NL9200043A - Dendritic macromolecule for electronics etc. - Google Patents

Abstract

A dendritic macromolecule contains a core and with branches emanating from it. The branches are prepd. from vinylcyanide units of formula R'-(CH2-CHR''-R''') (I) where R' = the core, or unit of the previous generation; R'' = H or CH3; R''' = formula -CH2-NR5R6 (II) where R5 and E6 = each, a H or unit of the next generation. The number of branches on the Nth generation is larger than or equal to the number of reactive sites of the core and is smaller than or equal to the number of reactive sites of the core multiplied by the 2N-1 and has a mol.wt. of 100-1,000,000. Also claimed is the prepn. of the macromol.

Description

DENDRITIC MACROMOLE COLUMN AND ITS PREPARATION

The invention relates to a dendritic macromolecule containing a core and branching branches.

Dendritic macromolecules are three-dimensional, highly ordered oligomeric and polymeric molecules with a very precisely defined chemical structure. Such molecules are known and are described, for example, by D.A. Tomalia et al. In Angew.Chem.Int.Ed.Engl. 29 (1990), 138-175. In this publication, a number of different dendritic macromolecules are disclosed, such as, for example, polyamidoamine {PAMAM) dendrimers, which are also described in US-A-4507466, and polyethyleneimine (PEI) dendrimers, which are also described in US-A-4631337.

The applications envisaged for dendritic macromolecules are as diverse as they are numerous. In the aforementioned publications various possible applications are mentioned, such as electronic applications, applications for calibration of sieves, catalyst (s), selective membranes and coatings, but also consider the use of dendritic macromolecules as impact strength improver or as cross-linking agent in various plastics.

A drawback of the above-mentioned dendritic macromolecules is, however, that they are very sensitive to degradation by hydrolysis reactions, while in particular the PAMAM dendrimers are also unstable at elevated temperature, so that a significant degradation of these macromolecules occurs when they become at higher temperatures. exposed.

The object of the invention is to provide a dendritic macromolecule which is both very insensitive to degradation by hydrolysis reactions and which is thermally very stable.

The dendritic macromolecule according to the invention is characterized in that the branches are prepared from vinyl cyanide units. The dendritic macromolecule according to the invention has been found to be very stable thermally, while also being very insensitive to degradation by hydrolysis reactions. The dendritic macromolecule according to the invention also has a very compact structure.

Dendritic macromolecules, also known as dendrimers or star-shaped dendrites, are three-dimensional, highly ordered oligomeric and polymeric molecules with an exactly defined chemical structure. These macromolecules are formed by alternating reaction steps starting from a nucleus or initiator core. Usually, the reactions that occur during the synthesis proceed almost completely and selectively, so that hardly any undesired side reactions occur and a dendritic macromolecule is obtained with an exactly defined chemical structure. A two-dimensional projection of a dendritic macromolecule is shown in figure 1:

The molecules that can be used as a core according to the present invention are molecules containing at least one functional group. Within the scope of the invention, a functional group is a group which, if desired in the presence of a suitable catalyst, can react with a vinyl cyanide unit. Groups which can react with a vinyl cyanide unit under favorable reaction conditions are, for example, hydroxyl groups, primary and secondary amine groups, thiol groups, carbon compounds with electronegative substituents, such as an ester group, an amide group, a ketone group, an aldehyde group, a carboxylic acid group and salts thereof. Preferably, the core as a functional group contains a hydroxyl group, a primary amine group and / or a secondary amine group.

Depending on the nature of a functional group, it can react with one or more vinyl cyanide units. When a functional group can react with F vinyl cyanide units, this functional group has a functionality F. A hydroxy 1 group can react with one vinyl cyanide unit and thus has a functionality F of 1. A primary amine group can react with two vinyl cyanide units and has thus a functionality F of 2. In general, the functionality F has a value of 1, 2 or 3.

A molecule is suitable as a core when the molecule contains at least one functional group G. This molecule preferably contains 1-10 functional groups G. A suitable core can be selected, for example, from the group of ammonia, water, methanol, polymethylenediamines, such as hexamethylenediamine, ethylenediamine and 1,4-diaminobutane (DAB), diethylene triamine, diethylene tetramine, tetraethylene pentamine, linear and branched polyethyleneimine, raethylamine, hydroxyethylamine, octadecylamine, polyaminoalkylarenes, such as 1,3,5-tris (aminomethyl) benzene, tris (aminoalkyl) amines, such as tris (aminoethyl) amine, heterocyclic amines, such as imidazolines and piperidines, hydroxyethylaminoethylamine, mercaptoethylamine, morpholine, piperazine, pentaerythritol, polyalkylene polyols, such as polyethylene glycol and polypropylene glycol, glycols, such as ethylene glycol, 1,2-dimercaptoethane, polyalkylene polymeric captanes, glyphapine, phosphine, , thiophenols, phenols, melamine and derivatives thereof, such as melamine tris (hexamethylenediamine). Preferably, a core selected from the group of polymethylenediamines, glycols and tris- (1,3,5-aminomethyl) benzene is used in the process according to the invention. More preferably 1,4-diaminobutane is used as the core.

If desired, it is possible to use a (co-) polymer, containing the above functional groups, as a core for the dendritic macromolecule. Examples of such (co-) polymers are styrene-maleimide copolymer, styrene-acrylonitrile copolymer, polyethyleneimine and polymers, such as, for example, polypropylene oxide, polystyrene and ethylene-propylene-diene copolymers, which have been functionalized with one or more of the above functional groups, such as, for example, NH2 groups.

The shape of the chosen core largely determines the shape of the macromolecule. when a small molecule is used as a core, a spherical shape can be obtained. When a polymer is used, the resulting dendritic macromolecule has a more elongated shape.

A number of branches, which are prepared from vinyl cyanide units, sprout from the core. When the reactions occurring proceed completely, the total number of branches of the desired generation N can be calculated as follows. When 6 is the number of functional groups containing the core, and P is the functionality of each individual functional group, the number of reactive positions R of the core is equal to the sum of the functionalities F of all - functional groups 6. The maximum number branches of the Nae generation can be described as the number of reactive sites R multiplied by 2H_1. When the reactions occurring do not proceed completely, the number of branches is smaller and lies between R and (R * 2S "1). Typically, the dendritic macromolecule contains 1-10 generations of branches, preferably 2-10, especially 3-9.

The molecular weight of the dendritic macromolecules of the invention is 100-1000000, preferably 700-100000, especially 1600-100000.

Suitable vinyl cyanide units in the light of the present invention contain a double bond, as well as an electron withdrawing group, which is conjugated directly with this double bond, and can be selected from the group of compounds of formula II

(formula 1), where

R2 = a hydrocarbon compound of 1-18 carbon atoms, containing 1-5 cyanide groups;

Particularly suitable vinyl cyanide units that can be used are acrylonitrile and methacrylonitrile (MACN).

The dendritic macromolecule comprises a core, as described in the previous section, and branches. The branches of the dendritic macromolecule comprise at least four units of formula 2:

(formula 2} where R1 = the nucleus or a unit of the previous generation;

R4 = a hydrocarbon compound with 1-18 carbon atoms, containing 1 to 5

groups contains; R5 = H or a next generation unit; R6 = H or a next generation unit, where in each

group the groups R5 and R6 may be the same or mutually different.

The branches usually comprise less than 1000, preferably less than 250 units according to formula 2. The branches preferably comprise more than 6, especially more than 10 units according to formula 2. If desired, the branches of the dendritic macromolecules contain different units according to formula 2.

The invention also relates to a method by which the dendritic macromolecule of the present invention can be prepared.

In Angew.Chem.ïnt.Ed.Engl. 29 (1990), p.138-175 describes two synthesis procedures with which dendritic macromolecules can be prepared. During one synthesis procedure, the so-called "protected group method", the construction of the dendritic macromolecules, being polyethyleneimine (PEI) dendrimers, is carefully controlled by the strategic use of protected groups, causing unwanted side reactions and unwanted structural imperfections. of the dendritic macromolecules are prevented. During the other synthesis procedure, the so-called "excess reagent method", which produces, for example, polyamidoamine (PAMAM) dendrimers, a very large excess of reagents is used, statistically minimizing the likelihood of undesired reactions and imperfections.

The above "protected group method" is based on the presence of protected aziridine rings. The aziridine rings are opened with the aid of primary amines, after which deprotection takes place with the aid of a strong acid. The complicated isolation procedures, the low yield of the synthesis procedure and the use of expensive reagents make this method for the preparation of dendritic macromolecules unsuitable for large scale application.

The above "excess reagent method" contains as the reaction step the complete Michael addition of primary amine groups to methyl methacrylate followed by an amidation with ethylenediamine. However, the synthesis of the polyamidoamine dendrimers thus formed requires a very large excess of reagents in order to avoid undesired side reactions. This drawback is also described by D.A. Tomalia in Angew.Chem.ïnt.Ed.Engl. 29 (1990), p. 148.

Most of the excess reagents are removed by evaporation in, for example, a rotary evaporator, after which the last residues of the reagents are removed from the viscous reaction product by a precipitation step. However, the intermediate product must be completely pure between the various synthesis steps, so that the precipitation step must be carried out several times. These complicating factors also make this synthesis procedure for dendritic macromolecules unsuitable for large-scale application.

The drawbacks of each of the aforementioned synthesis procedures are so great that the application of these procedures on a large, and thus commercially attractive scale, poses insurmountable problems, as already noted by J. Alper in Science 251 (March 1991), p. . 1562-1564; "The most important stumbling block for most applications is that the scaling up of the synthesis procedures has yet to be developed."

The present invention provides a method of preparing dendritic macromolecules which does not have the above-mentioned drawbacks.

The method by which the dendritic macromolecule according to the invention is prepared is characterized in that the method comprises steps a) to c); a) each functional group of the core is reacted with a vinyl cyanide unit; b) each built-in nitrile unit is reduced to an araine group; c) each amine group is reacted with vinyl cyanide units; , wherein steps b) and c) (N-1) are performed alternately to arrive at a macromolecule of the desired generation N. The value of N usually ranges from 1 to 10, preferably N has a value of 3-10. It is possible to stop the preparation method after reaction step b). This results in a dendritic macromolecule of a generation 1V2, 2x / 2 or higher.

It. it has been found that the synthesis procedure by which the dendritic macromolecule of the invention is prepared does not have the above-mentioned drawbacks, making this method very suitable for large-scale use. In addition, with the method according to the invention it is not necessary to isolate and purify the product obtained in the individual intermediate steps. Thus, the dendritic macromolecule of the present invention can be easily obtained on a large scale.

In step a) of the method according to the invention, each functional group of the core with functionality F is reacted with F vinyl cyanide units. The reaction that occurs, for example the Michael addition of a primary amine group to a vinyl cyanide unit, generally takes place in solution. The solvent used for this is usually chosen in such a way that neither the course of the reactions that occur, nor the absence of undesired side reactions is adversely affected. It is thus important that the solvent used does not react with the functional groups of the core under the reaction conditions employed. Such solvents can be selected, for example, from the group of water, tetrahydrofuran, various alcohols, such as methanol, ethanol, isopropanol and the like, various ethers, and mixtures of these solvents. The choice of the final solvent is largely determined by the nature of the functional groups of the core. Preferably, water, methanol, or a mixture of both is used as the solvent.

When it is desired during this reaction step to react each reactive site H of the core with a vinyl cyanide unit, the ratio of the reactants, which can be described as the ratio between the number of vinyl cyanide units and the number of reactive sites, should be at least 1. Usually this ratio is between 1 and 5, more preferably between 1 and 3. When this ratio is less than 1, not all reactive site R reacts with a vinyl cyanide unit.

The temperature during step a) is usually between 0 and 100 ° C, preferably between 5 and 70 ° C.

If desired, a catalyst is added to the reaction mixture during step a) to allow the reaction of the functional groups with the vinyl cyanide units to proceed smoothly. Examples of suitable catalysts for this are weak acids, such as acetic acid. Typically, the amount of the catalyst added to the reaction mixture is 0-5% by weight relative to the number of reactive sites R.

In step b) of the process of the invention, each built-in vinyl cyanide moiety is reduced to an amine group. Preferably this is a primary amine group. Thus, when the built-in vinyl cyanide unit is acrylonitrile, a propylamine (PA) unit is formed. The resulting reduction reaction generally takes place in solution. The solvent used for this is usually selected from the group of diamines (such as, for example, ethylenediamine), water, ammonia, alkane diamines, various alcohols, such as methanol, ethanol, isopropanol and the like, dioxane, various ethers, such as tetrahydrofuran, and mixtures of these solvents. Preferably, water, methanol, ethyldiamine or a mixture of these solvents is used as the solvent.

The reduction reaction can take place, for example, by reacting the built-in vinyl cyanide unit with H 2 gas. When a complete reduction reaction is desired, the molar ratio of H 2 to nitrile groups is at least 2. When this molar ratio is less than 2, complete reduction does not take place. Typically, the reduction step is performed in the presence of a suitable catalyst. Generally, a reducing catalyst is used, preferably a heterogeneous reducing catalyst.

The catalyst used in accordance with the invention is a catalyst comprising a Group VIII metal of the Periodic Table of Elements as set forth in the cover of the Handbook of Chemistry and Physics, 58th Edition, CRC Press, 1977- 1978. It is known that group VI1 metals exhibit activity in the hydrogenation of nitriles. See, for example, EP-A-0077911. Nickel, cobalt, platinum, palladium and rhodium are well suited. In order to have sufficient catalytic activity, the metal must have a large contact surface. The metal can be used as such or on a suitable support.

Particularly suitable as a catalyst according to the invention is Raney nickel or Raney cobalt. For a description of these Raney catalysts and their preparation, see US-A-1628190.

Raney nickel mainly comprises nickel and aluminum, the latter in the form of metallic aluminum, aluminum oxides or aluminum hydroxides. Small amounts of other metals, such as iron and / or chromium, in elemental or bonded form may be added to the Raney nickel to enhance the activity and selectivity for hydrogenation of certain groups of compounds. It is known that iron and / or chromium promoted Raney nickel is ideally suited for the reduction of nitrile groups, see, e.g., S. R. Montgomery, Catalysis of Organic Reactions 5, pages 383-409 (1981).

Raney cobalt also contains aluminum and may be equipped with promoters. It is known, for example, that chromium-promoted Raney cobalt is suitable for the hydrogenation of nitriles.

Before use, the Raney nickel or cobalt catalyst is often pretreated with a lye, such as, for example, KOH or NaOH, to favorably influence the selectivity of the reduction reaction. The amount of lye to be used for this depends on the amount of catalyst. Usually 0.01 to 0.2 grams of lye per gram of catalyst (dry weight) is used. Preferably, it is 0.03 to 0.18 grams of caustic per gram of catalyst, most preferably 0.05 to 0.15 grams of caustic per gram of catalyst. The pretreatment is carried out by dissolving the desired amount of caustic solution in the smallest possible amount of suitable solvent, for example water, after which the resulting solution is added to the pre-rinsed catalyst. The resulting mixture is stirred intensively.

The concentration of the catalyst, based on the total weight of the reaction mixture, is generally between 1 and 35% by weight, preferably between 5 and 20% by weight, and most preferably between 6 and 12% by weight. .

For example, the reduction reaction (step b) can be performed in a sealed reactor under an H 2 atmosphere. The absolute hydrogen pressure prevailing therein is usually between 1 and 500 atm, preferably between 10 and 200 atm, and most preferably between 10 and 100 atm. The reaction temperature is not critical and is usually between 0 and 200 ° C, preferably between 10 and 100 ° C.

In step c) of the process of the invention, each functional group is reacted with vinyl cyanide units (Michael addition reaction). When the functional group is a primary amine group, it can react with two vinyl cyanide units. The reaction conditions during this reaction step can be chosen analogously to those during reaction step a).

When the reaction steps a) to c) have been carried out once, a dendritic macromolecule of the second generation (N = 2) is obtained. By alternately repeating reaction steps b) and c), a higher-generation dendritic macromolecule can be obtained. Alternately performing the reaction steps b) and c) N times results in a dendritic macromolecule of the (N + 1) th generation. If desired, the reaction product after reaction step b) can be isolated to yield a dendritic macromolecule with a generation of 11 / zt 21/2 or higher. The reaction product obtained can be isolated after any reaction step.

The resulting dendritic macromolecule can, if desired, be fully or partially modified with a variety of functional groups. This can be achieved, for example, by reacting all or part of the amine groups present, if desired in the presence of a suitable catalyst, with suitable reagents. Examples of such reagents are unsaturated aliphatic esters and amides, such as, for example, acrylic ester, methacryl ester, crotyl ester and acrylamide, ethylene oxide, acid halides, such as, for example, acid chloride, acryloyl chloride, alkyl halides, such as, for example, epichloridrine, ethyl bromoacetate and allyl bromide, aryl halides, such as, for example, benzyl chloride, to such as, for example, tosyl chloride, anhydrides, such as, for example, maleic anhydride, dicarboxylic acids, such as terephthalic acid and adipic acid, (a) cyclic aldehydes, such as formaldehyde, ethanal and hexanal, p-formylphenylacetic acid and 1,4,5,8-naphthalene tetraacetaldehyde .

The dendritic macromolecules according to the invention are, in part due to their good thermal stability and their very low hydrolysis sensitivity, extremely suitable for mixing with a thermoplastic polymer or a polymer composition.

The thermoplastic polymer can be selected, for example, from the group of polyolefins, such as polyethylene and polypropylene, polyesters, such as, for example, polyalkylene terephthalates (such as, for example, polyethylene terephthalate and polybutylene terephthalate) and polycarbonates, polyamides, such as, for example, nylon-6, nylon-4.6, nylon-8, nylon- 6.10 and the like, polystyrene, polyoxymethylene, acrylonitrile-butadiene-styrene copolymers, styrene-acrylonitrile copolymers, styrene-maleimide copolymers, polysulfonic acid, polyimides, styrene-maleic anhydride copolymers, poly (methyl methacrylate), or multiple polyvinyl alcohol compositions, or polymers. However, this list is by no means exhaustive.

If desired, additives can be added to a mixture of dendritic macromolecules according to the invention with a thermoplastic polymer or a polymer composition. Examples of such additives are impact strength improvers, stabilizers, antioxidants, lubricants, fillers, flame extinguishers, dyes, pigments, reinforcing fibers and conductive fibers.

The invention is further illustrated by the following examples without being limited thereto.

Example I

1200 ml of methanol and 150 grams (1.7 mol) of 1,4-diaminobutane (DAB, substrate) were placed in a 2-liter three-necked flask equipped with a stirrer, a cooler, a thermometer and a dropping funnel. . After this mixture was cooled to a temperature of 10 ° C, a solution of 400 grams (7.6 moles) of acrylonitrile (ACN) in 100 ml of methanol was added dropwise over 2 hours. Then the reaction mixture thus obtained was heated (temperature 40 ° C) for 16 hours.

After the mixture was then cooled to room temperature, both the methanol and the excess acrylonitrile were evaporated under reduced pressure. The residue thus obtained was dissolved in methanol at a temperature of 50 ° C, after which the desired product, being the desired tetranitrile, after crystallization and isolation, was obtained pure as white needles, which was found to have a melting point of 52.8 ° C. The yield obtained was 92%.

The isolated product was analyzed by -H- and 13 C-NMR spectroscopy and mass spectrometry, which showed that the product obtained was DAB (ACN) 4.

i-LC NMR (50 MHz, Ρ, Ο): 119 ppm, CNf 53.1 ppm, NCH, (CH2),; 49.4 ppm, NCH, CH, CH; 24.9 ppm, NCH, CH, CN: 16.9 ppm CH, CN.

IN NMR f200 MHz, CDCl 3: 2.85 ppra, t, 2H, NCH2CH2CN? 2.55 ppm, m, 1H, NCH, (CH,),? 2.48 ppm, t, 2H, CH 2 CN; 1.55 ppm, m, 1H, CH, CH, N.

Example II

8.0 grams of Raney nickel catalyst (BLM 112 W11 from Degussa, the composition contains 85% by weight Ni, 2.0% by weight Fe and 2.5% by weight Cr and 9.7% by weight, according to the manufacturer's instructions. % A1) was pretreated with 0.8 grams of KOH dissolved in 10 ml of demineralized water. The catalyst was then 'flushed' three times with 50 ml of ethylenediamine (EDA).

During this pretreatment, the temperature was 20 ° C.

The catalyst was then placed in an autoclave with a volume of 160 ml with 100 ml of EDA. After this, the autoclave was closed, purged several times with H 2 gas, and then below 60 atm. H2 heated to a temperature of 40 ° C while stirring the reactor contents.

Then, 4 grams of DAB (ACN) 4 was dissolved in 10 grams of EDA and transferred to the autoclave using a so-called dosing vessel, which had been flushed several times with H 2 gas and pressured at 70 atm. At a pressure of 70 atm. the reduction reaction took place. After 120 minutes, the reduction was complete. The isolated product was analyzed by 13 C-NMR spectroscopy, which showed that the resulting product was 1,4-diaminobutane-n, n'-tetra-1-propylamine, DAB (FA) 4.

HC NMR f50 MHz. D.OW 53.4 ppm, NCH, CH, CH, CH, (2x); 51.1 ppm, NCH, CH? CH? NH? (4x) 39.5 ppm, C 1 N 5 (4 x); 28.8 ppm, CH2CH2NH2 (4x); 23.9 ppm, NCH, CH, CH, CH, N (2x).

Example lil

Example I was repeated, instead of 1.4-diaminobutane now using 5.0 grams of DAB (FA) 4 as substrate.

The isolated product was analyzed by 13 C-NMR spectroscopy to show that the resulting product was DAB (PA) 4 (ACN) e. The yield obtained was 91%.

--C NMR f50 MHz, CDCl 4 U 118.9 ppm, CN (8x); 53.9 ppm, NCH, CH, CH, CH, (2x); 51.5 and 51.4 ppm, NCH, CB, CH, N (8x); 49.6 ppm, NCH, CH, CN (8x); 25.0 and 24.9 ppm, NCH, CH, CH, CH, and NCH, CH, CH, N (6x); 16.9 ppm, CH2CN (8x).

Example IV

Example II was repeated, 2.0 grams of DAB (PA) 4 (ACN) 8 being reduced to DAB (PA) 4 (PA) e for 1200 minutes, as shown by analysis of the isolated product by 13 C-NMR spectroscopy .

lie NMR (50 MHz, DoOU 53.6 ppm, NCH, CH, CH, CH, (2x); 51.7 ppm, NCH2CH2CH2N (8x), 51.2 ppm, NCH, CH, CH, NH, <8x); 39.6 ppm CHj [NH2 (8x); 28.9 ppm, CH 2 CH 2 NH 2 (8x); 24.1 ppm, NCH, CH, CH, CH, N (2x); 22.3 ppm, NCH, CH, CH, N (4x).

Example V

Example III was repeated using 2.0 grams of DAB {PA) 4 (PA) 8 as the substrate instead of DAB (PA) 4.

The isolated product was analyzed by 13 C-NMR spectroscopy, which showed that the product obtained was DAB (PA) 4 {PA) 8 (ACN) 16.

~ C NMR (50 MHz, CDCl ^ i; 119.0 ppm, CN (16x); 54.1 ppm, NCH, CH, CH.CH, (2x); 52.2 ppm, NCH, CH, CH. (8x); 51.5 and 51.4 ppm, NCH, CH, CH, (16x); 49.5 ppm, NCH, CH, CN (16x); 25.0 and 24.9 ppm NCH, CH, CB, CH, and NCH, CH, CH, N (10x); 24.3 ppm , NCH, CH, CH, N (4x), 16.9 ppm, CH 2 CN (16x).

Example VI

Example IV was repeated, reducing 2.0 grams of DAB (PA) 4 (PA) a (ACN) 16 for 4200 minutes at a temperature of 40 ° C to DAB (PA) 4 (PA) S (PA) 1S, as evidenced by analysis of the results obtained by 13 C-NMR spectroscopy.

UlC NMR (50 MHz. Ρ, Ο): 53.6 ppm, NCH, CH, CH, CH, (2x)? 51.7 ppm, NCH, CH, CH, N (24x); 51.2 ppm, NCH, CH, CH, NH, (16x)) 39.6 ppm, CH, NH, (16x); 28.9 ppm, CH, CH, NH, (16x); 24.1 ppra, NCH, CH, CH, CH, N (2x); 22.3 ppm, NCH, CH, CH, N (12x).

Example VII

Example V was repeated, using instead of DAB (PA) 4 (PA) 8 3.0 grams of DAB (PA) 4 (PA) 8 (PA) 16 as the substrate.

The isolated product was analyzed by 13 C-NMR spectroscopy, which showed that the product obtained was DAB (PA) 4 (PA) e (PA) 16 (ACN) 32.

UC NMR (50 MHz. CDCl-J i 119.0 ppm, CN (32x); 54.2 ppm NCH, CH, CH, CH? (2x) i 52.2 ppm, NCH, CH, CH, (24x); 51.4 ppm, NCH, CH, CH, (32x); 49.4 ppm, NCH, CH, CN (32x); 24.9 ppm NCH, CH, CH, CH, and NCH, CH, CH, N (18x); 24.4 ppm, NCH, CH, CH , N (12x), 16.8 ppm, CH 2 CN (32x).

Example VIII

Example VI was repeated, reducing 2.0 grams of DAB (PA) 4 (PA) g (PA) 16 (ACN) 32 to DAB (PA) 4 (PA) 8 for 4200 minutes at a temperature of 60 ° C. (PA) 16 (PA) 32, which was shown by analysis of the results obtained by 13 C-NMR spectroscopy.

—C NMR (50 MHz, Ρ, Ο): 51.7 ppm, NCH, CH, CH, N (56x), 51.2 ppm, NCH, CH, CH, NH, (32x); 39.6 ppm, CH2NH2 (32x); 28.8 ppm, CHjCHaNHa (32x); 22.3 ppm, NCH, CH, CH, N (28x).

Example IX

Example VII was repeated using 2.0 grams of DAB (PA) 4 (PA) 8 (PA) 16 (PA) 32 as the substrate instead of DAB (PA) 4 (PA) 8 (PA) 16.

The product obtained was analyzed by 13 C-NMR spectroscopy, which showed that the product obtained was DAB (PA) 4 (PA) e (PA) 16 (PA) 32 (ACN) 64.

tlC NMR (50 MHz, CDCl ^: 119.0 ppm, CN (64x); 54.2 ppm, NCH2CH2CH2CH2 (2x); 52.2 ppm, NCH, CH, CH, (56x), 51.4 ppm, NCH, CH, CH, (64x ); 49.5 ppm, NCH, CH, CM (64x) j 25.0 ppm, NCH, CH, CH, CH, and NCH, CH, CH, N (34x); 24.2 ppm, NCH, CH, CH, N (28x) 16.9 ppm, CH 2 CN (64x).

Example X.

Example VIII was repeated, reducing 2.0 grams of DAB (PA) 4 (PA) 8 (PA) 36 (PA) 32 (ACN) 6 4 to DAB (PA) at a temperature of 80 ° C for 4200 minutes. 4 (PA) e (PA) 16 (PA) 32 (PA) 64, as indicated by analysis of the results obtained by 13 C-NMR spectroscopy.

HC NMR (50 MHz, D2Q): 51.7 ppm, NCH, CH, CH, N (120x); 51.2 ppm, NCH, CH, CH, NH, (64x); 39.6 ppm, CH, NH, (64x); 28.8 ppm, CHjCH2NHj (64x); 22.3 ppm, NCH, CH, CH, N (60x).

Example XI

20 grams of acrylonitrile were dissolved in 10 ml of methanol. This solution was then added dropwise to a solution of 5.0 grams of ethanolamine (ETAM) in methanol at a temperature of 10 ° C. Then the reaction mixture was heated for 16 hours (temperature 40 ° C). After evaporation of the solvent and washing of the residue with ether, the reaction product dinitrile ethanol (ETAM (ACN) 2) was obtained, which was shown by analysis of the results obtained by 3 H- and 13 C-NMR spectroscopy.

UjC. NMR (50 MHz, CDCl 2: 119.0 ppm, CN; 59.5 ppm, CH 2 OH; 55.5 ppm, CH 2 CH 2 OH; 49.7 ppm NCH 2 CH 2 CN; 17.4 ppm CH, CN.

H NMR 1200 MHz, CDCl 3; 3.66 ppm, t, 1H, Cl 2 OH; 2.91 ppm, t, 2H, CH 2 CH 2 CN; 2.72 ppm, 1H, t, NCH 2 CH 2 OH; 2.53 ppm, 2H, t, CH 2 CN.

Example XII

Example II was repeated using 2.0 grams of ETAM (ACN) Z dissolved in methanol as the substrate. After 60 minutes at a temperature of 40 ° C, the reduction reaction in methanol appeared to have occurred completely and selectively, and the desired ETAM (PA) 2 had been obtained, as shown by analysis of the obtained product by 13 C-NMR spectroscopy.

L3jC NMR f50 MHz. D, O): 59.1 ppm, CH 2 OH 5 55.0 ppm, NCH, CH, OH; 51.8 ppm, NCH, CH, CH, NH, (2x); 39.5 ppm, (2x); 28.9 ppm, CH2CH2NH2 (2x),

Example XIII

To 0.5 grams of anion exchanger (Lewatit HP 500 MB *, brought in hydroxy form using a 3% NaOH solution, followed by rinsing with water to a neutral pH) and 2.0 grams of polyethylene glycol (PEG, Mn = 455, 4.4 mmol), 10 grams of acrylonitrile (189 mmol) are added dropwise at a temperature of 5 ° C. The resulting mixture was stirred at a temperature of 20 ° C for 12 hours. The product obtained was filtered and rinsed with dichloromethane. After evaporation of the dichloromethane and the excess acrylonitrile, the product was washed with diethyl ether (three times). The isolated oil was PEG (ACN) 2, as shown by analysis of the results obtained by 13 C-NMR spectroscopy.

12JC NMR (50MHz, CDCl2: 70.5ppm, OCH2-CH2O; 65.9ppm, OCH, -CH, CN; 18.8ppm, CH2CN; 118.2ppm, CN.

example χιν

Example II was repeated using 2.0 grams of PEG (ACN) 2 as the substrate and methanol as the solvent for the reaction. After 300 minutes at a temperature of 37 eC, the reduction reaction was found to have occurred completely and selectively, and the desired FEG (PA) 2 was obtained, as shown by analysis of the results obtained by 13 C-NMR spectroscopy.

3JjC NMR f50 MHz. ; 70.0 ppm, 0CH2-CH2O; 69.3 ppm, OCH2CH2CH2NH2; 38.2 ppm, CHjNHj? 32.0 ppm, CH2CH2NH2.

Example XV

1.0 gram of ε-aminocaproic acid {sAC, 8.0 mmol) was dissolved in 10 ml of water and deprotonated with 0.5 equivalents of K2CO3. An excess of acrylonitrile (4 molar equivalents) was then added at a temperature of 0 ° C. Then the mixture was heated for 12 hours (temperature 40 ° C). After evaporation of the solvents and the excess acrylonitrile, a colorless oil remained, which was sAC (ACN) 2, as shown by analysis of the results obtained by 13 C-NMR spectroscopy.

UjC NMR (50 MHz, CDCl 2: 184.0 ppm, CO; 121.4 ppm, CN; 53.0 ppm, NCH, CH, CH, CH,? 48.8 ppm, NCH, CH, CN; 38.1 ppm, CH2CO; 27.0 ppm, NCH, CH, CH, 2626.2 / 26.1 ppm CHjC ^C CCH ^CO ?15.6 ppm, CH, CN.

Example XVI

Example II was repeated, 2.0 g of sAC (ACN) 2 being dissolved in water and used as a substrate. After 120 minutes at a temperature of 40 ° C, the reduction reaction in water appeared to have occurred completely and selectively, and the desired sAC (PA) 2 had been obtained, which was shown by analysis of the results obtained by 13 C-NMR spectroscopy.

- = ^ = - C nmr (50 MHz, CDC1,1: 182.6 ppm CO; 53.9 ppm, NCH, CH, CH, CH, i 51.6 ppm, NCH, CH, CB, NH, (2x); 40.0 ppm, CHaNHj (2x); 38.8 ppm, CH2CO; 29.5 ppm, CHjCH2NH2 (2x); 27.8 ppm, NCH, CH,; 26.5 ppm / 25.8 ppm, NCH, CH, CH, CH, CH ,.

Example xvii

Example II was repeated, but now n-butanol was used as a rinsing agent for the catalyst, and as a solvent for the substrate and for the reaction. After 180 minutes of reaction at a temperature of 40 ° C, the reduction to the desired DAB (PA) 4 was complete and selective.

L1C NMR (50 MHz. Ρ, ΟΙ: 53.4 ppm, NCH, CH, CH, CH, (2x)? 51.1 ppm, NCH, CH, CH, NH, (4x); 39.5 ppm, CH2NH2 (4x); 28.8 ppm CH2CH2NH2 (4x); 23.9 ppm, NCH, CH, CH, CH, N (2x).

Example XVIII

Example IX was repeated with the catalyst now purged with tetrahydrofuran (THF). Then 2.0 grams of DAB (ACN) 4 were dissolved in THF and THF was also used as the solvent for the reaction. An H2 pressure of 30 atmospheres was applied, and a temperature of 80 ° C. After 120 minutes of reaction, the reduction to the desired DAB (PA) 4 was complete and selective.

1 C NMR (50 MHz, D, _>>; 53.4 ppm, NCH7CH? CH, CH, (2x); 51.1 ppm, NCH, CH, CH, NH, (4x); 39.5 ppm, CH2NH2 (4x); 28.8 ppm, CH2CH2NH2 (4x); 23.9 ppm, NCH, CH, CH, CH, N (2x).

Example XIX

Example XVIII was repeated, but now a reaction temperature of 40 ° C was used. After 240 minutes of reaction, the reduction to the desired DAB (PA) 4 was complete and selective.

CC NMR (50 MHz, D, O): 53.4 ppm, NCH, CH, CH, CH, (2x); 51.1 ppm, NCH, CH, CH, NH, (4x); 39.5 ppm, C 1 NH 3 (4x); 28.8 ppm, CH2CH2NH2 (4x); 23.9 ppm, NCH, CH, CH, CH, N (2x).

Example XX

8.0 grams of Raney nickel catalyst (BLM 112 W® from Degussa, the composition contains 85 wt% Ni, 2.0 wt% Fe and 2.5 wt% Cr and 9.7 wt% Al) was pretreated with KOH analogous to Example II. After this pretreatment, the catalyst was rinsed once with 50 ml of demineralized water. The catalyst was then transferred to the autoclave reactor with 100 ml of demineralized water, rinsed with H2 gas and heated to a temperature of 60 ° C. After this, 4.0 grams of DAB (ACN) 4 was dissolved in 5.0 ml of methanol and transferred to the autoclave. A complete and selective reduction to DAB (PA) 4 took place in 90 minutes at an H2 pressure of 70 atmospheres.

11 C NMR (50 MHz, D, O): 53.4 ppm, NCH, CH, CH, CH, (2x); 51.1 ppm, NCH2CH2CH2NH2 (4x); 39.5 ppm, CH2NH2 (4x); 28.8 ppm, CH2CH2NH2 (4x), 23.9 ppm, NCH, CH, CH, CH, N (2x).

Example XXI

Example xx was repeated, using as catalyst Raney Cobalt (type Grace 2724R, promoted with Cr). After 15 minutes of reaction, the reduction to the desired DAB (PA) 4 was complete and selective.

11 C NMR (50 MHz, Ρ, Ο) 53.4 ppm, NCH, CH, CH, CH, (2x); 51.1 ppm, NCH, CH, CH, NH, (4x) y 39.5 ppm, CHaNHj (4x); 28.8 ppm, CH2CH2NH2 (4x); 23.9 ppm, NCH2CH2CHCH2N2 (2x).

Example XXII

10 grams of melamine (1,3,5-trishexamethyleneamine) (23.6 mmol MEL (HMA) 3) was dissolved in 150 ml of methanol. The resulting solution was added to 15 grams of acrylonitrile (283 mmol) at a temperature of 0 ° C. The mixture thus obtained was stirred at a temperature of 20 ° C for 1 hour, then at a temperature of 45 ° C for 12 hours. The solvent and excess acrylonitrile were removed at reduced pressure using a

Rotavapor at a temperature of 40 ° C. After precipitation in diethyl ether and isolation, pure MEL (HMA) 3 (ACN) 6 was obtained, which was shown by analysis of the product / a viscous red oil using 13 C-NMR spectroscopy.

--C NMR (50 MHz, CDCl 3) 165 165.8 ppm, NCN (3x); 118.7 ppm, CN (6x); 53.4 ppm, NCH, CH, CH, CH, (3x); 49.6 ppm, NCH, CH, CN (6x); 40.5 ppm, NHCH, (3x); 29.7 ppm, NHCH, CH, (3x); 27.3 ppm, 26.8 ppm, 26.7 ppm, NCH, CH, CH, CH, CH, CH, NH (9x) f 17.0 ppm, CH, CN (6x).

Example XXIII

Example XX was repeated, dissolving 2.3 grams of MEL (HMA) 3 (ACN) 6 as substrate. The reduction reaction was carried out at a temperature of 60 ° C. After 1020 minutes of reaction, the reduction to the desired melamine (HHA) 3 (PA) 6 was complete and selective, as evidenced by the 13 C and 1 H NMR spectra.

Ü-C NMR (50 MHz.165.7 ppm, NCN (3x); 53.7 ppm, NCH, CH, CH, CH, (3x); 51.3 ppm, NCH, CH, NH, (6x); 40.8 ppm, NHCH, ( 3x); 39.7 ppm, CHjNHj, (6x); 29.8 ppm, NHCH, CH, (3x); 29.1 ppm, CH, CH, NH, (6x); 27.6 ppm, 26.9 ppm, 25.6 ppm, NCH, CH, CH , CH, CH, CH, NH (9x).

Example XXIV

25 grams of Jeffamine D-2000 * (a modified polypropylene oxide, Mw = 2000, Texaco Chemical Company) was dissolved in 50 ml of methanol. The resulting solution was added to 6.0 grams of acrylonitrile at a temperature of 0 ° C. The resulting mixture was stirred at a temperature of 20 ° C for 1 hour, then at a temperature of 40 ° C for 12 hours. The product obtained was then dissolved in a mixture of 100 ml of pentane and 5.0 ml of diethyl ether. After isolation, Je ff (ACN) 4 was found to have formed (a colorless liquid, yield 94%), as indicated by analysis of the product by 13 C-NMR spectroscopy * NMC NMR 5050 MHz, CDCl 3): 118.7 ppm, CN? 75.1-75.7 ppm, OCH,; 73.0-73.6 ppm, NCH; 52.2-52.5 ppm, NCH, CH, CN; 17.2-17.5 ppm, CCH ,; 19.1 ppm, CH, CN.

Example XXV

8.0 grams of Raney Nickel catalyst (BLH 112 W® from Degussa, the composition contains 85 wt% Ni, 2.0 wt% Fe and 2.5 wt% Cr and 9.7 wt% Al) was pretreated with 0.8 grams of KOH dissolved in 10 ml of de-mineralized water. After precipitation of the catalyst thus obtained, the water layer was decanted, and then 50 ml of ethylenediamine was added while the mixture was stirred. Then, the catalyst thus washed was filtered off and added to 100 ml of ethylenediamine in a 160 ml autoclave. The autoclave was closed and purged several times with H 2 gas. Then 70 bar Hj gas was introduced into the autoclave, at a temperature of 38 ° C, and the contents were stirred intensively.

Then 2.0 grams of Jeff (ACN) 4, dissolved in 10 grams of ethylenediamine, was autoclaved. After 3 hours the reduction reaction appeared to be complete. Analysis of the product by 13 C-NMR spectroscopy showed pure Jeff (PA) 4 to have been formed.

ÜC NMR (50 MHz, D, 0i: 74.8-75.9 ppm, OCH ,; 72.4-73.3 ppm, NCH; 53.0-52.7 ppm, NCH, CH, NH,: 39.1 ppm, CHjNH-j; 32.3 ppm, CH2CH2NH2; 16.5 -17.3 ppm, CCH ,.

Example XXVI

900 ml of water and 75 grams (0.85 mol) of 1,4-diaminobutane (substrate) were placed in a 2-liter three-necked flask equipped with a stirrer, a cooler, a thermometer and a dropping funnel. After this mixture was cooled to a temperature of 10 ° C, a solution of 200 grams (3.8 moles) of acrylonitrile was added dropwise over 2 hours. Then the reaction mixture thus obtained was heated for 9 hours (temperature 65 ° C).

After the mixture was then cooled to room temperature, the water and the excess acrylonitrile were evaporated azeotropically. The residue thus obtained, containing DAB (ACN} 4 and water, was then reduced with Raney Cobalt catalyst, which had not been pretreated. After 1 hour, the reaction was stopped and the desired product was obtained as a colorless oil. The product was found to have formed pure DAB (PA) 4 by 13 C-NMR spectroscopy. The yield was 98%.

ilC NMR (50 MHz .: 53.4 ppm, NCH2CH2CH2CH2 (2x); 51.1 ppm, NCH2CH2CH2NH2 (4x)? 39.5 ppm, CH2NH2 (4x); 28.8 ppm, CH2CH2NH2 (4x)} 23.9 ppm, NCH, CH, CH, CH, N (2x).

Example XXVII

The heat stability of the dendritic macromolecules obtained in Examples I to VIII was measured by ThermoGraphic Analysis (TGA). For this purpose, approximately 2.5 mg of the respective product was obtained by means of a Perkin Elmer (7 series) heated in a neon atmosphere from 30 ° C to 900 ° C at a rate of 20 ° C / rain. Table 1 lists the temperature values at which maximum decomposition of the product occurs.

Table 1: Results of the TGA measurements of the products from Examples I to VII.

Product Temp. [e C] DAB (ACN) 4 330.1 DAB (PA) 4 330.0 DAB (PA) 4 (ACN) 8 331.8 DAB (PA) 4 (PA) „378.0 DAB (PA) 4 ( PA) 8 (ACN) 16 332.0 DAB (PA) 4 {PA) 8 (PA) l6 424.0 DAB (PA) 4 (PA) 8 (PA) 16 (ACN) 32 331.5

Example XXVIII

900 ml of water and 75 grams (0.85 mol) of diaminobutane were placed in a 2-liter three-necked flask equipped with a stirrer, a cooler, a thermometer and a dropping funnel. After this mixture was cooled to a temperature of 10 ° C, a solution of 200 grams of acrylonitrile in 50 ml of methanol was added dropwise at such a rate that the temperature of the reaction mixture remained below 15 ° C. After all had dripped in, the reaction mixture was kept at room temperature for two hours, then heated to a temperature of 65 ° C for 9 hours. Then the reaction mixture was cooled to room temperature and the product obtained was isolated.

The isolated product was analyzed by 1 H and 13 C-NMR spectroscopy and mass spectrometry, which showed that the product obtained was DAB (ACN) 4.

LLC NMR (50 MHz, DoOI: 119 ppm, CN? 53.1 ppm, NCH, (CH, 49 49.4 ppm, NCH, CH CN CN; 24.9 ppm, NCB, CH, CN: 16.9 ppm CH, CN.

1 H NMR 1,200 MHz, CDCl 3; 2.85 ppm, t, 2H, NCH, CH.CN; 2.55 ppm, m, 1H, NCH2 (CH2) 3; 2.48 ppm, t, 2H, CH 2 CN; 1.55 ppm, m, 1H, CH, CH, N.

Example XXIX

In a 250 ml three-necked flask equipped with a stirrer, a cooler, a thermometer and a dropping funnel, 30 ml of water and 5.0 grams (58 mmol) of diaminobutane were placed. After the mixture was cooled to a temperature of 10 ° C, a solution of 15 grams (280 mmol) acrylonitrile was added dropwise at such a rate that the temperature remained below 15 ° C. After everything was added, the temperature of the mixture was kept at room temperature for two hours, after which the reaction mixture was heated at a temperature of 45 ° C for 16 hours.

After cooling the reaction mixture to room temperature, the water and excess acrylonitrile were evaporated. 2.5 grams of the obtained product (DAB (ACN) 4) were dissolved in 4 ml of methanol. This solution was combined with 8.0 grams of Raney

Cobalt catalyst (type Grace 2724 *, promoted with Cr) placed in a 160 ml autoclave. The autoclave was then closed, rinsed several times with H 2 gas and heated under H 2 pressure under atmospheres to a temperature of 80 ° C with stirring of the reactor contents. These reaction conditions were maintained for one hour.

After filtering off the catalyst and evaporating the water, 2.0 grams of the residue (DAB (PA) 4) was dissolved in 20 ml of water. 5.4 grams of acrylonitrile were added dropwise to this at a temperature of 10 ° C. The mixture was kept at room temperature for two hours, then heated at 40 ° C for 16 hours.

After cooling, the water and excess acrylonitrile were evaporated under reduced pressure. The resulting colorless residue (pure DAB (PA) 4 (ACN) 8) was then reduced, analogous to the method for reducing DAB (ACN) 4, as described in this example. The reduction is complete and selective within 90 minutes.

The DAB (PA) 4 (PA) 8 thus formed was dissolved in 30 ml of water. Then 5.0 grams of acrylonitrile were added dropwise at a temperature of 10 ° C. The temperature of the reaction mixture was then kept at room temperature for two hours, after which the reaction mixture was heated at 40 ° C for 16 hours. After cooling, the water and excess acrylonitrile were evaporated under reduced pressure, after which the colorless residue, being daB (PA) 4 (PA) e (acn) 16, was completely and selectively reduced in 2 hours to DAB (PA) 4 (PA ) 8 (PA) 16 r analogous to the method for reducing DAB (ACN) 4, as described in this example.

Example XXX

Ethyl acrylate (6.3 grams of EAC, 63 mmol) was dissolved in 20 ml of methanol. The resulting solution was cooled in an ice bath, while 0.5 grams of DAB (PA) 4 was added with stirring. The resulting mixture was stirred at room temperature for 20 hours. Then the product, a light yellow liquid, was isolated. Analysis of the product by 13 C-NMR spectroscopy showed pure DAB (PA) 4 (EAC) 8 to have been formed.

12 C NMR (50 MHz, CDCl 3): 172.5 ppm, CO (8x); 60.2 ppm, COOCH, (8x); 54.1 ppm, NCH, CH, CH, CH, (2x); 51.9 ppm, NCH, CH, CH, N (8x); 49.1 ppm, NCH, CH, CO (8x); 32.6 ppm, CH, CO (8x); 25.0 ppm, NCH, CH, CH, CH, (2x); 24.7 ppm, NCH, CH, CH, N (4x); 14.2 ppm, CH3 (8x).

Example XXXI

DAB (PA) 4 (EAC) 8 (0.5 grams, 0.45 mmol) was dissolved in 3.0 ml of methanol. The resulting solution was cooled to a temperature of 0 ° C with an ice bath while a large excess of ethanolamine (EA) was added dropwise. The product was then isolated. Analysis of the product, a yellow oil, by 13 C-NMR spectroscopy showed pure DAB (PA) 4 (EA) 8 to have been formed.

lie NMR f50 MHz, D 1 cn; 175.6 ppm, CONH (8x); 60.3 ppm, CH, OH (8x); 53.3 ppm, CH2CH2CH2CH2 (2x); 51.5 ppm and 51.2 ppm, NCH, CH, CH, N (8x); 49.1 ppm, NCH, CH, CO (8x), 41.8 ppm, CONHCH, (8x); 32.9 ppm, CH2CO (8x); 24.0 ppm, NCH, CH, CH, CH, (2x).

In the examples, it has been shown that different generations of dendritic macromolecules according to the invention can be synthesized. The synthesized macromolecules of the invention are not susceptible to degradation by hydrolysis reactions. The synthesis can be performed in various solvents, using different catalysts and under different reaction conditions. It has also been shown that the different reaction steps can be carried out one after the other without the resultant (intermediate) product having to be isolated after each separate step, which makes scaling up the process very simple. The outer generation of the dendritic macromolecules can be modified with various functional groups. Finally, it has been shown that the dendritic macromolecules according to the invention are thermally very stable.

Claims (26)

Dendritic macromolecule containing a core and branching branches, characterized in that the branches are prepared from vinyl cyanide units. Dendritic macromolecule according to claim 1, characterized in that the core is a molecule containing 1-10 functional groups, each of which independently has a functionality of 1, 2 or 3. Dendritic macromolecule according to claim 1, characterized in that the core is a (co) polymer containing functional groups, each of which independently has a functionality of 1, 2 or 3 · Dendritic macromolecule according to any one of claims 1-3, characterized in that the core as functional group contains a hydroxyl group, a primary amine group and / or a secondary amine group. Dendritic macromolecule according to either of Claims 1 and 3, characterized in that the core is selected from the group consisting of polymethylenediamines, glycols and tris- (1,3,5-aminomethyl) benzene. Dendritic macromolecule according to any one of claims 1 to 5, wherein a number of generations of branches are present, characterized in that the number of branches of the Nth generation is greater than or equal to the number of reactive sites R of the core, and smaller or equal to the number of reactive positions R of the core multiplied by 2H_1. Dendritic macromolecule according to any one of claims 1-6, characterized in that the number of generations N is 3-10. Dendritic macromolecule according to any one of claims 1-7, characterized in that the monomeric vinyl cyanide unit is acrylonitrile or methacrylonitrile. 9. Dendritic. macromolecule, the branches of which contain units of the formula

where R1 = the core or unit of the previous generation; R2 - -H or -CH3;

R4 = a hydrocarbon compound with 1-18 carbon atoms / 1 to 5

groups contains; R5 ss H or a next generation unit; R6 * H or a next generation unit, where in each

group the groups R5 and R6 may be the same or mutually different. Dendritic macromolecule according to any one of claims 1 to 9, characterized in that it is wholly or partly modified with functional groups. Dendritic macromolecule according to claim 10, characterized in that the functional groups are selected from the collection of unsaturated aliphatic esters and amides, acid halides, alkyl halides, aryl halides, tosyl halides, anhydrides, dicarboxylic acids and (a) cyclic aldehydes. Dendritic macromolecule according to claim 10 or 11, characterized in that the functional groups are ethyl acrylate. Dendritic macromolecule according to any one of claims 1-12, characterized in that the molecular weight is 100-1000000. Process for the preparation of a dendritic macromolecule according to any one of claims 1 to 13, characterized in that the process comprises steps a) to c): a) each functional group of the core is reacted with a monomeric vinyl cyanide unit; b) each built-in nitrile unit is reduced to an amine group; c) each amine group is reacted with monomeric vinyl cyanide units; wherein steps b) and c) (N-1) are performed alternately to arrive at a macromolecule of the desired generation N. Process according to claim 14, characterized in that during steps a) and / or c) the ratio between the number of vinyl cyanide monomer units and the number of reactive sites is at least 1. Process according to claim 14 or 15, characterized in that at least one of steps a) and c) is carried out in the presence of a weak acid. A method according to any one of claims 14-16, characterized in that step a) is carried out at a temperature between 0 and 100 ° C. A method according to any one of claims 14-17, characterized in that step b) is carried out in the presence of a reducing catalyst comprising at least one Group VIII metal of the periodic table of the elements. Process according to claim 18, characterized in that the catalyst is selected from the group Raney nickel and Raney cobalt. The process according to claim 19, characterized in that 1-35 wt.% Catalyst is used, based on the total weight of the reaction mixture. 21. Process according to any one of claims 14-20, characterized in that step b) is carried out under an H 2 atmosphere at an absolute hydrogen between 1 and 500 atm. and at a temperature between 20 and 200 ° C. A method according to any one of claims 14-21, characterized in that the reaction steps take place in water, methanol, or a mixture of both. A method according to any one of claims 14-22, characterized in that the reaction steps take place without the respective reaction products being isolated in the meantime. Polymer composition comprising a thermoplastic polymer and a dendritic macromolecule according to any one of claims 1-13. 25. Dendritic macromolecule as substantially described and illustrated by the examples. 26. Process for the preparation of a dendritic macromolecule as substantially described and illustrated by the examples.