume, more preferably 5 to 500, most preferably 10 to 300 and particularly preferably 50 to 200 liters of gas per hour per liter of free reactor volume, the free reactor volume as the difference between the reactor void volume and the volume of the catalyst charge (including internals). The free reactor volume corresponds to the volume of a liquid which is required to fill the catalyst-filled reactor (including all internals).

When the gas supply is in the above range, both a high polymerization rate and high molecular weights can be achieved.

The supply of the gas is preferably carried out continuously, i. essentially without interruption. However, the supply can also be periodic or aperiodic with periodic or aperiodic interruptions, in which case it is advantageous for the average interruptions to be shorter than the average phases of the supply. Preferably, the average breaks are shorter than 15 minutes, preferably shorter than 2 minutes and most preferably shorter than 1 minute.

Preferably, the supply of the gas is uniform over the duration of the reaction, i. without major fluctuations over time. In a batch or semi-batch

Method, the feed stream of gas may increase with increasing reaction time, but the upper limit of the preferred range should preferably not be exceeded. As a result, the amount of monomers, which is possibly entrained with the gas from the reactor, is reduced.

Most preferably, the gas supply is continuous, i. essentially without interruption. In a batch process, the supply of the gas is preferably carried out separately from the supply of the diamines. In a batch process, the gas may be simultaneously fed together with the diamines via one or more separate feeders.

Gas dispersion

In a very particularly preferred embodiment, the supplied gas is dispersed in the liquid phase. Dispersion is understood to be the fine and as homogeneous as possible distribution of the gas in the liquid phase. In a preferred embodiment, a dispersion of the gas in the liquid phase can be achieved by passing the gas into the reactor via suitable inlet openings.

In a further preferred embodiment, a dispersion of the gas in the liquid phase can be achieved, in which a shear stresses generated by flow acts on the supplied gas and on the supplied gas causes a sufficient deformation against the stabilizing effect of the interfacial tension, so that Fragmentation of the gas flow is done in bubbles. The energy input for generating a shear stress acting on the gas or the gas bubbles, for example, by the introduction of energy into the dispersion medium, for example by generating a flow in the dispersion medium, i. the liquid phase, take place. Preferably, a turbulent flow is generated. A flow, as described below, for example, by stirring or circulation of the liquid phase take place. The largest contiguous volume of gas in the liquid phase should preferably not exceed 1%, better 0.1% of the stirred tank volume (above the liquid phase, in the upper part of the reactor, a larger volume of gas may be present). It is preferred that the diameter of the gas bubbles, and thus the largest contiguous gas space in the liquid phase in the range of 0.1 mm to 100 mm diameter, more preferably in the range of 0.5 to 50 mm and most preferably in the range of 1 to 10 mm.

The dispersion of the gas in the liquid phase has the advantage that the resulting in the implementation of the diamines to polyamine ammonia can be converted into the gas phase and removed from the reactor. By removing the resulting ammonia along with the gas supplied, polyamines of high molecular weight and low degree of branching can be achieved.

Access openings In a preferred embodiment, the introduction of the gas takes place through one or more access openings.

Preferred access openings are a gas inlet tube, a distributor ring or a nozzle. The term nozzle designates in the usual way a tube which tapers in the direction of flow. In order to achieve a homogenization of the distribution of the gas-liquid phase mixture, it is further preferred to use distribution devices, such as sintered or perforated plates in the region of the feed openings. The perforated plates or sintering trays may be distributed over the entire cross-section or part of the cross-sectional area of the reactor.

Most preferably, the distribution of the gas in the liquid is improved by distributing the access openings uniformly over the cross-section of the reactor, such as a distributor ring.

Festbettreakor

In the case of a fixed bed reactor, which has essentially a plug flow characteristic, the dispersion of the gas in the liquid phase preferably takes place via access openings. In order to achieve a homogenization of the distribution of the gas-liquid phase mixture and to avoid the problems described, it is preferred to use distribution devices, such as sintered or perforated plates in the region of the feed openings. The

Perforated plates or sintered trays may be distributed over the entire cross section or part of the cross sectional area of the reactor.

In a further preferred embodiment, the supply of the gas takes place via access openings, which are distributed as uniformly as possible over the cross-section of the reactor, as for example in the case of a distributor ring. Furthermore, it is preferable to pass the gas via perforated plates or sintered trays with largely uniformly distributed passage openings into the reactor. In a particularly preferred embodiment, apart from the hydraulic flow induced by the introduction of the liquid and the gas, no additional flow is generated in the reactor, for example by stirring or pumping over the liquid phase.

This embodiment has the advantage that the characteristic plug flow of the reactor is not significantly disturbed and backmixing is limited. This has the advantage that polyamines can be prepared with a narrower molecular weight distribution and a smaller proportion of monomers.

In a very particularly preferred embodiment, the supply of the gas, as described in DE102005050283, to which reference is expressly made, described distribution device for a gas-liquid phase mixture in which a gas and a liquid phase via at least one feed opening into the interior of the apparatus and characterized in that the distribution device comprises a horizontal bottom at which the rising gas phase dammed into a gas cushion, and arranged at the bottom vertical upstream liquid phase guide elements, which extends in the direction of the feed opening through the forming gas cushion into the liquid phase at least one opening for the gas phase in the region of the forming gas cushion is provided on the circumference of the liquid phase guide elements.

slurry reactor

If the reaction is carried out in suspension mode, the dispersion can be improved by generating a flow, preferably a turbulent flow, in the region of the gas feed. Shear stresses generated by the flow will generally cause a sufficient deformation against the stabilizing effect of the interfacial tension on the gas supplied, so that a division of the gas flow into bubbles takes place. The energy input for generating a shear stress acting on the gas or the gas bubbles, for example, by the introduction of energy into the dispersion medium, for example by generating a flow in the dispersion medium, that is, the liquid phase, take place. Preferably, a turbulent flow is generated. A flow can be carried out as described below, for example by stirring or circulation of the liquid phase.

In a particularly preferred embodiment, the turbulent flow can be generated in that the gas to be dispersed is introduced into the reactor at a sufficiently high pressure or at a sufficiently high rate. Most preferably, the velocity of the gas supplied is higher than the flow rate of the dispersion medium. The supplied gas may be introduced into the reactor through a gas inlet tube, a distributor ring or a nozzle, as described above. A high flow rate can be generated by passing the gas into the reactor at a sufficiently high pressure. The velocity of the exiting gas can also be regulated by the size of the exit opening of the gas inlet to the dispersion medium.

For example, by decreasing the diameter of the outlet openings, the flow rate of the supplied gas can be increased. However, if the size of the outlet openings is chosen too small, the outlet openings can become clogged. The diameter of the outlet openings is preferably in the range of 0.1 to 50 mm, more preferably 1 to 20 mm and most preferably 2 to 10 mm. It is particularly preferred to introduce the supplied gas in countercurrent to the flowing liquid.

In another particularly preferred embodiment, the turbulent flow may be generated by circulating the dispersion medium through the reactor at a sufficiently high rate. The circulation of the dispersion medium through the reactor can be achieved either by feeding the supplied gas to the reactor at a sufficiently high rate and / or by pumping the dispersion medium itself through the reactor. If the supplied gas is fed to the reactor at a sufficiently high rate, the dispersion medium in the reactor is also circulated via impulse transmission.

The dispersion medium is preferably fed to the reactor by means of a nozzle. Most preferably, the reactor is equipped with corresponding internals or baffles that disturb a laminar flow such that a turbulent flow is formed. As baffles, the catalyst packing may also preferably function

Furthermore, the reactor may be provided with baffles to increase the circulation within the reactor.

In a further preferred embodiment, the reaction takes place in a stirred reactor and the turbulent flow in the dispersion medium is generated by stirring.

Suitable mixing units are stirrers with different stirring geometries, such as disk stirrers, impeller stirrers, inclined blade stirrers, lattice stirrers, Mig stirrers or propeller stirring. The feed point for the introduced gas, for example the gas inlet tube, the distributor ring or the nozzle, is preferably located below the stirrer so that the ascending gas bubbles are shattered by the stirrer and largely homogeneously distributed in the dispersion medium. If the supply of the gas is separate from the supply of the liquid, it is preferred that the gas is supplied to the region of the reactor in which the turbulent flow is generated.

In a stirred tank reactor, it is preferable to supply the gas below the stirrer via a gas inlet pipe, a gas distributor ring or a nozzle, so that the gas stream is broken by the energy input of the stirrer into smaller bubbles, which are homogeneously distributed in the reaction volume.

discharging

In a preferred embodiment, the supplied gas is removed from the reactor together with ammonia formed in the reaction of the diamines into polyamine.

The removal of ammonia from the reactor has the advantage that high degrees of polymerization and a good space-time yield can be achieved.

The supplied gas and the ammonia formed in the reaction can be substantially separated or removed from the reactor together with the liquid phase. Separate discharge of the gas flow

In a preferred embodiment, the gas and ammonia are removed from the reactor substantially separately from the liquid phase.

The supplied gas is preferably discharged together with the resulting ammonia at a gas outlet from the reactor. The gas outlet is preferably a valve, since the reaction of the diamines is preferably carried out at higher pressures. The gas outlet can also be a simple opening, for example a pipeline. If the supplied gas, together with the resulting ammonia, is to be discharged separately from the liquid phase, measures can be taken to ensure that the liquid phase is not discharged out of the reactor together with the gas. For this purpose, the gas outlet in the upper region of the reactor in the gas space above the level of the liquid phase can be attached. However, a membrane, a sinter plate, or a frit that is only permeable to the gaseous phase may also be placed in front of the gas outlet to retain the liquid phase in the reactor.

The gas stream removed from the reactor may be appropriately disposed of or worked up.

In a particularly preferred embodiment, the removed from the reactor

Gas stream returned to the reactor.

This has the advantage that the material costs can be reduced. In a most preferred embodiment, ammonia is separated from the gas stream prior to its recycling.

This is preferably carried out in the ammonia is condensed from the gas stream, so that a gas stream is obtained, which is substantially free of ammonia, and a liquid stream is obtained, which contains ammonia.

Furthermore, it is preferable if necessary to separate entrained or entrained diamine or oligomers of the diamine from the gas stream before it is recycled. In a very particularly preferred embodiment, entrained or entrained diamine or oligomers of the diamine are first separated off from the gas stream and subsequently the separation of ammonia from the gas stream takes place.

To remove any entrained or entrained amounts of liquid, for example diamines, oligomers of diamine and / or solvent, the discharged gas is introduced into a phase separator or liquid separator. In the phase separator the entrained liquid phase is separated from the gaseous phase containing ammonia and fed gas.

The liquid phase separated in the phase separator, which consists essentially of unreacted monomers or lower oligomers, can preferably be returned to the reactor or used in a subsequent reaction. This has the advantage that yield losses, based on the diamine used, can be reduced. It is preferred that the recycled stream of diamine, oligomers of the diamine and optionally solvent is substantially free of ammonia. This is generally achieved after the liquid separator. If the recirculated stream still contain ammonia, so ammonia can be removed from the liquid phase deposited in the phase separator, for example by distillation or degassing (stripping).

The separation of ammonia from the discharged gas stream can preferably take place in that the gas stream is cooled by a cooling device to a temperature at which ammonia passes into the liquid state, and the supplied gas remains in the gas phase. The cooling device is preferably a condenser.

In general, ammonia is condensed out of the gas stream, so that a gas stream is obtained, which is substantially free of ammonia, and a liquid stream is obtained which contains ammonia, and if necessary, the gas separated from ammonia can lead back into the reactor ,

The capacitor can be made up of almost all capacitors known to those skilled in the art, e.g. Plate capacitor, tube bundle condenser or snake cooler. Preferably, the capacitor is designed as a tube bundle capacitor. The condenser can be operated standing or lying, the condensation can take place in the shell space or in the pipes. After the cooling device, the gas stream usually contains only the gas supplied, since the ammonia contained in the gas stream was condensed out.

The uncondensed gas stream is preferably recycled to the reactor. It is preferred that the recycle stream contains substantially no ammonia. This is generally achieved after the cooling device. Should the ammonia levels be higher, the gas stream can be cooled again, for example at lower temperatures.

In a less preferred embodiment, ammonia is first separated from the gas stream together with the entrained or entrained liquid phase in which the gas stream is cooled, so that liquefied ammonia, and the liquid phase is separated from the gas phase. The separation of ammonia from the discharged gas stream can then preferably take place in that the gas stream is cooled by a cooling device to a temperature at which ammonia passes into the liquid state, and the gas supplied remains in the gas phase. The cooling device is preferably a condenser. The cooling device is preferably a condenser.

The capacitor can be made up of almost all capacitors known to those skilled in the art, e.g. Plate capacitor, tube bundle condenser or snake cooler. Preferably, the condenser is designed as a tube bundle condenser. The condenser can be operated standing or lying, the condensation can take place in the shell space or in the pipes.

The separated liquid phase contains, in addition to ammonia, possibly entrained or entrained amounts of diamine, oligomers of diamine and possibly solvent.

Preferably, ammonia is separated from the liquid phase diamine or oligomers of the diamine, for example by distillation, degassing (stripping) or evaporation of the ammonia. The liquid phase remaining after the removal of the ammonia can be returned to the reactor or used in a subsequent reaction. The liquid phase of diamine, oligomers of diamine and optionally solvent which is recycled or reused is preferably substantially free of ammonia.

The uncondensed gas phase, containing inert gas and / or hydrogen, can be discharged from the reactor or preferably recycled to the reactor.

Extraction together with reaction discharge

In a further particularly preferred embodiment, the supplied gas and the resulting ammonia are discharged together with a portion of the liquid phase from the reactor.

This procedure is preferred in continuous operation, especially when using a fixed bed reactor.

Preferably, the liquid phase is discharged together with the gas dispersed in the liquid phase and the resulting ammonia through a liquid outlet from the reactor. The liquid outlet is usually a pipe at the end of which is a valve.

If the catalyst is not used as a fixed bed but as a suspension, then it is preferable to separate the catalyst from the reactor effluent before further workup. To For example, the reactor effluent can be filtered. For example, in a continuous process, the catalyst may be by cross-flow filtration. The catalyst can also be separated from the reactor by centrifugation or sedimentation. Flash evaporation

It is further preferred that the reactor discharge is expanded at the reactor outlet, so that still in the liquid phase ammonia present, which is still in the liquid state, is largely completely transferred to the gas phase.

For this purpose, the reactor discharge is usually transferred through a valve in a space with less than in the reactor prevailing pressure, in which, however, unreacted diamine monomer still remains in the liquid phase Preferably, the reduced pressure in the container, in which the reaction effluent is expanded by about 10 to 50% lower than the pressure in the reactor.

Preferably, the gaseous phase containing ammonia and the gas fed in is separated from the liquid phase containing polyamine, oligomers of diamine and diamine and optionally solvent. The liquid phase is preferably recycled to the reactor as described below. It is preferred that the recycled liquid phase containing diamine, oligomers of the diamine and optionally solvent is substantially free of ammonia. This is generally achieved already after the flash evaporation. If the ammonia contents should nevertheless be higher, ammonia can be removed from the liquid phase separated in the phase separator, for example by distillation or degassing (stripping).

The proportion of the components which are present in gaseous form after the flash evaporation is preferably partially condensed in a cooler, the condensation preferably being operated so that ammonia is essentially completely condensed. The supplied gas, e.g. Inert gas and or hydrogen are preferably not condensed. Ammonia is preferably discharged from the process.

The uncondensed gas, which consists essentially of inert gas and / or hydrogen, is preferably recycled to the process. The recirculated gas preferably contains substantially no ammonia.

Workup - Column K1

In a very particularly preferred embodiment, the reaction product is discharged into a distillation column. The column is generally operated so that ammonia and fed gas are withdrawn at the top of the column and the remaining liquid phase (monomer, oligomers and polymers) are withdrawn at the bottom of the column (variant 1). However, the column K1 can also be operated in such a way that ammonia and the supplied gas are withdrawn from the top, monomeric and oligomeric diamine is withdrawn from a withdrawal in the central region of the column and higher molecular weight polyamine is withdrawn at the bottom of the columns (variant 2). The exact operating conditions of the distillation column can be routinely determined according to the separation efficiency of the column used by the skilled person on the basis of the known vapor pressures and evaporation equilibria of the introduced into the distillation column components according to conventional calculation methods. version 1

The reactor discharge is preferably expanded into the central region of a distillation column K1. The distillation column K1 is particularly preferably carried out in a tray column. In a tray column are located in the interior of the column shelves on which the mass transfer takes place. Examples of different soil types are sieve trays, tunnel trays, dual-flow trays, bubble trays or valve trays. In a further preferred embodiment, the distillative internals can be in the form of an ordered packing, for example as a sheet-metal package, such as Mellapak 250 Y or Montz Pak, type B1 -250, or as a structured ceramic packing or as a disordered packing, e.g. from Pallringen, IMTP rings (Koch-Glitsch), Raschig-Superringen, etc.

At the top of the column K1 is usually obtained a gaseous stream of the supplied gas and ammonia.

In a particularly preferred embodiment, ammonia is separated from the overhead stream of gas. The separation of ammonia from the discharged gas stream can preferably take place in that the gas stream is cooled by a cooling device to a temperature at which ammonia passes into the liquid state, and the supplied gas remains in the gas phase. The cooling device is preferably a condenser.

The condenser of the distillation column K1 is generally operated at a temperature at which the ammonia is largely completely condensed at the corresponding top pressure.

The condensed ammonia is preferably discharged from the process. The uncondensed gas, which consists essentially of inert gas and / or hydrogen, is preferably recycled to the process. Preferably, the recycle gas is substantially free of ammonia. The column K1 usually requires no additional evaporator at the bottom of the column, since the difference between the boiling points of ammonia and monomeric diamine is usually so high that a good separation of ammonia and monomeric diamine succeeds without additional bottom heating. However, it is also possible to heat the bottom of the column, for example with a bottom evaporator.

The temperature in the bottom of the column should then be adjusted so that at the prevailing in the column head pressure ammonia largely completely evaporated, while monomeric diamine remains in the liquid phase.

The bottoms discharge of the column K1 essentially contains diamine, oligomers of the diamine, polyamine and optionally solvent.

Part of the bottoms discharge can be recycled a) to the reactor, or b) introduced into a further column K2, in which monomeric diamine and low-boiling oligomer are separated from higher-boiling polyamine, or c) are removed from the reactor as reaction product. a) A part of the bottom product from the column K1 can be returned to the reactor, where a further condensation takes place. Thus, polymers with a particularly high molecular weight can be achieved.

It is preferred that the recirculated bottoms discharge contains substantially no ammonia. This is generally achieved already after the flash evaporation (distillation). If, however, the ammonia contents are higher, the ammonia content can be reduced, for example by distillation or degassing (stripping). b) The bottoms discharge from the column K1 can be introduced into a further distillation column K2, which is operated so that at the top of the column monomeric diamine and low-boiling oligopolyamine is obtained and withdrawn at the bottom of the column polyamine. The column K2 will be described in more detail below. c) A portion of the bottom product from the column K1 can be discharged as a reaction product from the process.

Variant 2

The column K1 can also be operated so that at the top of the column ammonia and the supplied gas incurred in the central region, a fraction is taken as a side draw containing monomeric diamine and low-boiling oligomers and obtained at the bottom of the column K1 polyamine.

The reactor discharge is, as in the variant 1 described above, preferably in the central region, a distillation column K1 as described above relaxed.

The condenser of the distillation column K1 is generally operated at a temperature in which the ammonia is largely completely condensed at the corresponding top pressure.

The condensed ammonia is preferably discharged from the process.

The uncondensed gas, which consists essentially of inert gas and / or hydrogen, is preferably recycled to the process.

The column K1 usually requires no additional evaporator at the bottom of the column, since the difference between the boiling points of ammonia and monomeric diamine is usually so high that a good separation of ammonia and monomeric diamine succeeds without additional bottom heating.

However, it is also possible to heat the bottom of the column, for example with a bottom evaporator.

The temperature in the bottom of the column should be adjusted so that at the head pressure prevailing in the column, ammonia is largely completely evaporated, while monomeric diamine remains in the liquid phase. As a side draw of the column K1, a fraction is preferably withdrawn which essentially contains oligomers of the diamine and diamine.

The side draw can be a) discharged from the process, or b) be returned to the process (preferred variant). When the side draw is recycled to the process, it is preferred that the side draw contain substantially no ammonia. This is generally achieved already after the flash evaporation (distillation). If the ammonia levels are nevertheless higher, the ammonia content can be reduced, for example by distillation or degassing (stripping).

Part of the bottom product can, as described under Variant 1, be recycled to the reactor, or b) introduced into a further column K2, in which monomeric diamine and low-boiling oligomer are separated from higher-boiling polyamine, or c) taken from the reactor as reaction product become.

Workup - Column K2 The bottoms discharge from column K1 can be introduced into a further column K2, which is operated such that monomeric diamine and low-boiling oligomers and polyamine polymer at the top of the column are obtained at the top of the column. However, the column K2 can also be operated in such a way that predominantly monomeric diamine can be attracted to the top, predominantly oligomeric diamine on a side draw, and polymeric diamine at the bottom.

The bottoms discharge from column K1 is preferably fed into the middle region, a distillation column K2.

Preferably, the distillation column K2 internals to increase the separation efficiency. The distillative internals may, for example, be in the form of an ordered packing, for example as a sheet-metal package such as Mellapak 250 Y or Montz Pak, type B1 -250. There may also be a package with a lesser or increased specific surface, or a tissue packing or a pack of other geometry such as Mellapak 252Y. The advantage of using these distillative internals is the low pressure loss and the low specific liquid hold-up in comparison to, for example, valve trays. The installations can be in one or more beds.

The bottom of the column K2 is preferably equipped with a bottom evaporator.

The temperature in the bottom of the column should be adjusted so that at the top pressure prevailing in the column ammonia monomer diamine evaporates almost completely and part of the oligomers, while polymeric polyamine remains in the liquid phase.

At the top of the column K2, a gaseous stream is usually withdrawn, which contains essentially of monomeric diamine.

Preferably, the overhead gas stream is fed to a condenser which is connected to the distillation column K2.

The condenser of the distillation column K2 is generally operated at a temperature in which the diamine is condensed to the greatest extent at the corresponding top pressure.

The condensate of the column K2, which consists essentially of monomeric diamine, can be discharged or recycled to the process.

The recycled diamine is preferably substantially free of ammonia.

This has the advantage that polyamines of high molecular weight and low branching degrees can be obtained. Furthermore, the reaction time can be reduced until reaching a certain degree of conversion (increasing the reaction rate). If the ammonia content is higher, the diamine may be subjected to further distillation or degassing, for example stripping.

A portion of the resulting condensate as diamine can be recycled as reflux in the column.

A portion of the bottoms discharge can be recycled to the reactor or removed from the reactor as a reaction product. Preferably, the bottom product of the column K2 is discharged as a reaction product.

In column K2, a side draw can be taken, which contains a fraction of low-boiling oligomers. These oligomers can be discharged, or recycled into the reactor together with the diamine discharged at the top. Preferred process variants In the figures 1 to 6 special embodiments of the method according to the invention are described.

Variant D-1

Figure 1 shows a batch process in which monomer is placed in a stirred tank reactor R 1 containing the catalyst in suspended or fixed form, e.g. contains in a metal net. Then inert gas and / or hydrogen is continuously fed. The introduction preferably takes place through a gas inlet tube, a gas distributor ring or a nozzle, which is preferably arranged below a stirrer. The introduced gas stream is smashed by the energy input of the stirrer into small gas bubbles and homogeneously distributed in the reactor. A mixture of formed ammonia and inert gas and / or hydrogen is continuously discharged from the reactor through an outlet opening in the upper region of the reactor.

If the discontinuous polycondensation is not carried out in the presence of a fixed catalyst, but rather of a suspended catalyst, the suspension catalyst is first removed as part of the working up of the desired product during the discharge of the product, eg. B. by filtration or centrifugation.

The reaction product obtained in the discontinuous polycondensation can be passed into a distillation column K1, in which a stream of diamine and oligomers of the diamine is separated at the top. Polyamine is obtained in the bottom of the column.

The reaction product obtained in the batchwise polycondensation can alternatively be passed into a distillation column K1 in which a stream of diamine is removed at the top and a fraction consisting essentially of oligomers of the diamine is removed as side draw. In the bottom of the column polyamine is withdrawn. Variant D-2

FIG. 2 shows a variant of the method in which the discharged gas stream is expanded after the discharge. For the separation of entrained liquid, the withdrawn gas stream is introduced into a liquid separator. The liquid deposited in the liquid separator is discharged from the process. After the liquid separator, the mixture of ammonia and inert gas and / or hydrogen discharged from the reactor is preferably cooled, wherein the ammonia is liquefied and can be separated off from the inert gas and / or hydrogen. The inert gas and / or hydrogen can be compressed again, if necessary mixed with fresh inert gas and / or hydrogen and recycled to the polymerization stage. Variant D-3

FIG. 3 shows a further variant in which the liquid deposited in the liquid separator, which consists essentially of diamine, oligomers of the diamine and optionally solvent, is returned to the process. Should the mixture of diamines and / or oligomers of the diamines contain by-products, they may be separated off, for example by distillation, from the diamines and their oligomers prior to their recycling. Thus, in the polycondensation of ethylenediamine according to the invention, for example piperazine can be formed as a by-product which can be separated off by distillation.

Variant K-1

FIG. 4 shows a continuous process for the preparation of polyamines. Diamine is passed together with inert gas and / or hydrogen over a catalyst which is fixedly arranged in an inertized pressure reactor R1.

The reaction is passed to a column K1. At the top of the column K1 is a mixture of ammonia and hydrogen, which is discharged from the process. The bottom product of the column K1 is fed to a column K2. At the top of the column K2 unreacted diamine is separated and recycled to the reactor R1. From a

If appropriate, oligomers are withdrawn from the side of the column K2, which are discharged and / or returned to the reactor R1. The bottom product of the column K2 contains polyamine.

Variant K-2

FIG. 5 shows a continuous process for the preparation of polyamines. Diamine is passed together with inert gas and / or hydrogen over a catalyst which is fixedly arranged in an inertized pressure reactor R1. The reaction is passed to a column K1. At the top of the column K1 is a mixture of ammonia and hydrogen, from which the ammonia is condensed out. Inert gas and / or hydrogen can be recycled to the reactor R1.

The bottom product of the column K1 is fed to a column K2. At the top of the column K2, unreacted diamine and low-boiling oligomer are separated off and recycled to the reactor R1. From a side take-off of the column K2, if appropriate, oligomers are withdrawn, which are discharged and / or returned to the reactor R1. The bottom product of the column K2 contains polyamine. Variant K-3

FIG. 6 shows a variant of the continuous process.

Diamine is passed together with inert gas and / or hydrogen over a catalyst which is fixedly arranged in an inertized pressure reactor R1. Under the reaction conditions results in a reaction, which is passed to a column K1. The column K1 is operated in such a way that a mixture of ammonia and inert gas and / or hydrogen mixture is obtained as the top product, a mixture of diamine and oligomers of the diamine taken from a side draw and polyamine as the bottom product. The column K2 in Figure 4 or 5 is omitted.

Polyamines By means of the process described above, polyamines (hereinafter also "polymers") can be prepared with particular properties.

The present invention therefore also relates to homopolymers and copolymers which are obtainable by reacting the abovementioned diamine monomers according to the invention.

The polymers may be prepared from repeat units of only one kind of diamine monomer (hereinafter referred to as homopolymers). However, the polymers may also be prepared from mixtures of two or more different types of diamine monomer (hereinafter referred to as copolymers). Preferred polymers are polymers of at least one diamine selected from the group consisting of 1, 3-propylenediamine, 1, 2-propylenediamine, 1, 4-butylenediamine, 1, 2-butylenediamine, 1, 5-diaminopentane, 1, 2-diaminopentane , 6-diaminohexane, 1, 2-diaminohexane 1, 7-diaminoheptane, 1, 2-diaminoheptane, 1, 8-diaminooctane, 1, 2-diamino octane, 1, 9-nonamethylenediamine, 1, 10-decamethylenediamine, 1, 1 1 Undecamethylenediamine, 1,12-dodecamethylenediamine, 2,2-dimethylpropan-1,3-diamine and 3- (methylamino) propylamine.

Further preferred polymers are polymers of at least one diamine selected from the group consisting of N, N-bis (3-aminopropyl) methylamine, N, N'-bis (3-aminopropyl) ethylenediamine, 3- (2-aminoethylamino) propylamine, Diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), di-1,3-propylenetriamine, tri-1,3-propylenetetramine, tetra-1,3-propylenepentamine, di-1,2-propylenetriamine, tri-1 , 2-propylenetetramine, tetra-1,2-propylenepentamine, dihexamethylenetriamine, trihexamethylenetetramine and tetrahexamethylenepentamine. Further preferred polymers are polymers of at least one diamine selected from the group consisting of 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, isophoronediamine, 1, 3-bis (aminomethyl) cyclohexane, [To 4- amino-cyclohexyl) -methane], [bis (4-amino-3,5-dimethyl-cyclohexyl) -methane], [bis (4-amino-3-methyl-cyclohexyl) -methane], 3- (cyclohexylamino propylamine, piperazine and

piperazine bis (aminomethyl). Also preferred polymers are polymers of at least one diamine selected from the group consisting of 4, 7, 10-Trioxatridecane-1, 13-diamine, 4, 9-dioxadodecane-1, 12-diamine and so-called Jeffamine® Fa. Huntsman, in particular Jeffamin D230, Jeffamine D400, Jeffamine D2000, Jeffamin D4000, Jeffamine ED600, Jeffamin ED900, Jeffamine ED2003, Jeffamin EDR148, and Jeffamin EDR176

The polymers prepared by the process described above contain diamine monomers of the formula

H ₂ NRNH ₂ as monomers, the aforementioned diamines can be used.

The polymers contain repeating units of the formula

N R N

H H

The repeating units may be linearly linked or branched.

In the case of the linear linkage (L), two repeating units are linked via a secondary amine (--NH-).

Branch (D) is a linkage in which three repeat units are linked via a tertiary amine (-N <).

The polymers may have primary amine end groups (-NH 2) (T).

From the proportion of linear linkages (L), the primary amine end groups (TO) and the branches (D), the degree of branching (DB) can be calculated. DB is defined as follows:

DB = (D + T) / (D + T + L), where D (dendritic) corresponds to the number of tertiary amino groups in the polymer,

L (linear) corresponds to the number of secondary amino groups in the polymer, and

T (terminal) corresponds to the number of primary amino groups in the polymer.

The degree of branching can be determined by determining the primary, secondary and tertiary amine numbers. The determination of the primary, secondary or tertiary amine number can be carried out in accordance with ASTM D2074-07.

The degree of branching can also be determined qualitatively by means of ¹⁵ N-NMR.

The polyamines according to the invention preferably have no signal or only a weak signal in the range typical for tertiary N atoms. This can be considered as an indicator of a low degree of branching.

The linking of the repeat units can thus be carried out to unbranched or branched polymer chains or unbranched or branched polymeric rings. In rings, at least two end groups of the same linear or branched chains are linked, so that a ring structure is formed. The probability that two primary amine groups of the same chain become linked to a ring decreases with the number of repeat units between the linking primary amine groups. The polymers according to the invention may preferably have at least one or any combination of 2 or more of the following properties a) to i): a) Degree of branching The polymers generally have a high proportion of linearly linked repeat units.

The degree of branching (DB) is preferably in the range of 0 to 1, more preferably in the range of 0 to 0.5, and most preferably in the range of 0.01 to 0.3

Polymers with a low degree of branching have good processing properties. They are particularly suitable for subsequent reactions in which the polymer is chemically modified (alkoxylation, reaction with isocyanates, reaction with acrylonitrile, reaction with epichlorohydrin, reaction with ethylene dichloride, reaction with esters / acids, quaternization with methyl chloride), as in the Reaction of polyamines according to the invention usually a lesser increase in viscosity takes place, in comparison to branched polyamines. b) degree of polymerization The average number of repeating units Pn of the monomers in the polymers is generally between 3 and 50,000. In a particularly preferred embodiment, the polymers have a high average molecular weight, ie a degree of polymerization Pn of 4 or more, preferably 10 or more, more preferably 15 or more and most preferably 20 or more.

The number of repeating units is preferably in the range from 4 to 1000, very particularly preferably in the range from 10 to 500, particularly preferably in the range from 15 to 100 and very particularly preferably in the range from 20 to 50.

Polymers with a high average degree of polymerization Pn have good mechanical and / or processing properties. c) polydispersity

The polydispersity (Pw / Pn) of the polymers is generally in the range of 1.2 to 20, preferably 1.5 to 7.5, where Pn is the number average degree of polymerization and Pw is the weight average degree of polymerization.

The polydispersity (Pw / Pn) of the polymers is preferably in the range from 1.3 to 15, particularly preferably in the range from 1.5 to 10 and very particularly preferably in the range from 2 to 7. Such polymers have a good property profile work well. d) metal content

The polymers preferably have a low metal content.

The metal content is preferably less than 500 ppm, more preferably less than 100 ppm, even more preferably less than 10 ppm, and most preferably less than 1 ppm. Such polymers have a low reactivity. Low reactivity means that the reaction rate of the polymers in subsequent reactions, for example, the reaction with diisocyanates to polyureas, is low. Furthermore, polymers with a low metal content have increased stability to environmental influences, such as light, ultraviolet radiation, temperature or humidity. e) Phosphorus content

The polymers preferably have a low phosphorus content.

The phosphorus content is preferably less than 500 ppm, more preferably less than 100 ppm, most preferably less than 10 ppm, and most preferably less than 1 ppm. Polymers with a low phosphorus content generally have an increased stability to environmental influences, such as light, ultraviolet radiation, temperature or humidity. f) color number

The polymers also preferably have a low color number.

The color number is preferably less than 200 Hazen, more preferably less than 150 Hazen, most preferably less than 100 Hazen and even more preferably less than 80 Hazen.

The Hazen color number preferably ranges from 0 to 200, more preferably from 5 to 150, most preferably from 10 to 100, and most preferably from 20 to 60.

The Hazen color number is typically measured according to ASTM D1209 or DIN 53409.

A low color number allows the application of the polymers in areas in which the color is regarded as a quality feature. These are most industrial applications, especially applications in paints, inks or adhesives. g) OH number

In contrast to polyamines, which are prepared by homogeneously catalyzed reaction of diamines and diols or by reaction of amino alcohols, the polymers preferably have a low OH number and are less branched. A low OH number has the advantage that the polymers have a higher charge density and a lower water solubility. A higher charge density can be advantageous when using the polymers a) as adhesion promoters, for example for printing inks for laminate films;

b) as an aid (adhesion), for example for the production of multilayer composite films, whereby not only different polymer layers but also metal foils are compatibilized;

c) as a bonding agent for adhesives, for example in conjunction with polyvinyl alcohol, butyrate, and acetate and styrene copolymers, or as a cohesion promoter for label adhesives; d) as a primer in paint applications to improve adhesion to substrates such as glass, wood, plastic and metal;

e) to improve wet adhesion, for example in standard emulsion paints, as well as to improve the instantaneous rainfastness of paints, for example for road markings; f) as a complexing agent, in particular with high binding capacity for heavy metals such as Hg, Pb, Cu, Ni;

g) as a flocculant, for example in water treatment / water treatment;

h) as a penetration aid, for example for active metal salt formulations in wood preservative;

k) for blocking and sealing, for example oil and gas industry;

n) as auxiliaries in the paper industry, for example for dewatering acceleration, impurity elimination, charge neutralization and paper coating as versatile;

o) for the separation of oil and water, for example in the metalworking industry; p) as an additive for landfill gaskets;

q) as a flocculant;

r) as swimming pool gallbladder;

s) for the production of bitumen chemicals by conversion with fatty acids;

t) as an anti-swelling agent for delaying the absorption of water;

u) as an emulsifier or emulsion breaker;

v) as a surfactant in industrial cleaning (IC) and home, textile and personal care w) as a wood preservative;

x) for the preparation of complexing agents (polycarboxylates);

(y) for the production of ore mining and mineral processing equipment;

bb) for water softening;

cc) as a crystallization inhibitor;

dd) as a rheology modifier (thickener);

ff) for the production of synthetic rubber and rubber chemicals;

gg) as an additive in coolants, lubricants and coolants;

hh) as auxiliaries in the field of construction chemistry;

ii) as part of electroplating baths;

jj) for the production of non-viral gene vectors;

kk) as a hardener for epoxy;

II) as a formulation of pesticides; mm) as crosslinker for profile modification (English) and selective water shut-off (water shut-off) in the field of oil and gas production;

nn) as a biocide for the prevention and treatment of biofilms;

oo) for the production of flame retardants;

pp) as a starter for polyols, as crosslinkers and scavengers of aldehydes in the field of polyurethanes or

qq) for the production of polyureas.

The OH number is preferably less than 5 mg KOH / g, more preferably less than 2 mg KOH / g, most preferably less than 1 mg KOH / g and most preferably less than 0.5 mg KOH / g.

The OH number can be determined by means of DIN 53240. h) chloride content

The polymers preferably have a low chloride content.

Preferably, the chloride content is less than 500 ppm, more preferably less than 100 ppm, even more preferably less than 10 ppm and most preferably less than 1 ppm.

Low chloride polymers tend to be less corrosive and may find applications in the field of corrosion protection. i) proportion of deaminated products

The polymers preferably have a low degree of deamination.

The proportion of deaminated polymers is preferably less than 3 wt .-%, more preferably less than 2 wt .-% and particularly preferably less than 1 wt .-%.

In a preferred embodiment, after the preparation and before the preparation, the polymers have at least one or any combination of at least two of the following properties: a) a degree of branching of 0 to 0.5, preferably 0.01 to 0.3; and or

b) an average degree of polymerization Pn of 5 or more, preferably in the range of 10 to 500; and or

c) a polydispersity in the range of 1, 5 to 10, preferably 2 to 7; and or

d) a metal content of less than 10 ppm, preferably less than 1 ppm; and / or e) a phosphorus content of less than 10 ppm, preferably less than 1 ppm; and / or f) a color number of less than 80 Hazen, preferably in the range of 20 to 60 Hazen; and or g) an OH number of less than 5 mg KOH / g, preferably less than 2 mg KOH / g.

h) and chloride content of less than 500 ppm

i) a proportion of deaminated polymers of less than 3 wt .-%. In a very particularly preferred embodiment, the abovementioned polymers have all of the abovementioned properties a), b), c) d), e), f), and g).

In a very particularly preferred embodiment, the abovementioned polymers have all of the abovementioned properties a), b), c) d), e), f), g), and h)).

In a very particularly preferred embodiment, the abovementioned polymers have all the abovementioned properties a), b), c) d), e), f), g), h) and i).

The abovementioned polymers are preferably suitable for the following applications: a) as adhesion promoters, for example for printing inks for laminate films;

Road markings;

g) as a flocculant, for example in water treatment / water treatment;

h) as a penetration aid, for example for active metal salt formulations in wood preservation;

i) as corrosion inhibitors, for example for iron and non-ferrous metals and in areas of

Gasoline production, secondary oil production

k) for blocking and sealing, for example oil and gas industry;

I) as a fixing agent, for example in the textile industry, in particular as formaldehyde-free co-solvent

fixer;

q) as a flocculant;

r) as swimming pool gallbladder;

s) for the production of bitumen chemicals by conversion with fatty acids;

t) as an anti-swelling agent for delaying the absorption of water;

u) as an emulsifier or emulsion breaker;

v) as a surfactant in industrial cleaning (IC) and home, textile and personal care; w) as a wood preservative;

x) for the preparation of complexing agents (polycarboxylates);

(y) for the production of ore mining and mineral processing equipment;

bb) for water softening;

cc) as a crystallization inhibitor;

dd) as a rheology modifier (thickener);

ff) for the production of synthetic rubber and rubber chemicals;

gg) as an additive in coolants, lubricants and coolants;

hh) as auxiliaries in the field of construction chemistry;

ii) as part of electroplating baths;

jj) for the production of non-viral gene vectors;

kk) as a hardener for epoxy;

II) as a formulation of pesticides;

mm) as crosslinker for profile modification (English) and selective water shut-off (water shut-off) in the field of oil and gas production;

nn) as a biocide for the prevention and treatment of biofilms;

oo) for the production of flame retardants;

qq) for the production of polyureas. The present invention allows

the use of a large number of monomers, so that a large number of homo- and co-polymers can be achieved (the choice of monomers makes it possible to tailor the properties of the polymers produced),

the use of monomers that are commercially and / or cost-effectively available

and / or which can be handled without high safety-related use, or that are advantageous in terms of their toxicological properties, the preparation of polyamines from bifunctional monomers which are substantially linear and less branched,

the preparation of polyamines which have a low metal content,

the preparation of polyamines which have a low phosphorus content,

the preparation of polyamines which are essentially colorless or have only a slight degree of discoloration,

the preparation of polyamines having a high average degree of polymerization,

the preparation of polyamines which have a low OH number and, associated therewith, a high charge density,

the preparation of polyamines having a lower degree of deamination,

the preparation of polyamines which have a low chloride content,

- The production of polyamines, which have both a low degree of branching and a high average degree of polymerization. Furthermore, the method according to the invention can have the following advantages:

- comparatively short residence times or reaction times,

the catalyst used for the polymerization can easily be separated off from the polymer and reused for further polymerizations,

high service life and activity of the catalyst in the process, so that the frequency of complex catalyst changes can be reduced,

a high degree of polymerization or a high conversion of diamines can be achieved at low residence times,

- the return of unreacted diamine can be made possible, and / or

- The process can be operated continuously.

The invention is illustrated by the following examples:

Examples 1 to 3

Polymerization of 1,3-propanediamine (1,3-PDA) to Polypropylene Polyamine:

The experiments were carried out in a 300 ml steel pressure vessel stirred with a paddle stirrer. If necessary, hydrogen (Experiments 1 and 2) or nitrogen (Experiment 3) was fed via an inlet tube. In the upper part of the pressure vessel, exhaust gas could optionally be diverted, which was led without cooling into the center of a vertical steel pipe (inside diameter 1, 4 cm, height 16 cm). Here incurred liquid condensate was returned to the lower part of the pressure vessel, exhaust discharged via the steel pipe from the apparatus.

The catalyst precursor used consisted of in each case 28% by weight of NiO and CoO, 13% by weight of CuO and 31% by weight of ZrC "2. The shaped catalyst bodies (3 × 3 mm tablets) were added 280 ° C and atmospheric pressure for 72 hours by a continuous hydrogen flow of 50 Nl per hour reduced.

The starting materials used were 80 g of 1,3-propanediamine (1,3-PDA) under nitrogen in a pressure vessel. 32 g of the activated catalyst were fixed in a "metal cage", which was flowed through by the stirred reaction mixture.

The polymerization was carried out in all three experiments in each case for 4 hours at 160 ° C and 60 bar total pressure.

After the reaction time, the autoclave was cooled to room temperature and depressurized. The reaction mixture was removed from the autoclave.

Example 1 (comparative example)

The experiment was carried out as described above. In the pressure vessel, a total pressure of 60 bar was maintained during the entire test time by pressing in hydrogen. No exhaust gas was discharged from the pressure vessel. Example 2

The experiment was carried out as described above. During the four hour reaction time, 50 NL of hydrogen per hour were passed through the pressure vessel and disposed of. Liquid condensate was returned to the pressure vessel.

Example 3

The experiment was carried out as Example 2. Instead of 50 NL of hydrogen, 50 NL of nitrogen per hour were passed through the pressure vessel and disposed of. Liquid condensate was returned to the pressure vessel.

The reaction effluents were analyzed by gas chromatography (% by mass) and by gel permeation chromatography (absolute measurement by measuring defined polyamine standards). The analytical results are summarized in Table 1.

The highest molecular weights were achieved in Example 2, in which hydrogen was passed through the pressure vessel and while the ammonia formed was discharged from the reactor. With this procedure significantly higher Mn and more than twice as high Mw values were achieved than with the procedures of Examples 1 and 3. Table 1

Mn = number average molecular weight Mw = mass average molecular weight PDI = Mw: Mn

Extraction of ammonia

Example 4

1,3-PDA was passed continuously from bottom to top over a catalyst of the composition 4% Cu, 8% Co, 9% Ni on an alumina support. The pressure was 50 bar, the temperature 140 ° C.

The catalyst loading was 0.1 kg / Lh 1, 3-propanediamine.

No gas was passed through the apparatus.

The results are summarized in Table 2.

Example 5

1, 3-PDA was passed continuously from bottom to top over a catalyst of the composition 4% Cu, 8% Co, 9% Ni on an alumina support. The pressure was 50 bar, the temperature 140 ° C.

The catalyst loading was 0.1 kg / Lh 1, 3-propanediamine.

It was 50 NL / h of hydrogen passed through the reactor (exhaust gas mode).

The results are summarized in Table 2.

Table 2

⁴ > Removal of ammonia

From the table it can be seen that significantly more high molecular weight compounds are obtained in the case of the exhaust gas method (+ 24%). In addition, the reaction is much more selective, since without flue gas desaminated polyamines and other unknown substances in an order of magnitude of 10% occur, while with exhaust gas only about 1% of these impurities are measured. Example 6

1, 3-PDA was continuously passed from bottom to top over a catalyst. The catalyst used was a cobalt catalyst with a strand diameter of 4 mm, the preparation of which is described in EP-A-0636409 (Example Catalyst A).

The pressure was 50 bar, the temperature 160 ° C.

The catalyst loading was 0.8 kg / Lh 1, 3-propanediamine.

10 NL / h of hydrogen were passed through the reactor (exhaust gas mode)

The composition of the crude product is summarized in Table 3. The molecular weight determination was carried out after separation of mono-, di- and trimer.

The degree of branching (DB) of the polymer was determined by determining primary, secondary and tertiary amine numbers (prime / sec / tert = 269/786/1 1). This results in a DB of 0.26.

Example 7 (comparative example)

The pressure was 50 bar, the temperature 170 ° C.

The catalyst loading was 0.8 kg / Lh 1, 3-propanediamine. 10 NL / h of hydrogen were passed through the reactor (exhaust gas method)

The degree of branching (DB) of the polymer was determined by determining primary, secondary and tertiary amine numbers (prime / sec / tert = 203/816/21). This results in a DB of 0.22.

Table 3

Example T [° C] 1, 3-PDA Dimer Trimer Tetramer Higher Other Mw PDI

6 160 14 16 15 12 42 1 405 1, 4

7 170 8 9 12 10 56 5 524 1, 6 Example 8

The procedure is as in Example 7, but the temperature is 160 ° C. The catalyst loading was 0.4 kg per liter of catalyst and hour for 1, 3-diaminopropane and 0.4 kg per liter of catalyst and hour for tetrahydrofuran. The resulting average molecular weight of the polymer mixture was 335 g / mol.

Example 9 The procedure is as in Example 7, but the temperature is 160 ° C. The catalyst loading was 0.4 kg per liter of catalyst and hour for 1,3-diaminopropane and 0.4 kg per liter of catalyst and hour for dimethoxyethane. The resulting average molecular weight of the polymer mixture was 386 g / mol. Example 10

The procedure is as in Example 7, but the temperature is 160 ° C. The catalyst loading was 0.4 kg per liter of catalyst and hour for 1,3-diaminopropane and 0.4 kg per liter of catalyst and hour for toluene. The resulting average molecular weight of the polymer mixture was 507 g / mol.

Table 4

Example 1 1

The procedure is as in Example 7, but the temperature is 165 ° C. The catalyst loading was 0.2 kg per liter of catalyst and hour for "polyetheramine D230." The resulting average molecular weight of the polymer mixture was 745 g / mol.

Example 12

The procedure is as in Example 7, but the temperature is 160 ° C. The catalyst loading was 0.1 kg per liter of catalyst and hour for Jeffamine EDR-148. The resulting average molecular weight of the polymer mixture was 788 g / mol. Example 13

The procedure is as in Example 7, but the temperature is 160 ° C. The catalyst loading was 0.5 kg per liter of catalyst per hour for 4,9-dioxadodecane-1,2-diamine. The resulting average molecular weight of the polymer mixture was 1469 g / mol.

Example 14

The procedure is as in Example 7, but the temperature is 160 ° C. The catalyst loading was 0.5 kg per liter of catalyst per hour for 4,7,10-trioxatridone-can-1,13-diamine. The resulting average molecular weight of the polymer mixture was 1782 g / mol.

Example 15 The procedure is as in Example 7, but the temperature is 160 ° C. The catalyst loading was 0.2 kg per liter of catalyst and hour for N, N-bis (3-aminopropyl) methylamine. The resulting average molecular weight of the polymer mixture was 1696 g / mol. Example 16

The procedure is as in Example 7, but the temperature is 150 ° C. The catalyst loading was 0.4 kg per liter of catalyst and hour for hexamethylenediamine. The resulting average molecular weight of the polymer mixture was 1 169 g / mol.

Example 17

The procedure is as in Example 7, but the temperature is 160 ° C. The catalyst loading was 0.2 kg per liter of catalyst and hour for 3-methylaminopropylamine. The resulting average molecular weight of the polymer mixture was 1086 g / mol.

Example 18

The procedure is as in Example 7, but the temperature is 160 ° C. The catalyst loading was 0.2 kg per liter of catalyst and hour for N, N'-bis (3-aminopropyl) ethylenediamine. The resulting average molecular weight of the polymer mixture was 538 g / mol.

Example 19

The procedure is as in Example 7, but the temperature is 160 ° C. The catalyst loading was 0.8 kg per liter of catalyst per hour for 1, 3-diaminopropane in mixture with 10 weight percent N, N-bis (3-aminopropyl) methylamine. The resulting average molecular weight of the polymer mixture was 427 g / mol.

Example T [° C] monomer dimer trimer other higher Mw PDI

11 160 11 15 9 22 43 745 1.2

12 160 13 15 - 21 51 788 1.3

13 160 7 - - 1 92 1469 1.5

14 160 4 - - 3 93 1782 1.6

15 160 1 - - 8 91 1696 1.8

16 150 11 2 - 18 69 1169 1.5

17 160 1 - - 20 79 1086 1.6

18 160 13 - - 23 64 538 1.5

19 160 22 18 14 11 22 427 1.3

Claims

Patent claims

1 . Process for the production of polyamines in a reactor, by reacting diamines which are in the liquid phase in the presence of a catalyst which is in the solid phase, at temperatures in the range of 50 to 200 ° C and a pressure in the range of 1 to 400 bar, characterized in that a gas is supplied to the reactor, the amount of gas supplied being 1 to 1000 liters of gas per liter of free reactor volume per hour and the gas is introduced into the liquid phase and the gas together with ammonia formed during the reaction, removed from the reactor.

2. The method according to claim 1, characterized in that the gas is an inert gas.

3. Method according to at least one of claims 1 to 2, characterized in that the gas contains hydrogen.

4. The method according to at least one of claims 1 to 3, characterized in that the gas contains exclusively hydrogen.

5. The method according to at least one of claims 1 to 4, characterized in that the supplied gas is dispersed in the liquid phase.

6. The method according to claim 5, characterized in that the temperature in the reactor is 165 ° C or less.

7. The method according to at least one of claims 1 to 6, characterized in that the reaction of the diamines is carried out continuously or discontinuously.

8. The method according to claim 7, characterized in that the catalyst load in continuous operation is in the range of 0.1 to 1.5 kg of diamine per liter of catalyst per

hour or the residence time with discontinuous driving is in the range of 0.5 to 3 hours.

9. The method according to at least one of claims 1 to 8, characterized in that the gas is removed from the reactor separately from the liquid phase.

10. The method according to claim 9, characterized in that ammonia is condensed out of the gas stream, so that a gas stream is obtained which is essentially ammonia-free, and a liquid stream is obtained which contains ammonia, and if necessary that of ammonia separated gas returns to the reactor.

1 1 . Method according to claim 1, characterized in that diamines and oligomers of diamine that are carried along or entrained from the gas stream are separated off before the ammonia is separated off.

Method according to claim 2, characterized in that the diamines and oligomers of the diamine are separated from the gas stream by flash evaporation.

Method according to at least one of claims 1 to 8, characterized in that the gas is removed from the reactor together with at least part of the liquid phase.

14. The method according to claim 5, characterized in that the removed liquid phase is expanded into a column, so that gas and ammonia are withdrawn at the top of the column and the polyamine is withdrawn at the bottom of the column.

15. The method according to claim 5, characterized in that the gas withdrawn at the top is partially condensed, so that a gas is obtained which contains essentially no ammonia, and an ammonia-containing liquid phase is obtained.

16. The method according to claim 5, characterized in that diamines and oligomers of diamine are removed from a side draw of the column, which are optionally recycled into the reactor.

17. The method according to claim 5, characterized in that the bottom of the column is introduced into a further column and diamines and oligomers of diamine are removed at the top of the column and the polyamine is withdrawn at the bottom of the column.

18. The method according to claim 7, characterized in that a side draw is withdrawn from the further column, which contains oligomers of diamine, which if necessary in the

procedures are returned.

19. The method according to at least one of claims 1 to 8, characterized in that gas recycled into the reactor and / or diamines or oligomers of the diamine recycled into the reactor contain essentially no ammonia.

20. Polyamines available according to at least one of claims 1 to 19.

21. Polyamines obtainable according to one of the processes according to claims 1 to 19 by reacting one or more diamines, characterized in that the polyamines a) a degree of branching of 0 to 0.5, preferably 0.01 to 0.3; and b) an average degree of polymerization Pn of 5 or more, preferably in the range from 10 to 500; and

c) a polydispersity in the range from 1.5 to 10, preferably 2 to 7; and

d) a metal content of less than 10 ppm, preferably less than 1 ppm; and e) a phosphorus content of less than 10 ppm, preferably less than 1 ppm; and f) a color number of less than 80 Hazen, preferably in the range from 20 to 60 Hazen; and

g) an OH number of less than 5 mg KOH/g, preferably less than 2 mg KOH/g; and

h) and chloride content of less than 500 ppm and

i) have a proportion of deaminated polymers of less than 3% by weight.

22. Use of polyamines according to claim 20 a) as adhesion promoters, for example for printing inks for laminate films;

b) as an aid (adhesion), for example for the production of multi-layer composite films, whereby not only different polymer layers but also metal films are compatibilized;

c) as an adhesion promoter for adhesives, for example in conjunction with polyvinyl alcohol, butyrate, and acetate and styrene copolymers, or as a cohesion promoter for label adhesives;

d) as a primer in paint applications to improve adhesion to substrates such as glass,

wood, plastic and metal;

e) to improve wet adhesion, for example in standard emulsion paints, and to improve the instant rain resistance of paints, for example for road markings;

f) as a complexing agent, especially with a high binding capacity for heavy metals such as Hg, Pb, Cu, Ni;

g) as a flocculant, for example in water treatment/water treatment; h) as penetration aids, for example for active metal salt formulations in wood protection;

i) as corrosion inhibitors, for example for iron and non-ferrous metals and in areas of gasoline production and secondary oil production

j) for immobilizing proteins and enzymes; Microorganisms or as immobilizing carriers of enzymes and microorganisms

k) for blocking and sealing, for example oil and gas industries;

I) as a fixative, for example in the textile industry, in particular as a formaldehyde-free co-fixer;

m) as an additive in the cosmetics sector, for example for hair setting agents and conditioners; n) as an aid in the paper industry, for example to accelerate drainage,

Elimination of impurities, charge neutralization and paper coating as versatile; o) for separating oil and water, for example in the metal processing industry; p) as an additive for landfill seals;

q) as a flocculant;

r) as a swimming pool algaecide;

s) for the production of bitumen chemicals through conversion with fatty acids;

t) as an anti-swelling agent so that clay absorbs water with a delay;

u) as an emulsifier or emulsion breaker;

v) as a surfactant in the field of industrial cleaning (IC);

w) as a wood preservative;

x) for the production of complexing agents (polycarboxylates);

y) for the production of aids for ore mining and mineral processing;

z) as a dispersant for pigments, ceramics, soot, carbon, carbon fibers, metal powder; aa) for gas scrubbing as an absorbent of CO2, NOx, SOx, C and aldehydes and for neutralizing acidic components;

bb) for water softening;

cc) as a crystallization inhibitor;

dd) as a rheology modifier (thickener);

ee) as an aid or as a building block for aids for the extraction and processing of oil, coal and natural gas;

ff) for the production of synthetic rubber and rubber chemicals;

gg) as an additive in coolants, lubricants and cutting fluids;

hh) as auxiliary materials in the field of construction chemistry;

ii) as a component of electroplating baths; or

jj) for the production of non-viral gene vectors.