WO2008142100A1

WO2008142100A1 - Method for producing carbonate-terminated urethanes

Info

Publication number: WO2008142100A1
Application number: PCT/EP2008/056241
Authority: WO
Inventors: Andreas Job; Lars Rodefeld
Original assignee: Saltigo Gmbh
Priority date: 2007-05-21
Filing date: 2008-05-21
Publication date: 2008-11-27
Also published as: EP2152774A1; DE102007023866A1

Abstract

The invention relates to an improved method for producing carbonate-terminated urethanes using isocyanates. The method according to the invention is characterized by high yields with no phenol being produced as a secondary component.

Description

Process for the preparation of carbonate-terminated urethanes

The present invention relates to a process for the preparation of carbonate-terminated urethanes.

For a variety of materials and applications, the permanent function of surfaces is important. For example, material surfaces can be made biocompatible by coating with heparin. Other applications include stain-resistant and bacteriostatic finishes and improved adhesion of adhesives and paints.

Targeted modification of biomolecules is also desirable in many cases. For example, it is known that the biological half-life of various drugs can be improved by adding polyoxyalkylene residues

From EP-A-I 541 568, for example, reactive cychsche carbonates of the general formula 1 are known,

wherein R 'is C ₁ -C stands ₂ is alkylene and R "are different organic radicals can represent. These reactive cychschen carbonates can be with nucleophiles implement such as hydroxyl or primary or secondary amino groups of biomolecules, polymers, or to substrate surfaces, wherein the opening The cyan carbon ring comes with simultaneous covalent attachment to the biomolecule, the polymer or other substrate surfaces.

The preparation of the reactive cychschen carbonates of the formula (1) takes place by reaction of the phenyl-substituted cychschen carbonates of the general formula (2),

with amines of the general formula (3) H ₂ NR ^' (3)

A disadvantage of this synthesis is the release of phenol as a by-product of the substitution with the amine in equimolar amounts. Depending on the obtained reaction product of the formula (1), the separation of the toxicologically problematic phenol is associated with great expense US Pat. No. 5,115,045 relates to isocyanate-reactive compositions used to prepare polyurethanes. These isocyanate-reactive compositions are based on the reaction product of (a) a di- or polychloroformate ester of the type Q- [X-COY] _n , where X O and Y may be chlorine, n is at least 2 and Q is an organic radical, with (b) a multi-functional compound, which in addition to the functional groups which react with the di- or Polychlorformiatester (a), necessarily at least one Immo - or enum group must contain. No di- or polychloroformate esters (a) are described which have cyano carbonate groups. The di- or polychloroformate esters are prepared by reacting polyols with acylating agents such as phosgene. From the imino and / or enamino groups contained in the multi-functional compound (b), an isocyanate-reactive amino group can later be obtained by hydrolysis.

From DE-A-26 095 02 a method is known in which a bi-functional isocyanate can be reacted with a polyoxyalkylenepolyamine. This coupling products are obtained, which are interconnected via urea groups.

EP-A-0 328 150 discloses a process which describes the reaction of cyclocarbonate-terminated alcohols with carboxylic anhydrides. Cyclocarbonate-terminated esters are obtained which can be used for a variety of further reactions. Also described in Example 18 is the reaction of hexamethylene diisocyanate with

Glycerol cyclocarbonate in dimethoxyethane. In this case, a significant excess of 3 equivalents of hexamethylene diisocyanate based on 1 equivalent Glycerincyclocarbonat used. The removal of the remaining after the reaction hexamethylene diisocyanate is an economically and environmentally undesirable addition step.

Since there is a high demand for reactive cyclic carbonates for surface treatment, this invention has the object to provide an improved manufacturing process.

The invention relates to a process for the preparation of compounds of general formula (I),

embedded image in which

R ¹ is C _r Ci ₂ alkylene, R ² is C ₁ -C ₃₀ -alkyl, C ₂ -C ₃₀ -alkenyl, Ci-C ₃₀ haloalkyl, C ₁ -C ₆ -AIlCyIoXy-C ₁ -C ₃₀ - alkyl, QQ-alkylcarbonyloxy-d-q O- alkyl, di (C ₁ -C ₈ -alkyl) ammoCrC ₃ o-alkyl, di (C ₇ -C ₁₁ -aralkyl) ammo C ₁ -C ₃₀ -alkyl, di (allyl) aminoC _r C ₃ o-alkyl , ammonio-C _ϊ - C ₃₀ alkyl, polyoxyalkylene Q-Cso-alkyl, Polysiloxanyl-C _r C ₃₀ alkyl, (meth) acrylic oyloxy-QC ^ alkyl, di (C ₁ -C ₆ alkyl) phosphono-C ₁ -C ₃₀ alkyl, di (C _r C ₆ alkyl) - phosphonato-Q-Qo-alkyl, S-Imtdazolio-Cj-Qo-alkyl, - [C ₂ -C ₆ alkylene-O] _x - [C ₂ -C ₆ -alkylene-O] _y -R, wherein R is C ₁ -C ₆ -alkyl, x = 0-50 and y = 0-50, either x or y is at least 1 and the two alkylene radicals different smd, if x and y are both not equal to 0, or a Sacchaπdrest is, or

R ^{2 represents} a fluoresceinyl radical or a pyrene, fluorescem, coumarin, 4,4'-bisstyrylbiphenyl, pyrazohn, hydroquinone, benzoxazole, benzisoxazole, benzimidazole bonded via a C _r C ₃ o-alkylene group. or flavone acid residue. by reacting compounds of the general formula (II)

where R ^{1 has} the meaning given for the general formula (I), with an isocyanate of the general formula (III)

OCN - R ² (Mi) wherein R ^{2 has} the meaning described for the general formula (I).

The advantage of the process according to the invention is the avoidance of phenol as a minor component. It is particularly advantageous that this reaction is an addition reaction in which, in principle, no further secondary components are formed. It is thus a process which provides a complete atomic economy.

The isocyanates of the general formula (III) are obtainable by reacting the amines of the general formula (IV)

H ₂ N - R ² (IV) wherein R ^{2 has} the meaning described for the general formula (I), with phosgene

If the term "substituted" is used in this application, this means in the context of this application that em hydrogen atom on a given radical or atom by eme is replaced with the proviso that the valency of the specified atom is not exceeded and the substitution leads to a stable compound

Within the scope of this application and the invention, all definitions of residues, parameters or explanations mentioned above and mentioned below, general or preferred ranges can be combined with one another in any desired manner, ie also between the respective ranges and preferred ranges

The term "alkyl" is intended to include straight-chain, branched and cyclic alkyl groups, unless explicitly stated otherwise in this application, these alkyl groups each having 1 to 30, preferably 1 to 24 and particularly preferably 1 to 18 carbon atoms are suitable

Alkyl radicals, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-butyl

Pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbuutyl, neo-pentyl, 1-ethylpropyl, cyclohexyϊ,

Cyclopentyl, n-hexyl, 1,1-dimethylpropyl, 1, 2-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-

Dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-

Ethyl butyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n-octyl, p -macyl, adamantyl, the isomeric menthyls, n-nonyl, n-decyl, n-dodecyl, n-t-decyl, n-tetradecyl, n-hexadecyl and n-octadecyl.

The term "haloalkyl" accordingly means an alkyl group of the aforementioned meaning in which one or more hydrogen atoms are replaced by halogen, preferably chlorine or fluorine.

In the same way, within the definitions of the radicals R ² and R ^3, the terms "Al ky loxyalkyl", mean, "Alky Icarbonyl oxyalky 1", "di (alkyl) on inoalkyl"',"di (aralky l) amino alky 1 "," di (allyl) aminoalkyl "," ammonioalkyl "," polyoxyalkylenealkyl "," polysiloxanylalkyl "," (meth) acryloyloxyalkyl " ₅ and" dialkylphosphonoalkyl "," dialkylphosphonatoalkyl "and 3-" imidazolioalkyl "means an alkyl radical, m one or more hydrogen atoms through a

Alkyloxy group, an alkylcarbonyloxy group, eme Dialkylammo group, a Ammomo- group ((NR ⁵ ₃₎ ^T, wherein R ³ independently of one another example of _{Ci-C] g} alkyl, C ₂ -C _lg alkenyl or Benzyl), a polyoxyalkylene radical, a polysüoxanyl radical, eme (meth) acryloyloxy group or an imidazolio group of the following structure

wherein R ^{5 is} hydrogen, C ₁ -C ₁₈ alkyl, C ₂ -C ₈ alkenyl, preferably allyl, or benzyl replaced. When R ² and / or R ^{3 are} aminoalkyl or irmdazohoalkyl, the compound is accompanied by one equivalent of an anion, preferably a physiologically acceptable anion, such as a halide, especially chloride or bromide, sulphate, bisulphate, methosulphate or nitrate.

The term "alkenyl" means an alkyl group having 2 to 30, preferably 2 to 24 and especially 2 to 18 carbon atoms, but contains one or more middle or even terminal C = C double bonds.

The term "alkylene" means a divalent aliphatic, branched or unbranched hydrocarbon radical, preferably one - (CH ₂ -CH ₂ ) -, one - (CH ₂ -CH (CH ₃ )) -, one - (CH ₂ - CH (C ₂ H ₅ )) - or a - (CH ₂ -CH ₂ -CH ₂ -CH ₂ ) - radical.

The polyoxyalkylene radical is preferably derived from ethylene oxide, propylene oxide, butylene oxide or

Tetrahydrofuran, more preferably of ethylene oxide or propylene oxide. It is terminated at the distal end by a radical which is hydrogen or a C 1 -C 6 alkyl radical.

The Polysiloxanylrest is preferably derived from Porydrniethylsüoxanen and may be straight-chain or branched.

The saccharide residue is e.g. to a Glucoxyϊrest.

In the process according to the invention, preference is given to using compounds of the general formula (II) where R ^{1 represents} a C ¹ -C ₆ -alkylene radical, particularly preferably a methylene, ethylene, n-propylene, n-butylene or n-hexamethylene radical ,

If in the process according to the invention compounds of the general formula (III) are used in which R ^{2 is} a fluoresceinyl radical or a pyrene, fluorescein, coumarin or 4,4'-bis-styrylbiphenyl bonded via a C 1 -C ₃₀ -alkylene group, Pyrazolm, hydroquinone,

Benzoxazole, benzisoxazole, benzimidazole or flavonic acid radical, so the aforementioned radicals R ^{2 may} also be mono- or polysubstituted. Exemplary here are the

Called substitution pattern, the m of WO-A-2005/108961 are described, in particular those substitution patterns are preferred, in addition to the amino functionality of the general

Formula (IV) contain no further, reactive with phosgene groups. Suitably, compounds of general formula (III) are used in which R ² is C _r C ₃₀ alkyl, C _r C ₆ alkyloxy-C, -C ₃ O-alkyl, C iC ₆ alkylcarbonyloxy-C iC ₃₀ - alkyl , Di (C ₁ -C ₆ -alkyl) aminoC 1 -C ₃ 0-alkyl, di (C 7 -C 5 aralkyl) aminoC 1 -C ₃₀ -alkyl, di (allyl) arninoCrC ₃₀ -alkyl, ammonium ci C ₃₀ -alkyl _s polyoxyalkylene-C ₁ -C ₃₀ -alkyl, polysiloxanyl-C ₁ -C ₃₀ -alkyl, (meth) acryloyloxy-C ₁ -C ₃₀ -alkyl, 3-imidazolio-C ₁ -C ₃₀ -

Alkyl or [C ₂ -C ₆ -alkylene-O] _x - [C ₂ -C ₆ -alkylene-O] _y -C ₁ -C ₆ -alkyl, where x = 0-50 and y = 0-40, but either x or y is at least 1 and the two alkyl radicals are different if both x and y are not equal to zero.

Particularly suitable compounds of the general formula (HO, in which

R ^{2 is} Ci-Ci _S alkyl,

C JC ₆ - alkylcarbonyloxy-Q -C ₁₈ - -alkyl, di (C -C ₆ _alkyl!) Aτmno-C; -C _g alkyl, di (C ₇ -C _u -ar alkyl) amino-C ^ C ₁₈ alkyl, di (allyl) amino-Ci-C ₈ alkyl, Ammomo-Ci -C ₁₈ alkyl, polyoxyalkylene Ci-C _lg -alkyl, polysiloxanyl-Ci -C j _g -alkyl, (meth) acryloyloxy-C i -Ci ₈ alkyl, 3 -imidazolio-C i -C ₃₀ -alkyl or [C ₂ -C ₆ - Alkylene-O] _x - [C ₂ -C ₆ -alkylene-O] _y -C _I -C ₆ alkyl, where the two

Alkylene radicals are different and x = 1-50 and y = 1-40, is.

Also suitable are compounds of the general formula (III) in which R ^{2 is} - [C ₂ -C ₆ -alkylene-O] _x - [C ₂ -C ₆ -alkylene-O] _y -C ₁ -C ₅ -alkyl wherein the two alkylene radicals are different and x = 2-40 and y = 2-20.

Furthermore, compounds of general formula (III) can be used in which

- (CH ₂ ) _π -CH ((CH ₂ ) _m -CH ₃ ) - (CH ₂ ) ₀ -CH ₃ , where n + m + o give a maximum of 27, - (CH ₂ X ₁ - (CF ₂ ) _P -CF ₃ ,

- (CH ₂ V [O-Si (-O-Si (CH ₃ ) ₃ ) 3],

- (CH ₂ ) _π - (O-CH ₂ -CH ₂ ) _q -OR ⁴ -H,

-R «-OR ⁷ ,

-R ⁴ -NR ⁵ ₂ ,

.

-R ⁴ -OC (= O) -CR ⁶ = CH ₂ ,

R ⁴ -PO ₃ R ⁷ ₂ , -R ⁴ -OPO ₃ R ⁷ ₂ or a Sacchaπdrest, wherein

R ⁴ is Ci-C _β- alkylene, R ^{5 is} hydrogen, C ₁ -C ₁₃ alkyl, C ₂ -C ₁₈ alkenyl, preferably AHyI, or benzyl,

R ^{6 is} hydrogen or methyl, R ^{7 is} C _r C ₆ -alkyl and Y is one equivalent of an anion, preferably chloride, bromide,

Sulfate, hydrogen sulfate, methosulfate or nitrate, n, m, o are independently an integer from 0 to 17, p is an integer from 1 to 12 and q is an integer from 1 to 100, preferably 2 to 50

The amines of the general formula (IV) which can be used for the preparation of the compounds of the general formula (III) are either available commercially or can be prepared by methods familiar to the person skilled in the art.

Suitable amines of the general formula (IV) are, for example:

Polyether monoamine, n-octylamine, tert-octylamine, n-hexylamine, dihexylamine, dodecylamine, octadecylamine, methyloctadecylamine, diocrylamine, N, N-dimethylpropylenediamine, N ₅ N-dimethylethylenediamine, 3-aminopropylmethylammonium iodide, 3-aminopropylmethylammonium bromide, 3 Aminopropyltrimethylammonium bromide, 3-arnomethyltimethylammonium iodide ₃ 3-ammoethyltimetylammonium bromide, 3-aminomethylmethylammonium chloride, 3

3-aminopropyldimethyloctylammomum bromide, 3-aminopropyldimethyloctylammomum bromide, 3- (trimethylsilyl) -propylamm, 3- (tris (t-methylsilyloxy) silyl) -propylarmn, 3- (triethylsilyl) -ethyl-amm, 3- (tπs (t-methylsilyloxy) silyl) -ethyl-amine, 3- Aminopropylimidazole, 2-ammoethylimidazole, 4-ammobutyhmidazole, 3-aminopropyl-1-methylimidazolium methylsulfate, 3-ammopropyl-1-butylimidazolium methylsulfate, 3-aminoethyl-1-methyl-imidiazolium methylsulfate, 3-aminoethyl

1-butylimidiazoliummethyl sulfate, 3-aminopropyl-1-methylimidazolium chloride, 3-aminopropyl-1-butylimidazolium chloride, 3-aminopropyl-1-methylimidazolium bromide, 3-aminopropyl-1-butyl-imidiazohumbromide, 3-aminoethyl-1-methylimidazolium chloride, 3-aminomethyl - 1-butyl-imidiazolmmchloπd, 3-ammoethyl-l-methylimidiazoliumbromid and 3-aminoethyl-1-butyl imidiazolmmbromid.

Polyetheramines of formula (IV) may be in the form of commercial products of the Huntsman Corporation, e.g. Jeffamm M-600, Jeffamm M-1000, Jeffamm M-2005 and Jeffarmn M-2070.

Based on 1 equivalent of the compound of the general formula (II) used in the process according to the invention, 0.5-1 equivalents of the isocyanate of the general formula (JYi) used. Preferably, 0.6-1 equivalents and more preferably 0.8-1 equivalents of the isocyanate of the general formula (IH) are used relative to 1 equivalent of the compound of the general formula (II).

The inventive method is usually at a temperature in the range of ^{0 0} C to

220 ° C performed. Preference is given to working at a temperature in the range of 10 ⁰ C to 200 ⁰ C and particularly preferably from 2O ⁰ C to 150 ⁰ C.

The erfmdungsgemäße method can be carried out so that the isocyanate of the general formula (III), optionally dissolved in an inert solvent, and then the compound of general formula (II), optionally also dissolved in the same or in a different inert solvent to which isocyanate is added.

In an alternative embodiment, the compound of the general formula (II) is initially charged and then the isocyanate of the general formula (III) is added, where both substances may optionally be diluted with the same or different inert solvent.

The method according to the invention can also be operated continuously. In this case, the addition of the isocyanate of the general formula (III) takes place simultaneously with the addition of the compound of the general formula (II) in a suitable apparatus.

It should be expressly mentioned that both of the aforementioned embodiments can also be carried out in the absence of solvents.

Suitable solvents are, for example, toluene, xylene, chlorobenzene, 1, 2-dichlorobenzene,

Tetrahydrofuran, diethyl ether, dioxane, methyltetrahydrofuran, cyclopentylmethyl ether, dibutyl ether, 1,2-dichloroethane, dichloromethane, chloroform, dimethoxyethane, acetonitrile, cyclohexane, methylcyclohexane, cyclopentane, heptane, hexane, diethylene glycol dimethyl ether, ethylbenzene and methyl tert-butyl ether.

The isolation of the compounds of the general formula (I) can be carried out by distillation, crystallization, chromatography or freeze-drying.

The compounds of the general formula (I) obtained by the process according to the invention can be reacted with functional groups, e.g. Hydroxy groups or primary or secondary

Implement amino groups contained in biomolecules, polymers or substrate surfaces.

This leads to the opening of the cyclic carbonate ring with covalent attachment to the Biomolecule, the polymer or the substrate surface. In this way it is possible to introduce the above-defined plurality of radicals R ² and R ³ into biomolecules or polymers or to bind them to substrate surfaces.

The term "biomolecule" is intended to encompass all molecules which can be isolated from biological systems and / or which can interact with biological systems or parts thereof, in particular peptides, proteins, proteoglycans, enzymes, markers, antibodies, receptor molecules, Antigens and drugs Specific examples are heparin, tissue plasminogen activator, streptokinase and prostaglandins.

As polymers, for example, polyamines or polyols can be used. Examples of polyamines are polyvinylamine, polyallylamine, polyethyleneimines, chitosan, polyamide-epichlorohydrin resins (available as "Hercosett®" products), polyaminostyrene, peptides or proteins such as gelatin.

As surfaces that can be treated by this method, for example, the surfaces of materials are suitable which have amino and / or hydroxyl groups, or surfaces which have been treated by amino acid methods known per se.

EXAMPLES

Example 1 (Isocyanate-Her position)

In a 1-liter reactor with stirrer, condenser (0 ⁰ C) dropping funnel and Gaseinleitrohr 300 g of chlorobenzene were submitted and cooled to -10 ⁰ C. 47.5 g of phosgene were condensed into the cooled solvent. In 36 minutes, a solution of 200 g of Jeffamine M-1000 in 200 g of chlorobenzene was added to this mixture so that the temperature of +3 ⁰ C was not exceeded. After completion of the addition, the mixture was continuously heated to 126 ⁰ C within 2 hours , At the temperature of 20 ⁰ C, a phosgene stream of 40 g / h was started. After reaching the temperature of 126 ° C was stirred for one hour at this temperature with phosgene. In total, 106 g of phosgene were added. To remove the phosgene excess, the cooler was then heated to a temperature of

20 ⁰ C operated and passed a nitrogen flow of 25 l / h through the reaction mixture. The mixture was then cooled to 80 ^° C. and the chlorobenzene was distilled off under reduced pressure (20 mbar) until more distillate could be collected. 202.4 g of isocyanate (99% of theory) were obtained.

Example 2 (according to the invention)

In a 0.5 liter reactor with dehydrator, condenser (9 ° C) and dropping funnel were 12.28 g

Glycerol (90%) 75 g m submitted chlorobenzene via the dropping funnel 98.95 g of the isocyanate from Example 1 dissolved in 75 ml of chlorobenzene at 20 ⁰ C are added dropwise. The mixture was then heated to boiling (134 ° C). The conversion was monitored by IR spectroscopy. After a reaction time of 4 hours, no NCO band was detectable by IR spectroscopy. The mixture was heated to 130 ⁰ C and all volatile

Components removed at reduced pressure (2 mbar). There were obtained 107.15 g (97.5% of theory) of the desired isocyanate

Claims

claims:

1. Process for the preparation of compounds of general formula (I),

embedded image in which

R ^{1 is} C ¹ -C ₁₂ -alkylene,

R ² is C ₁ -C ₃₀ -alkyl, C ₂ -C ₃₀ alkenyl, Q-Qo-haloalkyl, _Ci-C6 alkyloxy-C ₃₀ - alkyl, _Ci-C6 alkylcarbonyloxy-Ci -C ₃₀ alkyl, di (Ci-Cig-alkyl) amino-Ci-C ₃₀ alkyl, di (C ₇ -Cii-aralkyl) _ammo-C] -C ₃ O-alkyl, di (allyl) amino-Ci-C ₃₀ alkyl, ammomo-C _r C ₃₀ -alkyl, polyoxyalkylene-Q-Qo-alkyl, polysiloxanyl-C 1 -C 6 -alkyl, (meth) acrylyloxy-C, C ₃₀ -alkyl, di (C _r C ₆ - alkyl) phosphono-C _o-3 alkyl, di (Ci -C ₆ alkyl) - phosphonato-Ci-Cjo-alkyl, 3-Imidazoho-C ₃₀ alkyl or - [C ₂ -C ₆ alkylene -O] _x - [C ₂ -C ₆ -alkylene-O] _y -R, wherein R is C ₁ -C ₆ -alkyl, x = 0-50 and y = 0-50, either x or y at least Is 1 and the two alkylene radicals are different, when x and y are both not 0, or a Sacchaπdrest is, or

R ^{2 represents} a fluoresceinyl radical or a pyrene, fluorescem, coumarin, 4,4'-bis-styrylbiphenyl, pyrazoline, hydroquinone, benzoxazole, benzisoxazole, benzimidazole bonded via a C 1 -C ₃₀ -alkylene group. or flavonic acid radical. by reacting compounds of the general formula (II)

where R ^{1 has} the meaning given for the general formula (I), with an isocyanate of the general formula (III) OCN - R ² (III) where R ^{2 has} the meaning described for the general formula (I).

2. The method of claim 1, wherein the isocyanates of the general formula (III) smd obtainable by reacting the nurse of the general formula (IV) H ₂ N - R ² (IV) embedded image in which the R ² for the general formula (I) beschπebene meaning has, with phosgene.

3. The method of claim 1 or 2, wherein compounds of general formula (II) are used, wherein R ^{1 is} a Ci-Q-alkylene radical, more preferably a methylene, ethylene, n-propylene, n-butylene or represents n-hexamethylene radical.

4. The method according to one or more of claims 1 to 3, wherein compounds of the general formula (III) are used, in which

R ² C ₁ -C ₃₀ -EIlCyI, CRCG alkylcarbonyloxy-C q O- alkyl for d-Cso-alkyl, C ₁ -C ₆ -AHCyIoXy-C, di (C _r C ₆ alkyl) amino-Ci-C ₃ o-alkyl, di (C ₇ -Ci

Di (allyl) amino-Ci-C ₃ o-alkyl, C-Arnmonio -C ₃₀ alkyl, polyoxyalkylene Ci-C ₃₀ alkyl,

Polysiloxanyl-C ₁ -C ₃₀ alkyl, (meth) _{acryloyloxy-Ci-C3} O-alkyl, 3 -ImMaZoIiO-C ₁ -C ₃₀ - alkyl or [C ₂ -C ₆ alkylene-O] _x - [C C ₂ -C ₆ -alkylene-O] _y -Cj-C ₆ -alkyl, wherein x = 0-50 and y = 0-40, but either x or y is at least 1 and the two alkylene radicals are different when x and y are both 0, stands.

5. The method according to one or more of claims 1 to 4, wherein compounds of general formula (HI) are used, in which

R ^{2 is} C _r C, a-alkyl, C 1 -C 6 alkyloxy-d-C 1 -C 4 -alkyl, C 1 -C 5 -alkylcarbonyloxy-d-C 1 -C 4 -alkyl,

Di (allyl) amino-Ci-Cj ₈ -alkyl, Ammomo-Ci-Cig-alkyl, polyoxyalkylene-Ci-Cig-alkyl,

Poly siloxanyl-C _; _Ci8 alkyl, (meth) acryloyloxy-C _r C ₁₈ -alkyl, 3-Q -Imidazolio -C ₃₀ - alkyl or [C ₂ -C ₆ alkylene-O] _x - [C ₂ -C ₆ alkylene -O] _y -Ci-C ₆ alkyl, wherein the two alkylene radicals are different and x = 1-50 and y = 1-40, is.

6. The method according to one or more of claims 1 to 5, wherein compounds of the general formula (III) are used, in which

R ^{2 is} - [C ₂ -C ₆ -alkylene-O] _x - [C ₂ -C ₆ -alkylene-O] _y -C _r C ₆ -alkyl, where the two alkylene radicals are different and x = 2-40 and y = 2-20.

7. The method according to one or more of claims 1 to 3, wherein compounds of general formula (III) are used, in which R ^{2 is} - (CH ₂ ) _n -CH ₃ ,

- (CH ₂ VCH ((CH ₂ ) _ra -CH ₃ ) - (CH ₂ ) ₀ -CH ₃ , where n + m + o give a maximum of 27, - (CH ₂ ) "- (CF ₂ ) _p -CF ₃ , - (CH ₂ ) _π - [O-Si (-O-Si (CH ₃ ) ₃ ) 3],

- (CH ₂ ) _n - (O-CH ₂ -CH ₂ ) _q -OR ⁴ -H, -R ⁴ -OR ⁷ , -R ⁴ -NR ⁵ ₂ ,

-R ⁴ -O-C (O) -CR ⁶ = CH ₂ , -R ⁴ -PO ₃ R ⁷ ₂ , -R ⁴ -OPO ₃ R ⁷ ₂ or a saccharide radical wherein

R ⁴ is d-Ce-alkylene,

R ^{5 is} hydrogen, C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, preferably allyl or benzyl,

R ^{6 is} hydrogen or methyl,

R ^{7 is} C ₁ -C ₆ -alkyl and

Y is one equivalent of an anion, preferably chloπd, bromide,

Sulfate, hydrogen sulfate, methosulfate or nitrate, n, m, o are independently an integer from 0 to 17, p is an integer from 1 to 12 and q is an integer from 1 to 100, preferably 2 to 50 ,

8. The method according to claim 2, being used for the preparation of the compounds of general formula (III) as the amine of general formula (IV): polyether monoamine, n-octyl, tert-octyl, n-hexyl, dihexyl, dodecyl, octadecyl, Methyl octadecylamine, dioctylamine, N, N-dimethylpropylene diamine, N, N-dimethylethylene diamine, 3-aminopropylmethylammonium iodide, 3-aminopropylmethylammonium bromide, 3-aminopropylmethylammonium chloride, 3-aminoethylmethylammomium iodide, 3-aminomethylmethylammonium bromide, 3-aminoethyl-methylammonium bromide, 3

Ammopropyldimethyloctylammonium chloride, 3-aminopropyldimethyloctylammonium bromide, 3- (t -methylsilyl) -propylamm, 3- (tπs (t-methylsilyloxy) silyl) -propylarmn, 3- (t -methylsilyl) -ethylamm, 3- (tpt (trimethylsilyloxy) silyl) -ethylamm, 3- Ammopropylimidazole, 2-ammoethylimidazole, 4-ammobutylimidazole, 3-ammopropyl-1-methylimidazole-methylsulfate, 3-aminopropyl-1-butylimidiazolemethylsulfate, 3-ammoethyl

1-methyl-imidiazohumethylsulfate, 3-ammoethyl-1-butylimidazoylthio sulfate, 3-ammopropyl-1-methyhmidiazohumchloride, 3-aminopropyl-1-butylimidiazolium chloride, 3-ammopropyl-1-methylimidazolium bromide, 3-aminopropyl-1-butylimidiazolium bromide, 3 Ammoethyl-1-methyhmidiazolium chloride, 3-ammoethyl-1-butyhmidiazolium chloride, 3-ammoethyl-1-methylimidiazohumbromide and 3-aminomethyl-1-butylimidiazohumbromide.

9. The method according to one or more of claims 1 to 8, wherein based on 1 equivalent of the compound of general formula (II) used 0.5-1 equivalents of the isocyanate of the general formula (III) are used, preferably 0.6-1 Equivalents, more preferably 0.8-1 equivalents.

10. The method according to one or more of claims 1 to 8, wherein operating at a temperature in the range of 0 ° C to 220 ⁰ C, preferably at a temperature in the range of 10 ⁰ C to 200 ⁰ C and particularly preferably in the range of 20 ⁰ C to 150 ° C.