DE10044164A1 - Vinyl amine compounds - Google Patents

Abstract

The invention relates to the production of compounds containing one or several groups of general formula (I) -CH2-CH(NR<1>R<2>)- with R<1> = R<2>, or independently = H, C1-20 alkyl, C6-18 aryl, C7-20 alkaryl, C7-20 aralkyl or a polyamino group, by reductive amination of compounds, containing one or several groups of general formula (II), -CH2-CH(O-C(O)-R<3>)- with R<3> = H, C1-20 alkyl, C6-18 aryl, C7-20 alkaryl, or C7-20 aralkyl with amines of general formula (III), HNR<1>R<2> and hydrogen.

Description

The present invention relates to compounds, in particular copolymers, which Basic vinylamine building blocks included. The invention further relates to a method for the preparation of such compounds or copolymers, their use as Excipients in mineral oils, mineral oil distillates, fuels and other areas containing concentrates and fuel and Fuel compositions.

Vinylamine polymers can only react indirectly via polymer analog reactions can be obtained since the base monomer, the vinylamine, cannot be isolated. Vinylamine polymers are, for example, by hydrolysis of poly-N- vinyl amides such as poly-N-vinylformamide, poly-N-vinyl acetamide, poly-N- vinylimides such as poly-N-vinyl succinimide or poly-N-vinylphthalimide as well due to Hofmann degradation of polyacrylamide when exposed to basic Hypochlorite produced. These synthetic routes start from difficult to obtain or expensive monomers and have complicated implementation or Processing steps. So far they are only in a few Special applications, such as flocculants and retention aids.

Mineral or petroleum distillates, especially middle distillates, such as gas oils, diesel oils or heating oils obtained by distillation and the further processing stages of the Refineries obtained from petroleum show depending on the origin of the crude oil different proportions of n-paraffins, which crystallize on cooling can. This point is called the cloud point or cloud point (CP). Upon further cooling, the flaky paraffin crystals form a kind  House of cards structure, so that a middle distillate (MD) stalls, although the most of it is still liquid. This point is called pour point or Pour point or pour point. Due to the unusual paraffins in the Temperature range between turbidity and pour point is the flowability, especially affected by fuels. The paraffins clog Filters and cause an uneven or total in fuels interrupted fuel supply to the engine. Similar disturbances occur Heating oils on.

It is known that the addition of suitable petroleum distillate Crystal growth of paraffins in middle distillates and kerosene middle distillate Mixtures can be modified. Well-effective additives prevent Paraffins in middle distillates form structures similar to those of a map house and the middle distillates at temperatures of a few ° C below The temperature at which the first crystals precipitate has already set. they seem thus as a flow improver. The improvement of the flow properties of Middle distillates are often used to lower cold filter plugging Point (CFPP) ", for example according to DIN EN 116. On the other hand these additives result in the formation of fine, well-crystallized, more separate ones Paraffin crystals that do not settle and that pass through the filters can, so that trouble-free fuel transport is ensured. Here they act as wax anti-settling additives (WASA).

As flow improvers for petroleum middle distillates, copolymers are often used by Ethylene and vinyl acetate are described, see for example DE-A-196 24 861. The copolymers described also contain (meth) acrylate Basic building blocks that are derived from, optionally alkoxylated, amino alcohols derived.

EP-A-0 964 052 relates to the use of nitrogen-containing ethylene copoly mers for the production of fuel oils with improved lubrication. The In addition to structural units derived from ethylene, copolymers contain also those structural units that differ from ethylenically unsaturated Derive compounds that are at least one aromatic or aliphatic have bound nitrogen atom. As such comonomers  Alkylamino (meth) acrylates, alkyl (meth) acrylamides, vinylamides, aminoalkyl vinyl ethers, allylamines and a vinyl group-bearing heterocycle. In particular, terpolymers are used which differ from ethylene, vinyl acetate and 1-vinyl-2-pyrrolidone, N-vinyl-N-methylacetamide or dimethylaminoethyl Derive methacrylate.

Some of the nitrogenous vinyl comonomers have one complicated structure and are usually not easy and out inexpensive raw materials can be represented.

EP-A-0 405 270 relates to a process for improving the flowability of Mineral oils and mineral oil distillates by adding a mixture of one Ethylene-vinyl acetate copolymer and an ethylene-vinyl acetate-N- Vinylpyrrolidone terpolymer.

WO 96/18706 relates to low fuel and fuel compositions Sulfur content, its flowability through the addition of nitrogenous Connections is increased. In particular, amine salts or amides used by the implementation of hydrocarbon-substituted amines can be obtained with alkanoic acids.

The object of the present invention is to provide a method for Manufacture of compounds containing structural elements derived from vinylamine included, the introduction of the amine group is inexpensive and inexpensive should be feasible.

In addition, copolymers are to be provided which are used as auxiliary substances in mineral oil, Mineral oil distillates, fuels and fuels a number of advantageous Have properties.

The object is achieved according to the invention by a process for the preparation of compounds which contain one or more groups of the general formula (I)

-CH ₂ -CH (NR ¹ R ² ) - (I)

with R ¹ , R ² independently of one another hydrogen, C _1-20 alkyl, C _6-18 aryl, C _7-20 alkaryl, C _7-20 aralkyl or polyamine radical
by reductive amination of compounds which contain one or more groups of the general formula (II),

-CH ₂ -CH (OC (O) -R ³ ) - (II)

with R ^{3 is} hydrogen, C _1-20 alkyl, C _6-18 aryl, C _7-20 alkaryl, C _7-20 aralkyl with amines of the general formula (III)

HNR ¹ R ² (III)

and hydrogen.

It has been found according to the invention that derived from vinyl esters Structural elements in chemical compounds, for example polymers reductive amination with amines and hydrogen in vinylamine-derived Structures can be transferred.

The compounds containing structures of the general formula (I) or (II) can be low molecular weight, oligomeric or polymeric structures. You can corresponding to 1, 2, 3, 4, 5, 6 or more of the structures of the formulas (I) or (II) exhibit. Preferably, the connections to the structures of the Formula (I) a total of 4 to 100,000 carbon atoms, particularly preferably 10 to 10,000 carbon atoms, in particular 10 to 1000 carbon atoms, if it is low molecular weight or oligomeric compounds.

The compounds are particularly preferably polymers which Basic vinylamine building blocks of the general formula (I) in the main chain contain. The polymers contain 1 or 2, 3, 4, 5, 6 or more of the Basic building blocks of the general formula (I).  

You can completely from basic building blocks of the general formula (I) be constructed. In this case they are homopolymers. Often acts are copolymers which, in addition to the structures of the general formula (I) have unreacted structures of the general formula (II). Further there may be other basic building blocks as described below.

Preferably the compounds are polymers which are one or more Basic vinylamine building blocks of the general formula (I) in the main chain contained and contained by reductive amination of polymers that one or more basic vinyl ester units of the general formula (II) in the Main chain included.

The polymers to be aminated are particularly preferably copolymers which contain C ₂ -C ₁₂ -olefin basic units and vinyl esters of C _1-12 monocarboxylic acids as basic units.

In particular, the copolymers to be aminated are ethylene-vinyl acetate Copolymers.

In the groups of the general formula (I) or in the amines of the general formula (III), R ¹ and R ^{2 are,} independently of one another, preferably hydrogen or C _1-12 alkyl, particularly preferably hydrogen or C _1-4 alkyl, in particular Hydrogen. Ammonia is particularly preferably used as the compound of the general formula (III).

In the structures of general formula (II), R ^{3 is} preferably hydrogen or C _1-12 alkyl, particularly preferably C _1-4 alkyl, especially methyl. These are, in particular, vinyl acetate building blocks.

Particularly preferred compounds that have the structures of general Formula (I) and (II) are polymers with a molecular weight (Number average) from 100 to 10,000,000, particularly preferably 500 to 100,000.

The reductive amination according to the invention can be carried out analogously to known processes for reductive amination of z. B. aldehydes, ketones or esters and  Alcohols are carried out. It is preferably made using more suitable ones Catalysts carried out. Suitable catalysts are known and described, for example, in the older, not prepublished DE-A-199 10 960.

Examples of catalysts which are customary for reductive amination are those based on Ni, Co, Cu, Fe, Pd, Pt, Ru, Rh, Al, Si, Ti, Zr, Nb, Mg, Zn or their combination. Typical reaction conditions are temperatures of 50 up to 300 ° C and pressures up to about 600 bar.

A preferred catalyst contains as a catalytically active mass before the reduction with hydrogen
20 to 85% by weight, preferably 22 to 65% by weight, particularly preferably 25 to 49.7% by weight of oxygen-containing compounds of zirconium, calculated as ZrO ₂ ,
1 to 30% by weight, preferably 5 to 25% by weight, particularly preferably 10 to 25% by weight of oxygen-containing compounds of copper, calculated as CuO,
14 to 70% by weight, preferably 29.7 to 70% by weight, particularly preferably 40 to 60% by weight of oxygen-containing compounds of nickel, calculated as NiO,
0 to 5% by weight, preferably 0.3 to 3.5% by weight of oxygen-containing compounds of molybdenum, calculated as MoO ₃ , and
0 to 10% by weight, particularly preferably 0 to 5% by weight, of oxygen-containing compounds of aluminum, calculated as Al ₂ O ₃ ,
the total amount of which is 100% by weight.

A particularly preferred catalyst has the composition 51% by weight NiO, 17% by weight CuO, 30.5% by weight ZrO ₂ and 1.5% by weight MoO ₃ .

The catalyst is preferably only composed of catalytically active material and optionally a deformation aid such as graphite or stearic acid  built up. The catalyst can be in any suitable form, for example used as tablets, balls, rings, extrudates.

The catalytically active composition may optionally also have one or more Elements or their inorganic or organic compounds selected from Groups IA to IVA and IB to VIIB and VIII of the Periodic Table of the Contain elements.

Catalysts are particularly preferred after the last heat treatment and less than 20% by weight, preferably before the reduction with hydrogen less than 10% by weight, in particular less than 5% by weight, very particularly contain less than 1% by weight of cobalt, calculated as CoO. Most notably the catalytically active composition preferably contains no catalytically active amounts of cobalt or its compounds.

The catalysts can be produced by different processes, for example by peptizing powdery mixtures of the hydroxides, carbonates, Oxides and / or other salts of the components with water and the following Extruding and tempering the mass thus obtained. Generally become Production of the catalysts, however, known precipitation methods applied. The individual components can be used individually or together as Mixed precipitation can be precipitated.

The precipitation products are generally at 80 to 200 ° C, preferably at Dried 100 to 150 ° C and then at 300 to 800 ° C, preferably 400 to Calcined 600 ° C, especially 450 to 500 ° C.

The amines of the general formula (III) can be used in stoichiometric amounts, based on the ester groups to be used. Is preferred however, worked with an excess of the amines, for example with one more than 5 molar excess. Ammonia in particular is generally used 5 to 250 times, preferably 10 to 100 times, in particular 25 to 80 times times molar excess.  

The process according to the invention can be carried out batchwise or continuously carry out, the catalyst preferably arranged as a fixed bed in the reactor is. The reaction can be in the liquid phase or in the gas phase be performed.

The reaction is usually carried out at temperatures from 50 to 300 ° C, preferably 80 to 250 ° C, particularly preferably 80 to 230 ° C, in particular 100 to 220 ° C.

In general, the reaction is carried out at a pressure of 1 to 400 bar, preferably 10 to 250 bar, in particular 20 to 200 bar.

The amount of hydrogen in the reaction is generally from 5 to 400 Nl, preferably 50 to 250 Nl per mole of ester component to be reacted fed.

The reaction can be carried out without an additional solvent. In the Implementation of high molecular weight, highly viscous or more solid at room temperature Starting compounds or products will be beneficial in one below Reaction conditions inert solvents worked, for example in Tetrahydrofuran, dioxane, N-methylpyrrolidone, mihagol, ethylene glycol dimethyl ether or cyclohexane and hexane or generally aliphatic or aromatic solvents.

The invention also relates to the copolymers produced by the process according to the invention, particularly preferably a copolymer containing polymerized vinylamine basic units of the general formula (I)

-CH ₂ -CH (NR ¹ R ² ) - (I)

with R ¹ , R ² independently of one another hydrogen, C _1-20 alkyl, C _6-18 aryl, C _7-20 alkaryl, C _7-20 aralkyl or polyamine radical,
and, optionally different, polymerized vinyl comonomer basic units of the general formula (IV)

-CH ₂ -CR ⁴ R ⁵ - (IV)

with R ⁴ hydrogen, C _1-4 alkyl,
R ⁵ , R ⁶ ,
-OC (O) -R ⁶ ,
-OR ⁶ ,
-C (O) -R ⁶ ,
-C (O) -OR ⁶ ,
CN,
-Halogen,
- (O-CH ₂ -CHR ⁷ ) _n -OR ⁶ with R ⁷ hydrogen, C _1-4 alkyl and
n average value from 1 to 100,
-C (O) -NHR ⁶
with R ^{6 is} hydrogen, C _1-20 alkyl, C _6-18 aryl, C _7-20 alkaryl, C _7-20 aralkyl, which may optionally be substituted by
-OR ⁸ ,
-NR ⁸ R ⁹ ,
with R ⁸ , R ⁹ independently of one another hydrogen or C _1-4 alkyl.

R ¹ and R ^{2 have} the preferred meaning given above. In the structure -OC (O) -R ⁶ , R ^{6 has} the preferred meaning given above for R ³ .

In the basic building blocks of the general formula (IV), R ^{4 is} preferably hydrogen or methyl, in particular methyl. R ⁵ preferably has the meaning R ⁶ or -OC (O) -R ⁶ . If the radical R ^{5 is} the radical R ⁶ , then R ⁶ preferably has the meaning hydrogen, C _1-12 alkyl, phenyl or C _7-10 alkaryl, R ⁶ is particularly preferably hydrogen, methyl, ethyl or phenyl.

In addition to the polymerized vinylamine basic units of the general formula (I), the copolymer particularly preferably contains basic units of the general formula (IVa)

-CH ₂ -CR ⁴ (-OC (O) -R ⁶ ) - (IVa)

and / or the formula (IVb)

-CH ₂ -CHR ⁵ - (IVb)

with R ^{5 is} hydrogen, C _1-20 alkyl, C ₆ -C ₁₈ aryl.

In particular, the copolymers have both the basic building blocks of the general Formulas (I), (IVa) and (IVb).

Such copolymers can still contain up to 20% by weight, based on the Whole copolymer, containing other basic building blocks, are particularly preferred they essentially or only from the basic building blocks of the general formulas (I), (IVa) and (IVb) built up. It is particularly preferably ethylene Vinyl acetate Vinylamia terpolymers. The copolymers or terpolymers have preferably a molecular weight (number average) of 100 to 10,000,000, in particular preferably 500 to 100,000.

The copolymers according to the invention can be prepared by any suitable method. The copolymers are particularly preferably prepared by radical copolymerization of vinyl esters of the general formula (V)

H ₂ C = CH (OC (O) -R ³ ) (V)

with R ^{3 is} hydrogen, C _1-20 alkyl, C _6-18 aryl, C _7-20 alkaryl, C _7-20 aralkyl,
optionally different vinyl comonomers of the general formula (VI)

H ₂ C = CR ⁴ R ⁵ (VI)

with the meaning given for R ⁴ and R ⁵ and optionally further vinylic comonomers to form a copolymer and subsequent reductive amination by the above process.

The ethylene-vinyl acetate copolymers are produced, for example, by radical polymerization according to the high pressure mass process, optionally in stirred autoclaves, tubular reactors or segmented tubular reactors.

Such methods are, for example, in DE-A-197 54 039, DE-A-197 19 689 and M. Rätzsch, petroleum and coal-natural gas petrochemicals combined with fuel Chemie, 42 (4) 1989.

The copolymers according to the invention can be used in a large number of applications be used. Preferred is the use as auxiliary substances in mineral oils, Mineral oil distillates and fuels, in chromatography, as Ion exchangers, in dispersions, as emulsifiers, in paper production (Wochenbl. Papierfabr. 1999, 127, pages 511 to 518), in membranes, in Adhesives (WO 00/01783), in the production of cellulose fibers (WO 99/36604), in printing inks and papers therefor (EP-A-0 878 323, EP-A-0 911 374, WO 98/42787), for coating fibers (US 6,077,794), as a fixing agent (US 6,039,768), as mold release agent, for waste water treatment (WO 96/38493), in detergent compositions, especially as color transfer inhibitors (US 5,863,879), for decoloring paper mill waste water (US 5,476,594), for Modification of metal surfaces (US 5,494,535), in films (US 5,492,765), in coating compositions and in other fields of application.

Special applications are e.g. B. the following:

• 1. The copolymers are suitable for optimizing retention and drainage and for fixing anionic substances in paper manufacture (Retention, drainage, flocculant and fixative). additionally the polymers achieve an improvement in dry and Wet paper strength (see also Wochenbl. Papierfabr. (1999), 127 (8), 511-518).  
• 2. The copolymers are suitable for dye (substance) removal from waste water Papermaking (according to US 5,476,594).
• 3. The polymers are suitable in fully or partially protonated form as a water-soluble or water-swellable, cationic polyelectrolyte for aqueous adhesive dispersions for the production of multilayer paper or paper materials (according to DE 198 29 757).
• 4. The copolymers are suitable for modifying cleaned or chemically pretreated metal surfaces, which then in particular are suitable for electrocoating (according to EP 0 672 467).
• 5. The copolymers are suitable as a dye transfer inhibitor for Detergent (according to DE 44 13 720).
• 6. The copolymers are suitable as a starting material for the production of Polymers containing carbamate units. These polymers are suitable itself as a retention, drainage and flocculant as well as Fixing agent in the manufacture of paper, as a protective colloid for the Production of aqueous alkyldiketene dispersions and as Dispersant for the production of aqueous Filler slurries (according to WO 98/35999).
• 7. The copolymers are suitable for furnishing and producing Viscose products with cationic polymers (according to WO 99/36604).
• 8. The copolymers are suitable as water-soluble amine-based Polymer components in multi-layer membranes for separation acidic gases from gaseous mixtures (according to DE 196 00 954).
• 9. The copolymers are suitable for the production of aqueous and organic dispersions, emulsions or solutions of amine-based Polymers. The amine-based polymers, dispersions, emulsions or  Solutions are particularly suitable for coating and Hydrophobicization of surfaces (lacquered surfaces, ver packaging coating, impregnation of building materials, chipboard, stone, metal, Textiles, plastics, leather, wood, paper), for furnishing various Materials (stone, metal, textiles, plastics, leather, wood, paper), as Process chemical in the textile industry, as an additive in printing inks and Paints, as well as mold release agents.
• 10. The copolymers are suitable as an effective corrosion inhibitor in Kühlerschutzmittelabmischungen.

The copolymers are particularly preferred as flow improvers, wax-anti- Settling additive, lubricity improver, friction wear reducer, Corrosion inhibitor and / or engine intake system cleaner in Mineral oils, mineral oil distillates and fuels are used.

When used as flow improvers, the copolymers according to the invention preferably in fuel and fuel compositions, especially in Middle distillates such as diesel fuels and light heating oils are used. she can be used together with other common additives.

The copolymers according to the invention can contain mineral oils, Mineral oil distillates and fuels, especially one Middle distillate directly, but preferably as 20 to 70% by weight solutions be incorporated. Preferred solvents are Hydrocarbon solvent used. Suitable solvents are described for example in DE-A-196 24 861 and DE-A-43 41 528. The Copolymers according to the invention can be used in a large amount in one Hydrocarbon solvents are dissolved, preferably contain the Solutions 5 to 80 wt .-%, preferably 20 to 70 wt .-%, in particular 40 to 60% by weight of one or more copolymers according to the invention alone or together with other excipients, e.g. B. according to the above Applications. The invention also relates to such concentrates or Mixtures.  

The concentrates can be used, for example, to produce fuel and Fuel compositions continue to be used, see DE-A-196 24 861.

The invention also relates to fuel and fuel compositions that 5 to 5000 ppm by weight, preferably 10 to 500 ppm by weight of the copolymer on the total weight of the composition, alone or together with others Contain auxiliaries.

The invention is explained in more detail below by examples.

Examples Preparation of the amination catalyst

An aqueous solution of nickel nitrate, copper nitrate and zirconium acetate containing 4.48% NiO, 1.52% CuO and 2.82% ZrO ₂ was simultaneously in a stirred vessel in a constant stream with a 20% aqueous sodium carbonate solution at one temperature of 70 ° C so that the pH measured with a glass electrode was maintained at 7.0.

The suspension obtained was filtered and the filter cake was washed with deionized water until the electrical conductivity of the filtrate was about 20 mS. Then 1.5% MoO ₃ was stirred in as an aqueous solution of ammonium heptamolybdate. The filter cake was then dried at a temperature of 150 ° C. in a drying cabinet or in a spray dryer. The hydroxide / carbonate mixture obtained in this way was then heated at a temperature of 500 ° C. over a period of 4 hours.

The catalyst thus obtained had the following composition:
51% by weight NiO, 17% by weight CuO, 30.5% by weight ZrO ₂ and 1.5% by weight MoO ₃ .

The catalyst powder was mixed with 3% by weight of graphite and 6 × 3 mm Tablets deformed.

Preparation of an ethylene-vinyl acetate-vinylamine terpolymer

First, an ethylene-vinyl acetate copolymer was made which was composed of 70.3% by weight of ethylene and 29.7% by weight of vinyl acetate. The melt viscosity at 120 ° C was 65 mm ² / s. The preparation was carried out as described in DE-A-197 54 039.

75 g of this copolymer was mixed with 75 g of cyclohexane as a solvent and mixed with 850 g of liquid ammonia in an autoclave. Subsequently they were at a hydrogen pressure of 200 bar in the presence of 50 g of catalyst described above heated at 200 ° C for 16 h. Subsequently was cooled, relaxed, and the contents of the autoclave were removed. To Filtering off the catalyst and separating off the cyclohexane were 80 g of a receive liquid, colorless product.

The content of ethylene, vinyl acetate and vinylamine was determined by NMR spectroscopy. The terpolymer contained 75.6% by weight of ethylene, 14.7% by weight of vinyl acetate and 9.7% by weight of vinylamine polymerized. The kinematic melt viscosity, determined with a rotary viscometer at 120 ° C., was 70 mm ² / s.

test oils

The terpolymer according to the invention described above was used as an additive in different test oils used. The test oils had the following Characteristics.  

Table 1

The terpolymers according to the invention were introduced into the test oils, and the Cold filter plugging point (CFPP value) was determined in accordance with EN116. moreover the cloud point (CP) was determined according to ISO 3015. The CFPP is in the Table 2 below.

Table 2

lubricity

The lubricating effect of the ethylene-vinyl acetate-vinylamine described Terpolymers (II) was in test oil 5 according to DIN ISO 121546-1 (HFRR measurement) carried out. The results in Table 3 are wear scar diameters (WS 1.4)  specified. A low wear scar shows a good lubricating effect. in the Comparison to the ethylene-vinyl acetate-vinylamine terpolymer according to the invention (T) became a commercially available lubricity enhancer product Kerokorr® LA 99 (K) used.

Table 3

paraffin sedimentation

The influence of paraffin sedimentation (wax anti-settling) in test oil 3 was determined using an ARAL method, see Table 4. 500 ml of the diesel fuel were stored at -13 ° C for 16 hours. The ethylene-vinyl acetate copolymer (C) described and the vinyl acetate-vinylamine terpolymer (T) according to the invention were tested as additives. The quality of the influencing of paraffin sedimentation (wax anti-settling) is carried out by visual assessment:

• - Case (A): the sample is evenly cloudy, the paraffins are complete dispersed.
• - Case (B): the sample consists of two phases of different turbidity.
• - Case (C): the sample consists of two phases, the lower phase being cloudy and the upper phase is clear.

Efficacy as a wax antisettling additive have substances that in Attempt to lead to the results case (A) and case (B). In addition, the  lower 20% determined by the cloud point (CP) and the CFPP. A positive effect on the cold behavior of the test oils is when the cloud point of 20% - Soil phase a little (1-2 ° C) above the cloud point before the storage attempt is at -13 ° C.

Table 4

Table 4 shows that this is for the preparation of the ethylene-vinyl acetate-vinylamine Terpolymers used ethylene-vinyl acetate copolymer no influence on the Paraffin sedimentation causes. By adding the ethylene vinyl acetate Vinylamine terpolymers to ethylene vinyl acetate copolymer will be a positive Influenced paraffin sedimentation achieved.

Claims (12)

1. A process for the preparation of compounds which contain one or more groups of the general formula (I)
-CH ₂ -CH (NR ¹ R ² ) - (I)
with R ¹ , R ² independently of one another hydrogen, C _1-20 alkyl, C _6-18 aryl, C _7-20 alkaryl, C _7-20 aralkyl or poly amine radical
by reductive amination of compounds which contain one or more groups of the general formula (II),
-CH ₂ -CH (OC (O) -R ³ ) - (II)
with R ^{3 is} hydrogen, C _1-20 alkyl, C _6-18 aryl, C _7-20 alkaryl, C _7-20 aralkyl
with amines of the general formula (III)
HNR ¹ R ² (III)
and hydrogen. 2. The method according to claim 1, characterized in that the compounds Polymers are one or more basic building blocks of vinylamine general formula (I) contained in the main chain and by reductive Amination of polymers that contain one or more Vinyl ester basic building blocks of the general formula (II) in the main chain contain.   3. The method according to claim 2, characterized in that the polymers to be aminated are copolymers containing C _2-12 olefin basic building blocks and vinyl esters of C _1-12 monocarboxylic acids as basic building blocks. 4. The method according to claim 3, characterized in that the to be aminated Copolymers are ethylene-vinyl acetate copolymers. 5. Copolymer containing polymerized vinylamine basic building blocks of the general formula (I)
-CH ₂ -CH (NR ¹ R ² ) - (I)
with R ¹ , R ² independently of one another hydrogen, C _1-20 alkyl, C _6-18 aryl, C _7-20 alkaryl, C _7-20 aralkyl or polyamine radical,
and, optionally different, polymerized vinyl comonomer basic units of the general formula (IV)
-CH ₂ -CR ⁴ R ⁵ - (IV)
with R ⁴ hydrogen, C _1-4 alkyl,
R ⁵ , R ⁶
-OC (O) -R ⁶ ,
-OR ⁶ ,
-C (O) -R ⁶ ,
-C (O) -OR ⁶ ,
CN,
-Halogen,
- (O-CH ₂ -CHR ⁷ ) _n -OR ⁶ with R ⁷ hydrogen, C _1-4 alkyl and
n average value from 1 to 100,
-C (O) -NHR ⁶
with R ⁶ hydrogen, C _1-20 alkyl, C _6-18 aryl, C _7-20 alkaryl, C _7-20 aralkyl, which may optionally be substituted by
-OR ⁸ ,
-NR ⁸ R ⁹ ,
with R ⁸ , R ⁹ independently of one another hydrogen or C _1-4 alkyl. 6. Copolymer according to claim 5, characterized in that in addition to the polymerized vinylamine basic units of the general formula (I) basic units of the general formula (IVa)
-CH ₂ -CR ⁴ (-OC (O) -R ⁶ ) - (IVa)
and / or the formula (IVb)
-CH ₂ -CHR ⁵ - (IVb)
with R ^{5 is} hydrogen, C _1-20 alkyl, C _6-18 aryl
contains. 7. A process for the preparation of the copolymers according to claim 5 or 6 by radical copolymerization of vinyl esters of the general formula (V)
H ₂ C = CH (OC (O) -R ³ ) (V)
with R ^{3 is} hydrogen, C _1-20 alkyl, C _6-18 aryl, C _7-20 alkaryl, C _7-20 aralkyl,
optionally different vinyl comonomers of the general formula (VI)
H ₂ C = CR ⁴ R ⁵ (VI)
with the meaning given for R ⁴ and R ⁵
and optionally further vinylic comonomers to a copolymer and subsequent reductive amination by the process according to claim 1. 8. Use of copolymers according to claim 5 or 6 as auxiliaries in Mineral oils, mineral oil distillates and fuels in which Chromatography, as an ion exchanger, in dispersions, as an emulsifier, at papermaking, in inks, membranes, adhesives, detergents, Mold release agents, in wastewater treatment, for coating and Hydrophobicization of surfaces, for equipping materials, as Process chemical in the textile industry, as an additive in printing inks and Paints. 9. Use according to claim 8, as a flow improver, wax anti-settling Additive, lubricity improver, friction wear reducer, corrosion inhibitor and / or engine intake system cleaner in petroleum distillates. 10. Concentrate containing a mineral oil, mineral oil distillate or a fuel and fuel and, based on the total amount of the concentrate, 5 to 80% by weight at least one copolymer according to one of claims 5 or 6. 11. Mixtures of at least one concentrate according to claim 10 and further auxiliaries, according to the areas of use mentioned in claim 8 be used. 12. Fuel and fuel composition containing a fuel and Fuel and, based on the total amount of fuel and Fuel composition, 5 to 5000 ppm by weight at least one Copolymers according to claim 5 or 6 alone or in admixture with others Mineral adjuvants.