JP2014534249A - Synthesis of polyalkylene polyamines with low color number by homogeneous catalytic amination of alcohols in the presence of hydrogen - Google Patents

Abstract

The present invention relates to a process for producing polyalkylene polyamines by homogeneous contact amination of alcohols. The present invention relates to a process characterized by reacting in the presence of hydrogen gas in the presence of a homogeneous catalyst. The invention further relates to polyalkylene polyamines obtained by such a process, as well as polyalkylene polyamines containing hydroxy groups, secondary amines or tertiary amines. The invention further includes fixing agents for printing inks, adhesion promoters in composite films, aggregation promoters for adhesives, cross-linking / curing agents for resins, primers in paints, wetting for dispersion paints. It relates to the use of such polyalkylene polyamines as adhesion promoters, complexing agents and flocculants, penetration aids in the protection of wood, anticorrosives, protein and enzyme immobilization agents.

Description

  The present invention relates to a process for the production of polyalkylene polyamines having a low color number by homogeneous catalytic amination of alcohols of alkanolamines or of diamines or polyamines with diols or polyols in the presence of hydrogen. The invention further relates to the polyalkylene polyamines obtained by this process, as well as the use of polyalkylene polyamines. Another subject of the present invention is certain polyalkylene polyamines having hydroxy groups, secondary amine groups or tertiary amine groups.

  Further embodiments of the invention will be apparent from the claims, the detailed description of the invention and the examples. Naturally, the features mentioned above and further described below of the subject matter according to the invention are not limited to the specific combinations in each case without departing from the scope of the invention. Other combinations can also be used. Embodiments according to the invention in which all features are preferred or have a highly preferred meaning are preferred or highly preferred.

  Polyethyleneimine is a useful product with many diverse uses. For example, polyethyleneimine is a) as a fixing agent for printing inks for laminate films; b) as an auxiliary (adhesive) for the production of multilayer composite films, in which not only various polymer films but also metals The foil is also compatibilized; c) as an adhesion promoter for adhesives, eg in combination with polyvinyl alcohol, polyvinyl butyrate, polyvinyl acetate and styrene copolymers, or as an aggregation promoter for label adhesives D) low molecular weight polyethyleneimines can also be used as crosslinkers / curing agents in epoxy resins and polyurethane adhesives; e) adhesion to substrates such as glass, wood, plastics and metals as primers in paint applications; F) to improve wet adhesion in standard dispersion paints Also, for example, to improve the rain resistance immediate effect of road marking paints; g) as a complexing agent having a high binding force to heavy metals such as Hg, Pb, Cu and Ni, and further in water treatment / water aftertreatment As flocculants; h) as penetration aids for active metal salt formulations in wood protection; i) as anticorrosives for ferrous and non-ferrous metals; j) used to immobilize proteins and enzymes. Other polyalkylene polyamines not derived from ethyleneimine can also be used for these applications.

  Currently, polyethyleneimine is obtained by homopolymerization of ethyleneimine. Ethyleneimine is a highly active, corrosive and toxic intermediate product that can be synthesized by various routes (Aziridine, Ulrich Steuerle, Robert Feuerhake; Ullmann's Encyclopedia of Industrial Chemistry, 2006, Wiley-VCH, Weinheim).

  In the β-chloroethylamine method, ethyleneimine is obtained by the reaction of β-chloroethylamine and NaOH. In so doing, care must be taken so that the elimination of HCl may cause undesirable polymerization of β-chloroethylamine. Further disadvantages are the use of 2 equivalents of NaOH and the formation of NaCl as a bound product.

  In the Dow method, ethyleneimine is obtained by reaction of 1,2-dichloroethane with 3 equivalents of ammonia. Disadvantages are the use of large amounts of ammonia, the formation of ammonium chloride as a bound product, the reaction mixture being corrosive and the product having impurities.

  In the Wencker method, 2-aminoethyl hydrogen sulfate is produced by the reaction of 2-aminoethanol and sulfuric acid in the first step. Thereafter, ethyleneamine is obtained from 2-aminoethyl hydrogensulfate by adding 2 equivalents of NaOH in the second step. Here too, the disadvantages are the use of sulfuric acid and NaOH and the formation of sodium sulfate as a binding product.

  In the case of catalytic dehydrogenation of 2-aminoethanol, ethyleneimine is obtained by catalytic dehydrogenation of 2-aminoethanol at 250 to 450 ° C. in the gas phase. The disadvantages of this method are that the post-treatment of the product by distillation is complicated, requires a lot of energy, and further has a short catalyst life.

  In addition to the above-mentioned drawbacks in the process for producing ethyleneimine, the synthesis of polyethyleneimine starting from this starting compound is problematic because it requires handling of highly active, toxic and corrosive ethyleneimine Because. Similarly, it must be ensured that no ethyleneimine remains in the resulting product or wastewater stream.

There is no method analogous to the aziridine route for the preparation of polyalkylene polyamines-[(CH ₂ ) _x N]-(x> 2) with alkylene groups greater than C ₂ , not derived from aziridine. For this reason, there has never been a low-cost method for manufacturing this.

  Homogeneous catalytic amination of alcohols is known from the literature on the synthesis of primary, secondary and tertiary amines starting from alcohols and amines, but can be obtained in any of the described embodiments. Is a monomer product.

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

Y. Watanabe, Y. Tsuji, Y. Ohsugi Tetrahedron Lett. 1981, 22, 2667-2670, [Ru (PPh ₃ ) ₃ Cl ₂ ] with amination of alcohol using aniline as a catalyst. For the preparation of arylamines.

  EP0034480A2 includes a reaction of a primary or secondary amine with a primary or secondary alcohol using an iridium catalyst, a rhodium catalyst, a ruthenium catalyst, an osmium catalyst, a platinum catalyst, a palladium catalyst or a ruthenium catalyst. , N-alkylamines or N, N-dialkylamines are disclosed.

  EP0239934A1 describes the synthesis of monoaminated and diaminated products using ruthenium-phosphane complexes and iridium-phosphane complexes, starting from diols such as ethylene glycol and 1,3-propanediol and secondary amines. Have been described.

  In KI Fujita, R. Yamaguchi Synlett, 2005, 4, 560-571, primary amines and diols are obtained by synthesizing secondary amines by reaction of alcohols with primary amines, and ring closure using iridium catalysts. The synthesis of cyclic amines by reaction is described.

  A. Tillack, D. Hollmann, K. Mevius, D. Michalik, S. Baehn, M. Beller Eur. J. Org. Chem. 2008, 4745-4750, A. Tillack, D. Hollmann, D. Michalik, M Beller Tetrahedron Lett. 2006, 47, 8881-8885, D. Hollmann, S. Baehn, A. Tillack, M. Beller Angew. Chem. Int. Ed. 2007, 46, 8291-8294, and M. Haniti, SA Hamid, CL Allen, GW Lamb, AC Maxwell, HC Maytum, AJA Watson, JMJ Williams J. Am. Chem. Soc, 2009, 131, 1766-1774 uses a homogeneous ruthenium catalyst with alcohol and primary Alternatively, the synthesis of secondary and tertiary amines starting from secondary amines is described.

  The synthesis of primary amines by reaction of alcohol with ammonia using homogeneous ruthenium catalyst was reported in C. Gunanathan, D. Milstein, Angew. Chem. Int. Ed. 2008, 47, 8661-8664. Yes.

  The applicant's unpublished patent application PCT / EP2011 / 058758 describes a general process for the preparation of polyalkylene polyamines by catalytic amination of alcohols of alkanolamines or of diamines or polyamines with diols or polyols. ing.

  The object of the present invention is to produce a polyalkylene polyamine without the use of aziridine, to obtain a product of a desired chain length without the formation of an undesired coupling product, and to further reduce the number of product colors Is to find

  The object is to produce a polyalkylene polyamine by homogeneous contact amination of alcohol, in which (i) aliphatic aminoalcohols or (ii) aliphatic diamine or aliphatic polyamine and aliphatic diol or aliphatic polyol. Is solved in the presence of a homogeneous catalyst and hydrogen gas in the presence of water. Preferably, this reaction is performed at a pressure of 0.1 to 25 MPa and a temperature of 100 to 200 ° C.

Within the scope of the present invention, the notation of the formula C _a -C _b represents a chemical compound or chemical substituent having a predetermined number of carbon atoms. The number of carbon atoms may be selected from the entire range of ab including a and b, where a is at least 1 and b is always greater than a. The chemical compound or chemical substituent is further defined by the notation of the formula C _a -C _b -V. Here, V represents a chemical compound class or a chemical substituent class, for example, an alkyl compound or an alkyl substituent.

Specifically, the generic names given for the various substituents have the following meanings:
C ₁ -C ₅₀ - alkyl: straight-chain or branched hydrocarbon radical having up to 50 carbon atoms, for example C ₁ -C ₁₀ - alkyl, or C ₁₁ -C ₂₀ - alkyl, preferably C ₁ -C ₁₀ - alkyl, for example C ₁ -C ₃ - alkyl, for example methyl, ethyl, propyl, isopropyl, or C ₄ -C ₆ - alkyl, n- butyl, sec- butyl, tert- butyl, 1,1-dimethylethyl, Pentyl, 2-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 2- Chirubuchiru, 1,1,2-trimethyl propyl, 1,2,2-trimethyl propyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, or C ₇ -C ₁₀ - alkyl, for example heptyl, Octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, 1,1,3,3-tetramethylbutyl, nonyl or decyl, and isomers thereof.

C ₃ -C ₁₅ -cycloalkyl: monocyclic saturated hydrocarbon group having _{3 to 15} carbon ring members, preferably C ₃ -C ₈ -cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl Or cyclooctyl and saturated or unsaturated ring systems such as norbornyl or norbenyl.

  Aryl: monocyclic to tricyclic aromatic ring systems having 6 to 14 carbon ring members, for example phenyl, naphthyl or anthracenyl, preferably monocyclic to bicyclic, particularly preferably monocyclic aromatic ring systems.

  The symbol “*” represents the valence in all chemical compounds within the scope of the present invention, and a chemical group is bonded to another chemical group via this valence.

  The polyalkylene polyamine is obtained by reacting (i) aliphatic aminoalcohols or (ii) aliphatic diamine or aliphatic polyamine and aliphatic diol or aliphatic polyol in the presence of a catalyst, respectively. . Surprisingly, it has been found that if hydrogen is injected during the reaction, the product color number is reduced. Here, for comparison, a product synthesized in the same way but without hydrogen is used. Therefore, according to the present invention, when hydrogen is injected before or during the synthesis of the polyalkylene polyamine, that is, when the reaction is carried out in the presence of hydrogen gas, a polyalkylene polyamine having a low color number can be obtained. The injection of hydrogen gas is preferably performed at a pressure of 0.1 to 25 MPa (hydrogen gas partial pressure), particularly preferably 1 to 10 MPa, particularly 1 to 7 MPa. Preferably, the temperature is adjusted to 100-200 ° C, particularly preferably 130-180 ° C. The number of colors will be at least one-half, preferably one-tenth to one-hundredth, by hydrogen injection.

  Aliphatic amino alcohols suitable for reaction under a hydrogen atmosphere contain at least one primary or secondary amino group and at least one OH group. Examples are linear, branched or cyclic alkanolamines such as monoethanolamine, diethanolamine, aminopropanol such as 3-aminopropan-1-ol or 2-aminopropan-1-ol, aminobutanol such as 4-aminobutane. -1-ol, 2-aminobutan-1-ol or 3-aminobutan-1-ol, aminopentanol, such as 5-aminopentan-1-ol or 1-aminopentan-2-ol, aminodimethylpentanol, such as 5-amino-2,2-dimethylpentanol, aminohexanol, such as 2-aminohexane-1-ol or 6-aminohexane-1-ol, aminoheptanol, such as 2-aminoheptan-1-ol or 7- Aminoheptan-1-ol, amino Octanol, such as 2-aminooctane-1-ol or 8-aminooctane-1-ol, aminononanol, such as 2-aminononan-1-ol or 9-aminononan-1-ol, aminodecanol, such as 2-aminodecane -1-ol or 10-aminodecan-1-ol, aminoundecanol, such as 2-aminoundecan-1-ol or 11-aminoundecan-1-ol, aminododecanol, such as 2-aminododecan-1-ol Or 12-aminododecan-1-ol, aminotridecanol, such as 2-aminotridecan-1-ol, 1- (2-hydroxyethyl) piperazine, 2- (2-aminoethoxy) ethanol, alkylalkanolamine, For example, butyl ethanolamine, propyl ethanol Triethanolamine, ethyl ethanolamine, methyl ethanolamine. Particularly preferred are monoethanolamine and monopropanolamine.

  Aliphatic diamines suitable for reaction under hydrogen atmosphere are at least two primary amino groups, or at least one primary and secondary amino group, or at least two secondary amino groups. And preferably contains two primary amino groups. Examples are linear, branched or cyclic aliphatic diamines. Examples are ethylenediamine, 1,3-propylenediamine, 1,2-propylenediamine, butylenediamine, such as 1,4-butylenediamine or 1,2-butylenediamine, diaminopentane, such as 1,5-diaminopentane or 1, 2-diaminopentane, 1,5-diamino-2-methylpentane, diaminohexane, such as 1,6-diaminohexane or 1,2-diaminohexane, diaminoheptane, such as 1,7-diaminoheptane or 1,2-diamino Heptane, diaminooctane, such as 1,8-diaminooctane or 1,2-diaminooctane, diaminononane, such as 1,9-diaminononane or 1,2-diaminononane, diaminodecane, such as 1,10-diaminodecane or 1,2- Diaminodecane, diaminoun Cans such as 1,11-diaminoundecane or 1,2-diaminoundecane, diaminododecane such as 1,12-diaminododecane or 1,2-diaminododecane, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane 4,4′-diaminodicyclohexylmethane, isophoronediamine, 2,2-dimethylpropane-1,3-diamine, 4,7,10-trioxatridecane-1,13-diamine, 4,9-dioxadodecane -1,12-diamine, polyetheramine, piperazine, 3- (cyclohexylamino) propylamine, 3- (methylamino) propylamine, N, N-bis (3-aminopropyl) methylamine.

  Suitable aliphatic diols are linear, branched or cyclic aliphatic diols. Examples for aliphatic diols are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propanediol, butanediol, such as 1,4-butylene glycol or butane-2. , 3-diol, or 1,2-butylene glycol, pentanediol, such as neopentyl glycol or 1,5-pentanediol or 1,2-pentanediol, hexanediol, such as 1,6-hexanediol or 1,2- Hexanediol, heptanediol, such as 1,7-heptanediol or 1,2-heptanediol, octanediol, such as 1,8-octanediol or 1,2-octanediol, nonanediol, such as 1,9-nonanediol, or 1,2-nonanediol Decanediol, such as 1,10-decanediol or 1,2-decanediol, undecanediol, such as 1,11-undecanediol or 1,2-undecanediol, dodecanediol, such as 1,12-dodecanediol, 1,2 -Dodecanediol, tridecanediol, for example 1,13-tridecanediol or 1,2-tridecanediol, tetradecanediol, for example 1,14-tetradecanediol or 1,2-tetradecanediol, pentadecanediol, for example 1,15 Pentadecanediol or 1,2-pentadecanediol, hexadecanediol, such as 1,16-hexadecanediol or 1,2-hexadecanediol, heptadecanediol, such as 1,17-heptadecanediol or 1 2-heptadecanediol, octadecanediol, such as 1,18-octadecanediol or 1,2-octadecanediol, 3,4-dimethyl-2,5-hexanediol, polyTHF, 1,4-bis- (2-hydroxy Ethyl) piperazine, diethanolamine, such as butyldiethanolamine or methyldiethanolamine, dialcoholamine and trialcoholamine.

Preferred polyalkylene polyamines obtained under hydrogen pressure according to the invention contain C ₂ -C ₅₀ -alkylene units, particularly preferably C ₂ -C ₂₀ -alkylene units. These may be linear or branched, but are preferably linear. Examples are ethylene, propylene, such as 1,3-propylene, butylene, such as 1,4-butylene, pentylene, such as 1,5-pentylene or 1,2-pentylene, hexylene, such as 1,6-hexylene, octylene, such as 1,8-octylene or 1,2-octylene, nonylene, such as 1,9-nonylene or 1,2-nonylene, decylene, such as 1,2-decylene or 1,10-decylene, undecylene, such as 1,2-undecylene , Dodecylene, such as 1,12-dodecylene or 1,2-dodecylene, tridecylene, such as 1,2-tridecylene, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, neopentylene. Cycloalkylene units such as 1,3-cyclohexylene or 1,4-cyclohexylene are also possible. Particularly preferably, the polyalkylene polyamine has C ₂ -alkylene units.

  In each reaction under hydrogen pressure, it is also possible to use a mixture of aliphatic aminoalcohols, or a mixture of alkanediols or a mixture of diaminoalkanes. The resulting polyalkylene polyamine can contain alkylene units of various lengths.

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

  Under hydrogen pressure, a polyol or a mixture of diol and polyol can also be reacted with a diamine. Polyamines or mixtures of diamines and polyamines can also be reacted with diols. Polyols or mixtures of diols and polyols can also be reacted with polyamines or mixtures of diamines and polyamines. In this case, a highly branched product is obtained. Examples for polyols are glycerin, trimethylolpropane, sorbitol, triethanolamine, triisopropanolamine. Examples for polyamines are diethylenetriamine, tris (aminoethyl) amine, triazine, 3- (2-aminoethylamino) propylamine, dipropylenetriamine, N, N′-bis- (3-aminopropyl) -ethylenediamine. .

  Particularly suitable compounds are alkyl or alkylene groups in which at least one of the starting aliphatic amino alcohol, aliphatic diamine or aliphatic polyamine or aliphatic diol or aliphatic polyol has 2 to 4 carbon atoms. It is a compound containing.

  Similarly, a compound particularly suitable for reaction under hydrogen pressure is at least one of the starting materials aliphatic amino alcohol, aliphatic diamine or aliphatic polyamine or aliphatic diol or aliphatic polyol, preferably 5 or more. Is a compound containing an alkyl group or an alkylene group having 7 or more, particularly preferably 9 or more, particularly 12 or more carbon atoms.

  Particularly suitable compounds are 5 to 50, preferably 5 to 20, particularly preferably at least one of the starting materials aliphatic amino alcohol, aliphatic diamine or aliphatic polyamine or aliphatic diol or aliphatic polyol. Is a compound containing an alkyl or alkylene group having 6 to 18, very particularly preferably 7 to 16, more preferably 8 to 14, more preferably 9 to 12 carbon atoms.

  Preferably, during synthesis, at least (i) monoethanolamine, (ii) monopropanolamine, or (iii) ethylene glycol and ethylenediamine are selected. More preferably, at least (i) ethylenediamine or (ii) 1,2-propylenediamine or (iii) 1,3-propylenediamine and 1,2-decanediol or 1,2-dodecanediol are selected.

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

  Polyalkylene polyamines can also react under hydrogen pressure. During the reaction, a diamine, or polyamine, or diol, or polyol, or amino alcohol can be added.

  Hydrogen can be injected while the reaction water is continuously or discontinuously separated from the system.

The preparation of polyalkylene polyamines is specifically illustrated by Formula 1 and Formula 2:

  A homogeneous catalyst is taken to be a catalyst which exists in the reaction medium in a homogeneous manner during the reaction.

  Homogeneous catalysts generally contain at least one element from the subgroup of the periodic table (transition metal). The amination of the alcohol under hydrogen pressure may be carried out in the presence or absence of a further solvent. The amination of the alcohol may be carried out in a multiphase, preferably single-phase or two-phase liquid system, generally at a temperature of 20 to 250 ° C. If the reaction system is biphasic, the upper phase can consist of a non-polar solvent containing the majority of the homogeneously dissolved catalyst and the lower phase can consist of a polar starting material, the polyamine formed and water. . Furthermore, the lower phase can consist of water and a homogeneously dissolved catalyst, and the upper phase can consist of a nonpolar solvent containing the majority of the polyamine formed and the majority of the nonpolar starting material.

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

  The number n of alkylene units in the polyalkylene polyamine is generally 3 to 50000.

The polyalkylene polyamine thus obtained can have not only NH ₂ groups but also OH groups as terminal groups at the chain ends.

Here, preferably,
R is the same or different independently of one another and represents H, C ₁ -C ₅₀ -alkyl,
l and m are the same or different independently of one another and represent an integer from 1 to 50, preferably 1 to 30, particularly preferably 1 to 20;
n and k are the same or different independently of one another, and represent an integer from 0 to 50, preferably 0 to 30, particularly preferably 0 to 20,
i represents an integer from 3 to 50000.

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

  The polyalkylene polyamine obtained by the method according to the present invention may be linear, branched or multi-branched, or may have a cyclic structural unit.

  Here, the distribution of the structural units (linear, branched or cyclic) is random. The polyalkylenepolyamine thus obtained differs from polyethyleneimine produced from ethyleneimine in that OH end groups are present and in some cases the alkylene groups are different.

  The homogeneous catalyst is preferably a transition metal complex catalyst containing one or more various metals of the subgroups of the periodic table, preferably at least one element of Groups 8, 9 and 10 of the periodic table. In particular, a transition metal complex catalyst containing ruthenium or iridium is particularly preferable. The subgroup metals are present in the form of complex compounds. A number of different ligands are possible.

  Suitable ligands present in the transition metal complex are, for example, phosphines substituted with alkyls or aryls, polydentate phosphines substituted with alkyls or aryls bridged with arylene groups or alkylene groups, nitrogen-containing complexes. Cyclic carbene, cyclopentadienyl and pentamethylcyclopentadienyl, aryl, olefin ligand, hydride, halide, carboxylate, alkoxylate, carbonyl, hydroxide, trialkylamine, dialkylamine, monoalkyl Amines, nitrogen-containing aromatic compounds such as pyridine or pyrrolidine, as well as polydentate amines. The organometallic complex can contain one or more of the various ligands described above.

Preferred ligands are at least 1-20, preferably 1-12, unbranched or branched, acyclic or cyclic aliphatic groups, aromatic groups or araliphatic groups. One (monodentate) phosphine or (polydentate) polyphosphine, such as diphosphine. Examples for branched alicyclic and araliphatic groups are —CH ₂ —C ₆ H ₁₁ and —CH ₂ —C ₆ H ₅ . Suitable groups include, for example: methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 1- (2-methyl) propyl, 2- (2-methyl) propyl 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, 1-nonyl, 1-decyl, 1-undecyl, 1-dodecyl, cyclopentenyl, cyclohexyl, cycloheptyl and cyclooctyl, methylcyclopentyl, methylcyclohexyl, 1- (2-methyl) -pentyl, 1- (2-ethyl) -hexyl, 1- (2-propylheptyl), adamantyl and norbornyl, phenyl, tolyl and xylyl, and 1-phenylpyrrole, 1- (2- Methoxyphenyl) -pyrrole, 1- (2,4,6-trimethylphenyl) -imidazole and - phenylindole. The phosphine group can contain one, two or three of the above-mentioned unbranched or branched, acyclic or cyclic aliphatic groups, aromatic groups or araliphatic groups. These groups may be the same or different.

  Preferably, the homogeneous catalyst comprises an unbranched, acyclic or cyclic aliphatic group having 1 to 12 carbon atoms, or an araliphatic group, or adamantyl or 1-phenylpyrrole as group. Contains monodentate or polydentate phosphine ligands.

  In the above unbranched or branched, acyclic or cyclic aliphatic group, aromatic group or araliphatic group, individual carbon atoms may be substituted by further phosphine groups. Thus, multidentate, for example bidentate or tridentate phosphine ligands, in which the phosphine group is bridged with an alkylene or arylene group are also included. Preferably, the phosphine group is 1,2-phenylene bridge, methylene bridge, 1,2-ethylene bridge, 1,2-dimethyl-1,2-ethylene bridge, 1,3-propylene bridge, 1,4-butylene bridge. And 1,5-propylene bridges.

  Particularly suitable monodentate phosphine ligands are triphenylphosphine, tolylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, trimethylphosphine and triethylphosphine, and di (1-adamantyl) -n-butylphosphine. , Di (1-adamantyl) benzylphosphine, 2- (dicyclohexylphosphino) -1-phenyl-1H-pyrrole, 2- (dicyclohexylphosphino) -1- (2,4,6-trimethyl-phenyl) -1H- Imidazole, 2- (dicyclohexylphosphino) -1-phenylindole, 2- (di-tert-butylphosphino) -1-phenylindole, 2- (dicyclohexylphosphino) -1- (2-methoxyphenyl) -1H -Pyrrole, 2- (di-tert -Butylphosphino) -1- (2-methoxyphenyl)-1H-pyrrole and 2- (di -tert- butyl - phosphino) -1-phenyl-1H-pyrrole. Very particularly preferred are triphenylphosphine, tolylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, trimethylphosphine and triethylphosphine, and di (1-adamantyl) -n-butylphosphine, 2- ( Dicyclohexylphosphino) -1-phenyl-1H-pyrrole and 2- (di-tert-butyl-phosphino) -1-phenyl-1H-pyrrole.

  Particularly suitable polydentate phosphine ligands are bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,2-dimethyl-1,2-bis (diphenylphosphino) ethane, 1 , 2-bis (dicyclohexylphosphino) ethane, 1,2-bis (diethylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 2,3 -Bis (diphenylphosphino) butane, 1,3-bis (diphenylphosphino) propane, 1,1,1-tris (diphenyl-phosphinomethyl) ethane, 1,1'-bis (diphenylphosphanyl) ferrocene and 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene.

  Furthermore, preferably a nitrogen-containing heterocyclic carbene is mentioned as a particularly suitable ligand. Here, a ligand that forms a water-soluble complex with Ru is extremely preferable. Particularly preferred are 1-butyl-3-methylimidazoline-2-ylidene, 1-ethyl-3-methylimidazoline-2-ylidene, 1-methylimidazoline-2-ylidene and dipropylimidazolin-2-ylidene.

  Particularly suitable ligands are cyclopentadienyl and its derivatives substituted 1 to 5 times with alkyl, aryl and / or hydroxy, such as methylcyclopentadienyl, pentamethylcyclopentadienyl, tetraphenylhydroxy Mention may also be made of cyclopentadienyl and pentaphenylcyclopentadienyl. Furthermore, particularly suitable ligands are indenyl and its substituted derivatives as described for cyclopentadienyl.

  Likewise particularly suitable ligands are chloride, hydride and carbonyl.

  The transition metal complex catalyst can of course include a plurality of the same or different ligands.

Homogeneous catalysts can be used directly in their active form, or they can be used in conventional standard complexes such as [Ru (p-cymene) Cl ₂ ] ₂ , [Ru (benzene) Cl ₂ ] _n , [Ru (CO). ₂ Cl ₂ ] _n , [Ru (CO) ₃ Cl ₂ ] ₂ , [Ru (COD) (allyl)], [RuCl ₃ · H ₂ O], [Ru (acetylacetonate) ₃ ], [Ru (DMSO ) ₄ Cl ₂ ], [Ru (PPh ₃ ) ₃ (CO) (H) Cl], [Ru (PPh ₃ ) ₃ (CO) Cl ₂ ], [Ru (PPh ₃ ) ₃ (CO) (H) ₂ ], [Ru (PPh ₃ ) ₃ Cl ₂ ], [Ru (cyclopentadienyl) (PPh ₃ ) ₂ Cl], [Ru (cyclopentadienyl) (CO) ₂ Cl], [Ru (cyclopentadi) _{enyl) (CO) 2 H],} [Ru ( _{cyclopentadienyl) (CO) 2] 2,} [Ru ( Bae Data _{methylcyclopentadienyl) (CO) 2 Cl],} [Ru ( _{pentamethylcyclopentadienyl) (CO) 2 H],} [Ru ( _{pentamethylcyclopentadienyl) (CO) 2] 2,} [Ru (Indenyl) (CO) ₂ Cl], [Ru (indenyl) (CO) ₂ H], [Ru (indenyl) (CO) ₂ ] ₂ , ruthenocene, [Ru (binap) Cl ₂ ], [Ru (bipyridine) ₂ Cl ₂ .2H ₂ O], [Ru (COD) Cl ₂ ] ₂ , [Ru (pentamethylcyclopentadienyl) (COD) Cl], [Ru ₃ (CO) ₁₂ ], [Ru (tetraphenylhydroxy) -Cyclopentadienyl) (CO) ₂ H], [Ru (PMe ₃ ) ₄ (H) ₂ ], [Ru (PEt ₃ ) ₄ (H) ₂ ], [Ru (P ⁿ Pr ₃ ) ₄ (H ) ₂ ], [Ru (P ⁿ Bu ₃ ) ₄ (H) ₂ ], [Ru (P ⁿ octyl ₃ ) ₄ (H) ₂ ], [IrCl ₃ .H ₂ O], KIrCl ₄ , K ₃ IrCl ₆ , [Ir (COD) Cl] ₂ , [Ir (cyclooctene) ₂ Cl] ₂ , [Ir (ethene) ₂ Cl] ₂ , [Ir (cyclopentadienyl) Cl ₂ ] ₂ , [Ir (pentamethylcyclopentadienyl) Cl ₂ ] ₂ , [Ir (cyclopentadienyl) ) (CO) ₂ ], [Ir (pentamethylcyclopentadienyl) (CO) ₂ ], [Ir (PPh ₃ ) ₂ (CO) (H)], [Ir (PPh ₃ ) ₂ (CO) (Cl )], [Ir (PPh ₃ ) ₃ (Cl)], and the addition of the corresponding ligand, preferably the above monodentate or polydentate phosphine ligand, or the above nitrogen-containing heterocyclic carbene Below, it can also be produced for the first time under reaction conditions.

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

  The process according to the invention can be carried out with or without a solvent. Of course, the process according to the invention can also be carried out in solvent mixtures.

  If the process is carried out in a solvent, the amount of solvent is often chosen so that the starting materials (i) and (ii) are just dissolved in the solvent. In general, the mass ratio of the amount of solvent to the amount of starting materials (i) and (ii) is 100: 1 to 0.1: 1, preferably 10: 1 to 0.1: 1.

  The reaction according to the invention is generally carried out in the liquid phase at a temperature of 20 to 250 ° C. Preferably, this temperature is at least 100 ° C, preferably up to 200 ° C. The reaction can be carried out at a total pressure of 0.1 to 25 MPa (absolute), this pressure may be a combination of the pressure of hydrogen and the intrinsic pressure of the solvent at the reaction temperature, For example, the pressure of gas such as nitrogen or argon and the pressure of hydrogen may be combined. The average reaction time is generally 15 minutes to 100 hours.

  The addition of a base can have a beneficial effect on product formation. Suitable bases here include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alcoholates, alkaline earth metal alcoholates, alkali metal carbonates and alkaline earth metal carbonates, which are used 0.01-100 equivalent can be used with respect to the metal catalyst to perform.

  In a preferred embodiment of the process according to the invention, the starting material is (i) an aliphatic aminoalcohol, (ii) an aliphatic diamine or aliphatic polyamine or an aliphatic diol or aliphatic polyol one heteroatom O or N is present in the α and β positions of the C atom chain and thus on adjacent C atoms.

  In a preferred embodiment of the process according to the invention, the starting material is (i) an aliphatic aminoalcohol, (ii) an aliphatic diamine or aliphatic polyamine or an aliphatic diol or aliphatic polyol one heteroatom O or N is present at the α- and ω-positions of the C atom chain, and thus at the opposite end of the C atom chain.

  Another subject of the invention is a polyalkylene polyamine, preferably polyethylene amine or polypropylene amine, produced by the above-described embodiment of the process according to the invention.

  Another subject of the invention is a polyalkylene polyamine containing a hydroxy group, a secondary amine or a tertiary amine. Preferably, these hydroxy groups, secondary amines or tertiary amines are present on the terminal carbon atoms of the alkylene group and are therefore terminal groups. Preferably, the polyalkylene polyamine contains a hydroxy group.

  For example, polyalkylene polyamines containing this hydroxy group, secondary amine or tertiary amine are obtained using the process according to the invention. In particular, this polyalkylene polyamine is obtained in a process by monomer polymerization in a single stage.

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

  In another preferred embodiment, the polyalkylene polyamine comprising a hydroxy group, secondary amine or tertiary amine has only hydroxy end groups or amine end groups (primary, secondary, primary). 3rd grade) only.

  The invention further provides: a) as a fixing agent for printing inks, b) as an auxiliary (adhesive) for producing composite films, c) as an aggregation promoter for adhesives, d) E) as a crosslinker / curing agent for resins, e) as a primer in paints, f) as a wet adhesion promoter for dispersion paints, g) as complexing agents and flocculants, h) wood It also relates to the use of this polyalkylene polyamine as a penetration aid in the protection of i), as an anticorrosive, and j) as a protein and enzyme immobilization agent.

  The present invention will be described in detail with reference to examples, but the examples do not limit the subject of the present invention.

  The average molecular weight of the oligomers was measured by gel permeation chromatography by the size exclusion chromatography method. As eluent, hexafluoroisopropanol was used with 0.05% potassium trifluoroacetate. The measurement was carried out at 40 ° C. at a flow rate of 1 ml / min with a styrene-divinylbenzene-copolymer column (8 mm × 30 cm) using an RI differential refractometer or UV photometer as the detector. Calibration was performed using a narrowly distributed PMMA standard.

  For the measurement of the Hazen color number (by APHA), the sample is diluted 1: 2500 with a diluent that does not absorb within the range of 380-720 nm. Thereafter, the Hazen color number is determined in increments of 10 nm within a range of 380 to 720 nm.

  Usually, the number of colors of polyethylene polyamines produced by known prior art methods exceeds 100, partly exceeds 200 and sometimes exceeds 600.

Example 1
In a 250 ml autoclave equipped with a paddle stirrer, 12.1 g (7.63 mmol), ethanolamine 450 g under inert conditions to exclude oxygen, [Ru (P ⁿ octyl ₃ ) ₄ (H) ₂ ] (7.37 mol), potassium-tert-butylate 10.05 g (89.56 mmol) and toluene 1620 ml were weighed in. Hydrogen was injected into the sealed autoclave to 40 bar. The reaction mixture was then heated to 140 ° C. and stirred for 20 hours. After the reaction was complete and cooled, two phases were formed. The upper phase containing the catalyst was separated from the lower phase containing the product. The product phase was shaken with toluene. Subsequently, the reaction water, unreacted starting materials and volatile components were removed on a rotary evaporator at 116 ° C. and 12 mbar, giving 115.66 g of pure product. The obtained oligomer had a mass average (RI) of 1470 g / mol and a dispersity (Mw / Mn) of 2.8. This corresponds to an average chain length n = 34 of the oligomer (CH ₂ CH ₂ NH) _n . The number of colors was 20.

Example 2
In a 250 ml autoclave equipped with a paddle stirrer, under inert conditions, 0.27 g (0.17 mmol) of [Ru (P ⁿ octyl ₃ ) ₄ (H) ₂ ], the effluent from Example 1. 5 g, 230 mg (2.05 mmol) of potassium tert-butylate and 37 ml of toluene were weighed in. The reaction mixture was stirred in a closed autoclave at 140 ° C. for 10 hours under the intrinsic pressure of the solvent. After the reaction was complete and cooled, the product precipitated as a solid. The batch was quenched with 200 ml of water and the product dissolved and two phases formed. The upper phase containing the catalyst was separated from the lower phase containing the product. The reaction water, unreacted starting materials and volatile components were removed on a rotary evaporator at 116 ° C. and 12 mbar to give 9.42 g of pure product. The obtained oligomer had a mass average (RI) of 1520 g / mol and a dispersity (Mw / Mn) of 3.4. This corresponds to an average chain length n = 35 of the oligomer (CH ₂ CH ₂ NH) _n . The number of colors was 71.

Example 3
In a 250 ml autoclave equipped with a paddle stirrer, under inert conditions, 0.27 g (0.17 mmol) of [Ru (P ⁿ octyl ₃ ) ₄ (H) ₂ ], the effluent from Example 1. 5 g, 230 mg (2.05 mmol) of potassium tert-butylate and 37 ml of toluene were weighed in. Hydrogen was pressed into a sealed autoclave to 15 bar. The reaction mixture was then heated to 140 ° C. and stirred for 10 hours. After the reaction was complete and cooled, the product precipitated as a solid. The batch was quenched with 200 ml of water and the product dissolved and two phases formed. The upper phase containing the catalyst was separated from the lower phase containing the product. The reaction water, unreacted starting materials and volatile components were removed on a rotary evaporator at 116 ° C. and 12 mbar to give a pure product. The obtained oligomer had a mass average (RI) of 1170 g / mol and a dispersity (Mw / Mn) of 3.4. This corresponds to an average chain length n = 27 of the oligomer (CH ₂ CH ₂ NH) _n . The number of colors was 54.

Example 4
In a 250 ml autoclave equipped with a paddle stirrer, 0.20 g (0.71 mmol) of [Ru (COD) Cl ₂ ], 0.50 g of 1-butyl-3-methylimidazolium chloride (2 0.9 mmol), 1,2-dodecanediol 12.1 g (0.06 mol), 1,3-propylenediamine 20.0 g (0.27 mol), potassium tert-butylate 0.50 g (4.46 mmol) and toluene 34 ml Weighed in. The reaction mixture was stirred in a sealed autoclave at 150 ° C. for 20 hours under the intrinsic pressure of the solvent. After the reaction was completed and cooled, 5 ml of water was added to the reaction mixture and shaken to obtain a product solution (50.0 g) in toluene and an aqueous catalyst solution (12.66 g). . These phases were separated from each other. From the product phase, unreacted starting materials and volatile components were removed on a rotary evaporator at 120 ° C. and 20 mbar to obtain 14.13 g of pure product. The obtained oligomer had a mass average (RI) of 1470 g / mol and a dispersity (Mw / Mn) of 3.9. This corresponds to an average chain length n = 6 of the oligomer (CH ₂ CH (C ₁₀ H ₂₁ ) NHCH ₂ CH ₂ NH) _n . The number of colors was 74.

Example 5
In a 250 ml autoclave equipped with a paddle stirrer, 0.20 g (0.71 mmol) of [Ru (COD) Cl ₂ ], 0.50 g of 1-butyl-3-methylimidazolium chloride (2 0.9 mmol), 1,2-dodecanediol 12.1 g (0.06 mol), 1,3-propylenediamine 20.0 g (0.27 mol), potassium tert-butylate 0.50 g (4.46 mmol) and toluene 34 ml Weighed in. Hydrogen was injected into the sealed autoclave to 40 bar. The reaction mixture was then heated to 150 ° C. and stirred for 20 hours. After the reaction was completed and cooled, 20 ml of water was added to the reaction mixture and shaken to obtain a product solution in toluene and an aqueous catalyst solution. These phases were separated from each other. From the product phase, unreacted starting materials and volatile components were removed on a rotary evaporator at 120 ° C. and 20 mbar to obtain 11.97 g of pure product. The obtained oligomer had a mass average (RI) of 1470 g / mol and a dispersity (Mw / Mn) of 3.9. This corresponds to an average chain length n = 6 of the oligomer (CH ₂ CH (C ₁₀ H ₂₁ ) NHCH ₂ CH ₂ NH) _n . The number of colors was 21.

Comparative Example 1
In an autoclave equipped with a paddle type stirrer, 10 g (0.36 mmol) of [Ru (COD) (Cl) ₂ ] ₂ , 0.22 g (0.36 mmol) of triphos, tri-n-octylphosphine under inert conditions 0.2 g (0.54 mmol), ethanolamine 10 g (0.16 mol), potassium tert-butylate 0.15 g (1.3 mmol) and toluene 60 g were weighed in. The reaction mixture was then heated to 140 ° C. and stirred for 20 hours. After the reaction was complete and cooled, the batch was mixed with 10 ml of water. The upper phase was separated from the lower phase containing the product. Water, unreacted starting material and volatile components were then removed on a rotary evaporator at 110 ° C. and 12 mbar to give 6.5 g of pure product. The number of colors was 871.

Claims (30)

In the process for producing a polyalkylene polyamine by homogeneous contact amination of alcohol, (i) aliphatic amino alcohols or
(Ii) an aliphatic diamine or aliphatic polyamine and an aliphatic diol or aliphatic polyol;
A method characterized by reacting in the presence of a homogeneous catalyst and in the presence of hydrogen gas under the elimination of water.   The process according to claim 1, wherein the reaction is carried out at a hydrogen gas partial pressure of 0.1 to 25 MPa.   3. A method according to claim 1 or 2, wherein hydrogen gas chemically intervenes in the catalytic amination of the alcohol, thereby reducing the formation of colored components.   The method according to any one of claims 1 to 3, wherein the catalyst is a transition metal complex catalyst.   The process according to claim 1, wherein the catalyst comprises ruthenium or iridium.   6. A process according to any one of claims 1 to 5, wherein the catalyst comprises a nitrogen-containing heterocyclic carbene ligand.   The catalyst is from the group consisting of 1-butyl-3-methylimidazoline-2-ylidene, 1-ethyl-3-methylimidazoline-2-ylidene, 1-methylimidazoline-2-ylidene, dipropylimidazolin-2-ylidene 7. A method according to claim 6, comprising a carbene ligand.   6. A process according to any one of claims 1 to 5, wherein the catalyst comprises a monodentate phosphine ligand or a polydentate phosphine ligand.   9. A process according to claim 8, wherein the catalyst comprises a monodentate phosphine ligand comprising an unbranched acyclic or cyclic aliphatic group having 1 to 12 carbon atoms or an aromatic group.   Catalysts are triphenylphosphine, tolylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, trimethylphosphine, triethylphosphine, di (1-adamantyl) -n-butylphosphine, di (1-adamantyl) benzyl 10. A process according to claim 8 or 9, comprising a monodentate phosphine ligand selected from the group consisting of phosphine, 2- (dicyclohexylphosphino) -1-phenyl-1H-pyrrole.   9. The catalyst according to claim 8, comprising a polydentate phosphine ligand consisting of at least one unbranched acyclic or cyclic aliphatic group having 1 to 12 carbon atoms or an aromatic group. the method of.   The catalyst is bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,2-dimethyl-1,2-bis (diphenylphosphino) ethane, 1,2-bis (dicyclohexylphosphino). ) Ethane, 1,2-bis (diethylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 2,3-bis (diphenylphosphino) butane 1,1,1-tris (diphenyl-phosphinomethyl) ethane, 1,1′-bis (diphenylphosphanyl) ferrocene and 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene 12. A process according to any one of claims 8 to 11 comprising a polydentate phosphine ligand selected from.   13. A process according to any one of claims 1 to 12, wherein the catalyst comprises a ligand selected from the group consisting of cyclopentadienyl, substituted cyclopentadienyl, indenyl and substituted indenyl.   14. A process according to any one of claims 1 to 13, wherein the catalyst comprises a ligand selected from the group consisting of hydroxide, hydride, carbonyl and chloride.   15. A process according to any one of claims 1 to 14, wherein the reaction is carried out in the presence of a solvent.   16. A process according to claim 15, wherein the solvent is selected from the group consisting of benzene, toluene, xylene, alkanes, acyclic ethers, cyclic ethers, alcohols having more than 3 C atoms.   16. The method of claim 15, wherein the solvent is selected from the group consisting of water, ionic liquid, sulfoxide, formamide, acetonitrile.   At least one of aliphatic amino alcohol, aliphatic diamine or aliphatic polyamine, aliphatic diol or aliphatic polyol as starting materials is 5 or more, preferably 7 or more, particularly preferably 9 or more, especially 12 The method according to any one of claims 1 to 17, comprising an alkyl group or an alkylene group having the above carbon atoms.   The method according to any one of claims 1 to 17, wherein at least (i) monoethanolamine or (ii) ethylene glycol and ethylenediamine are reacted.   The process according to any one of claims 1 to 17, wherein 3-aminopropan-1-ol is reacted.   18. The method according to claim 1, wherein at least ethylenediamine, 1,2-propylenediamine or 1,3-propylenediamine and 1,2-decanediol or 1,2-dodecanediol are selected. the method of.   At least one of the starting materials aliphatic amino alcohol, aliphatic diamine or aliphatic polyamine or aliphatic diol or aliphatic polyol contains an alkyl or alkylene group having 2 to 4 carbon atoms. Item 18. The method according to any one of Items 1 to 17.   At least one of aliphatic amino alcohol, aliphatic diamine or aliphatic polyamine or aliphatic diol or aliphatic polyol as a starting material is 5 to 20, preferably 6 to 18, particularly preferably 7 to 16, 18. A process according to any one of claims 1 to 17, in particular comprising an alkyl or alkylene group having 8 to 14 carbon atoms.   One heteroatom O or N of the starting material aliphatic amino alcohol, aliphatic diamine or aliphatic polyamine or aliphatic diol or aliphatic polyol is adjacent to the α-position and β-position of the C atom chain and thus adjacent 24. A method according to any one of claims 1 to 18, 22 and 23 present on a C atom.   One heteroatom O or N of the starting material aliphatic amino alcohol, aliphatic diamine or aliphatic polyamine or aliphatic diol or aliphatic polyol is in the α- and ω-positions of the C-atom chain and thus C-atoms 24. A method according to any one of claims 1 to 18, 22 and 23, present at the opposite end of the chain.   A polyalkylene polyamine obtained by the method according to any one of claims 1 to 25.   Polyethyleneimine obtained by the method according to claim 19.   Polypropyleneamine obtained by the method according to claim 20.   Polyalkylene polyamines containing hydroxy groups, secondary amines or tertiary amines. The following:
a) fixing agents for printing inks,
b) an adhesion promoter in the composite film;
c) an aggregation promoter for adhesives,
d) a crosslinker / curing agent for the resin,
e) primer in paint,
f) a wet adhesion promoter for the dispersion paint;
g) complexing agents and flocculants,
h) penetration aids in the protection of wood,
i) anticorrosive,
j) Use of the polyalkylene polyamine according to any one of claims 26 to 29 as a protein and enzyme immobilization agent.