PL171776B1 - Dendritic macromolecules and method of obtaining sames - Google Patents

Abstract

1. The method of producing a dendritic macromolecule which contains the core and ramifications protruding from the core. Characterized in that: In the case of producing macromolecules with the molecular weight of at least 1600, or with the number N of generations within the range of 3-10, the stages from a) through c) are carried out: a) the reaction of each functional group of the core with the monomeric monomer of acrylonitrile is produced; b) each bonded nitrile monomer is in principle reduced to an amino group, or in the presence of the reduction catalyst; c) the reaction of each amino group with the monomers of acrylonitrile is produced; The stages b) and c) are carried out alternately. 18. The method of producing dendritic macromolecule which contains the core and ramifications protruding from the core. Characterized in that: In the case of producing macromolecules with the desired generation N within the range of 2-10, the stages from a) through c) are carried out: a) the reaction of each functional group of the core with the monomeric monomer of acrylonitrile is produced; b) each bonded nitrile monomer is in principle reduced to an amino group in the presence of the reduction catalyst, which contains a metal from at least 8th> group of the periodic table and gaseous H2, and c) the reaction of each amino group with the monomers of acrylonitrile is produced; The stages b) and c) are carried out alternately (N-1) times.

Description

The invention relates to a process for the preparation of dendritic macromolecules having a core and branches extending from the core.

Dendritic macromolecules are three-dimensional, highly ordered oligomeric or polymeric molecules with a very well defined chemical structure. Such molecules are known and are described, for example, in the publication by D. A. Tomalia et al. in Angew. Chem. Int. Ed. Engl. 29 (1990). pp. 138-175. This publication describes a variety of dendritic macromolecules, e.g., polyamidoamine dendrimers (PAMAMs), also described in U.S. Patent No. 4,507,466, and polyethyleneimine (PEI) dendrimers, also described in U.S. Patent No. 4,607,466. No. 4,631,337.

The applications envisaged for dendritic macromolecules are as diverse as many. These publications give a number of possible applications, e.g. in electronics, use for screen calibration, as catalysts (and catalyst supports), as selective membranes and coatings, but their use as impact modifiers or crosslinkers in some plastics should also be taken into account. .

The disadvantage of the above-mentioned dendritic macromolecules, however, is that they are very sensitive to degradation by the hydrolysis reaction, and moreover, especially PAMAM dendrimers are not stable at elevated temperature, which means that these macromolecules degrade significantly when exposed to elevated temperatures.

In Angew. Chem. Int. Ed. Engl. 29 (1990), pp. 138-175, describe two synthetic methods by which dendritic macromolecules can be prepared. In one synthesis method, the so-called protecting group method, the composition of dendritic macromolecules, e.g. polyethyleneimine (PEI) dendrimers, is very carefully controlled through the strategic use of protecting groups, preventing undesirable side reactions and undesirable defects in the structure of the dendritic macromolecules. In the second synthesis method, the so-called excess reagent method, e.g. polyamidoamine dendrimers (PAMAs) are produced, a very large excess of reagents is used, which statistically reduces the risk of unwanted reactions and defects.

The previously mentioned method with protecting groups is based on the presence of protected aziridine rings. Aziridine rings are opened with primary amines followed by strong acid deprotection. Complicated product isolation methods, low synthesis yields and the use of expensive reagents make this method of producing dendritic macromolecules unsuitable for large-scale use.

The aforementioned excess reagent method involves as a reaction step the complete Michael condensation of the primary amino groups to methyl methacrylate, followed by amidation with ethylenediamine. However, the synthesis of the polyamidoamine dendrimers thus formed requires a very large excess of reagents to be prevented

171,776 unwanted side reactions. This drawback is also described in Angew. Chem. Int. Ed. Engl. 29 (1990), p. 148. Most of the excess reagents are removed by evaporation, e.g. in a Rotavapor, after which the rest of the remaining reagents are removed from the viscous reaction product in a precipitation step. The intermediate product between the various synthesis steps, however, must be completely pure, which means that the precipitation operation has to be repeated several times. These complex factors make this synthesis for producing dendritic macromolecules also unsuitable for large-scale use.

The disadvantages of each of the aforementioned synthetic methods are so significant that the application of these methods on a large - and hence industrially attractive - scale presents insurmountable difficulties, as commented in J. Alper, Science 251 (March 1991), p. 1562. - 1564: A major obstacle to most of these applications is that large-scale synthesis methods need to be developed.

The object of the invention is to provide a dendritic macromolecule which is not very sensitive to degradation by hydrolysis and also has very good thermal stability.

The invention provides a method for producing dendritic macromolecules which obviates the above drawbacks.

The method of producing dendritic macromolecules comprising a core and branches protruding from the core according to the invention is characterized in that, when producing a macromolecule with a molecular weight of at least 1600, or in which the generation number N is

3-10, the reaction steps a) to c) are carried out:

a) reacting substantially each core functional group with a monomeric vinyl cyanide unit;

b) reducing substantially each attached nitrile unit to an amino group;

c) reacting substantially any amino group with monomeric vinyl cyanide units;

wherein steps b) and c) are carried out alternately.

In another embodiment, the method for producing a dendritic macromolecule comprising a core and branches extending from the core according to the invention is characterized in that in the case of producing a macromolecule with the desired N 2-10 generation, the reaction steps a) to c) are carried out:

a) reacting substantially each core functional group with a monomeric vinyl cyanide unit;

b) reducing substantially each attached nitrile unit to an amino group in the presence of a reducing catalyst comprising at least a metal from Group VIII of the Periodic Table of the Elements and H2 gas, and

c) reacting substantially any amino group with monomeric vinyl cyanide units; wherein steps b) and c) are carried out alternately (N-1) times.

Preference is given to using a core containing functional groups selected from hydroxyl groups, primary and secondary amino groups, thiol groups and groups formed by carbon compounds with electronegative substituents. A core containing a hydroxyl group, a primary amino group and / or a secondary amino group as functional groups is particularly preferably used. Most preferably a core is used selected from the group consisting of polymethylene diamines and ammonia, in particular a 1,4-diaminobutane core.

Preferably, acrylonitrile or methacrylonitrile is used as the monomeric vinyl cyanide mer.

During steps a) and / or c), a ratio of the number of vinyl cyanide monomeric units to the number of reactive sites is at least 1.

A preferred method according to the invention is that:

a) at least 95% of the core functional groups are made to react with the monomeric vinyl cyanide unit,

b) reducing at least 95% of the attached nitrile units to an amino group, and

(c) at least 95% of the amine groups are reacted with vinyl cyanide monomeric units.

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Preferably: a) at least 99% of the core functional groups are reacted with the monomeric vinyl cyanide unit, b) at least 99% of the attached nitrile units are reduced to an amino group, and c) at least 99% of the amino groups are reacted with the monomeric cyanide units vinyl.

Step b) of the reaction is preferably carried out in the presence of a reducing catalyst containing at least a metal from the group consisting of nickel, cobalt, platinum, palladium and rhodium.

Preferably a catalyst is selected from the group consisting of Raney Nickel and Raney Cobalt.

The catalyst is preferably used in an amount of 1 to 35% by weight of catalyst, based on the total weight of the reaction mixture.

The reaction in step b) is preferably carried out under an atmosphere of H 2 under a hydrogen pressure of 110 ⁵ Pa - 500-10 ⁵ Pa and at a temperature of 20-200 ° C.

Preferably, the individual reaction steps are carried out in water, methanol or a mixture thereof.

In order to obtain the macromolecule of the desired generation N, steps b) and c) are performed alternately (N-1) times. The value of N usually varies from 1 to 10, preferably N is from 3 to 10. The production process can be interrupted after the reaction step b). This produces a dendritic macromolecule of generation 11/2, 21/2 or higher. In the following description of the invention, it generally means at least 80%. Preferably, it is at least 90%, more preferably at least 95% and most preferably at least 99%.

In step a) of the process of the invention, essentially each core functional group having functionality F is reacted with vinyl cyanide Fers. The following reaction, e.g. Michael condensation of the primary amine group with a vinyl cyanide unit, usually takes place in solution. The solvent used for this purpose is usually chosen such that it does not adversely affect either the course of the next reaction or cause undesirable side reactions. Thus, it is important that the solvent used does not react with the functional groups of the core under the reaction conditions used. Such solvents may be selected, for example, from the group consisting of water, tetrahydrofuran, various alcohols such as methanol, ethanol, isopropanol and the like, various ethers, and mixtures of these solvents. The final choice of solvent depends greatly on the nature of the core functional groups. Preferably, water, methanol, or a mixture thereof is used as the solvent.

If it is desired to cause each reactive site to react with a vinyl cyanide unit during this reaction step, then the ratio of the reactants, which can be described as the ratio of the number of vinyl cyanide units to the number of reactive sites, must be at least 1. Typically the ratio is from 1 to 5, more preferably from 1 to 3. If the ratio is less than 1 then not every reactive site R will react with vinyl cyanide units.

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

Optionally, a catalyst is added to the reaction mixture during step a) so as to ensure that the reaction of the functional groups with the vinyl cyanide units proceeds well. Examples of suitable catalysts are weak acids, e.g. acetic acid. Typically, the amount of catalyst added to the reaction mixture is 0-5 mol%, based on the number of reactive R sites.

In step b) of the process according to the invention, substantially each vinyl cyanide mer introduced is reduced to an amino group, preferably a primary amino group. If the input vinyl cyanide unit is acrylonitrile, a propylamine (PA) unit is formed. The following reduction reaction usually takes place in solution. The solvent used for this purpose is usually selected from the group consisting of diamines (e.g., alkane diamines such as ethylenediamine), water, ammonia, various alcohols such as methanol, ethanol, isopropanol and the like, various ethers such as tetrahydrofuran and dioxane, and mixtures these solvents. Preferably, water, methanol, ethyldiamine,

1,3-aminopropane or a mixture of these solvents.

For example, the reduction reaction can be carried out by causing the fed vinyl cyanide mer to react with H 2 gas. If complete reduction is desired, H / group molar ratio

The nitrile ratio must be at least 2. If this molar ratio is less than 2, no complete reduction takes place. Typically the reduction step is carried out in the presence of a suitable catalyst. Generally, a reducing catalyst is used, preferably a heterogeneous reducing catalyst.

The catalyst used in the process of the invention is a catalyst that contains a metal from Group VIII of the Periodic Table of the Elements as shown on the cover of the Handbook of Chemistry and Physics, 58th edition, CRC Press, 1977-1978. It is known that metals of the VIII group of the Periodic Table of the Elements are active in the hydrogenation of nitriles. See, e.g., European Patent No. EP-A-0077911. Nickel, cobalt, platinum, palladium and rhodium are very suitable. To have sufficient catalytic activity, the metal must have a large contact area. The metal can be used as such or it can be applied to a suitable support.

Raney Nickel or Raney Cobalt is particularly suitable for use as a catalyst in the process of the invention. For a description of these catalysts and their preparation, see U.S. Patent No. 1,628,190.

Raney nickel consists essentially of nickel and aluminum, the latter in the form of metallic aluminum, aluminum oxides or aluminum hydroxides. A small amount of other metals, such as iron and / or chromium, may be added to Raney nickel in elemental or bonded form to increase its activity and selectivity in the hydrogenation of specific groups or compounds. It is known that Raney nickel promoted with iron and / or chromium is very suitable for the reduction of nitrile groups; see, e.g., S. R. Montgomery, Catalysis of Organic Reactions 5, pp. 383-409 (1981). Raney cobalt also contains aluminum and may be supplemented with promoters. For example, it is known that chromium-promoted Raney cobalt is very suitable for the hydrogenation of nitriles.

Before use, the Raney nickel or cobalt catalyst is often pretreated with an alkaline solution, for example KOH or NaOH, which favorably influences the selectivity of the reduction reaction. The amount of hydroxide used for this purpose depends on the amount of catalyst. Typically from 0.01 to 0.2 g of hydroxide per gram of catalyst (dry weight) are used. Preferably, from 0.03 to 0.18 g of hydroxide per gram of catalyst is used, most preferably from 0.05 to 0.15 g of hydroxide per gram of catalyst. The pretreatment is carried out by dissolving the desired amount of hydroxide in as little as possible of a suitable solvent, e.g. water, and then the resulting solution is added to the catalyst previously sprinkled with water. The mixture thus obtained was stirred vigorously.

The concentration of the catalyst, based on the total weight of the reaction mixture, is usually from 1 to 35% by weight, preferably from 5 to 20% by weight, in particular from 6 to 12% by weight.

The reduction reaction (step b) can be carried out, for example, in a sealed reactor under an atmosphere of H2. The hydrogen pressure in the sealed reactor is usually from 1 to 10 bar to 500 10 ⁵ Pa, preferably from 10 10 ⁵ Pa to 20040 ⁵ Pa, in particular from 10 10 ⁵ Pa to 100 10 ⁵ Pa. The reaction temperature is not critical; usually it is from 0 ° C to 200 ° C, preferably from 10 ° C to 100 ° C.

In step c) of the process of the invention, substantially every functional group is reacted with vinyl cyanide units (Michael condensation reaction). If the functional group is a primary amino group, it can react with two vinyl cyanide units. The reaction conditions during this reaction step may be selected to be the same as for the reaction in step a).

When the reaction steps a) to c) are carried out once, a second generation dendritic macromolecule is obtained (N = 2). Higher generation dendritic macromolecules can be obtained by alternately repeating reaction steps b) and c). If the reaction steps b) and c) are alternated N times, a generation dendritic macromolecule is obtained (N +1). If desired, the reaction product may be isolated after the reaction step b) to obtain a dendritic macromolecule of generation 1.5, 2.5 or higher. The resulting reaction product can be isolated after any selected reaction step.

The resulting dendritic macromolecule may optionally be wholly or partially modified with all kinds of functional groups. This can for example be done through

Reaction, completely or partially, of the amino or nitrile groups present, optionally in the presence of a suitable catalyst, with the appropriate reagents. Examples of such reagents are inorganic acids such as HCl, unsaturated aliphatic esters and amides such as acrylic ester, methacrylic ester, crotonil ester and acrylamide, acid halides such as acid chlorides, acryloyl chloride, alkyl halides such as ethyl bromoacetate and bromide allyl halides, aryl halides such as benzyl chloride, hydroxyethyl methacrylate, tosyl halides such as tosyl chloride, anhydrides such as maleic anhydride, phthalic anhydride, dicarboxylic acids such as terephthalic acid and adipic acid, oxiranes such as ethylene oxide and epichlorohydrin , (a) cyclic aldehydes such as formaldehyde, ethanal and hexanal, p-formylphenylacetic acid and 1,4,5,8-tetraacetaldehyde naphthalene.

The dendritic macromolecule according to the invention is characterized in that it has branches from vinyl cyanide units. It was found that the dendritic macromolecule according to the invention has a very good stability at elevated temperature, and is also very insensitive to degradation by the hydrolysis reaction. Moreover, the dendritic macromolecule produced by the method of the invention has a very tightly packed structure.

Dendritic macromolecules, also known as dendrimers or stellar dendrites, are three-dimensional, highly ordered oligomeric and polymeric particles with a well-defined chemical structure. These macromolecules are formed by various reaction steps starting from the core or core initiator. Usually, the reactions taking place during the synthesis are truly complete and selective reactions, which means that no or virtually no side reactions take place and a dendritic macromolecule with a well-defined chemical structure is obtained. Fig. 1 shows a two-dimensional cross section of a denritic macromolecule.

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

Depending on the nature of the functional group, it may react with one or more vinyl cyanide units. If a functional group can react with vinyl cyanide facers, such functional group has a functionality of F. The hydroxyl group can react with one vinyl cyanide unit and thus has an F functionality of 1. Primary amino group can react with two vinyl cyanide units and thus has a functionality of F of 2. In general, the functionality of F is 1, 2 or 3.

A molecule is a suitable core if it contains at least one G functional group. Such a molecule preferably has 1-10 G functional groups. A suitable core may for example be selected from the group consisting of ammonia, water, methanol, polymethylene diamine, diethylene triamine, diethylene tetraamine, tetrafylene pentamine, linear and branched polyethyleneimines, methylamine, hydroxyethylamine, octadecylamine, polyaminoalkyl areines such as 1,3,5-tri (aminomethyl) benzene, tris (aminoalkyl) amines such as tris (aminoethyl) amine, heterocyclic amines such as imidazolines and piperidines, hydroxyethylamines mercaptoethylamine, morpholine, piperazine, pentaerythritol, sorbitol, mannitol, duleite, inosit, polyalkylene polyols such as polyethylene glycol and polypropylene glycol, glycols such as ethylene glycol, 1,2-dumericaptoethane, polyalkaaptoethane polymercaptans, mycinaphylene glycols , thiophenols, phenols, melamine and its derivatives, such as melamine tris (hexamethylenedi uamina). The process of the invention preferably uses a core selected from the group consisting of polymethylene diamines, glycols and tris (1,3,5-aminomethyl) benzene. Polyethylene diamines which are particularly preferably used as cores are hexamethyls8

171 776 nodiamine, ethylenediamine and 1,4-diammonobutane (DAB). 1,4-Diammonobutane is most preferably used as the core.

If desired, a (co) polymer containing the above functional groups may also be used as the core for the dendritic macromolecule. Examples of such (co) polymers are styrene maleimide copolymers, styrene acrylonitrile copolymers, polyethyleneimine and polymers such as polyoxypropylene, polystyrene and ethylene propylene diene copolymers containing one or more of the above-mentioned functional groups such as NH2 groups.

The shape of the selected core largely determines the shape of the macromolecule. When a small particle is used as the core, a spherical shape can be obtained. If a polymer is used as the core, the resulting dendritic macromolecule will have an elongated shape.

Numerous branches sticking out of the core are made of vinyl cyanide units. When the reactions taking place are complete reactions, the total number of branches of the desired generation N can be calculated as follows. If G denotes the number of functional groups that the core contains and F denotes the functionality of each individual functional group, then the number of reactive R sites in the core is equal to the sum of the F functionalities of all G functional groups. The maximum number of generation N branches can be described as the number of reactive sites R multiplied by 2 ^NJ . If the reactions are not complete then the number of branches will be less, that is between R and (R-2N ' ¹ ). Typically, the dendritic macromolecule has 1-10 branch generations, preferably 2-10, especially 3-9).

The molecular weight of the dendritic macromolecules according to the invention is 100-100,000, preferably 700-100,000, especially 1600-100,000.

The vinyl cyanide units used in the process of the invention contain a double bond as well as an electron-attracting group directly coupled to the double bond, and may be selected from the group of compounds of formula I:

wherein R ¹ is -H or -CH 3; A is -C = N, R2 is a hydrocarbon compound with 1-18 carbon atoms containing 1-5 cyanide groups.

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

The dendritic macromolecule according to the invention comprises a core as previously described and branches. Branching of a dendritic macromolecule

contain at least four units of formula 2: H. j R ² I R ¹ - (ΟΙ 1, C - R ³ ) 1 (pattern 2) 1 H. 1 H.

wherein R ¹ is a previous generation core or mer; R ₂ is -H or -CH ₃ ; R ₃ is

R ⁵

-ch ₂ -n

R ⁶

R ⁵ is H or a next generation mer; R ⁶ is H or a next generation mer; wherein the r5 and r6 groups in each -CH2-Nos. ^{6 group} may be the same or different from each other.

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The branches usually contain less than 1000, preferably less than 250, units of formula 2. The branches preferably contain more than 6, especially more than 10, units of formula 2. Optionally, the branches of the dendritic macromolecule contain different units of formula 2.

It has been found that the method of producing a dendritic macromolecule according to the invention does not suffer from the aforementioned drawbacks, which means that it is very suitable for large-scale use. Moreover, in the process according to the invention it is not necessary each time to isolate and purify the product obtained in the individual intermediate steps. Thus, the dendritic macromolecules of the invention can be obtained in a large scale in a simple manner.

Due in part to their good heat stability and very limited susceptibility to hydrolysis, the dendritic macromolecules of the present invention are very compatible with thermoplastic polymers or polymer compositions.

The thermoplastic polymer may be selected e.g. from the group consisting of polyolefins such as polyethylene and polypropylene, polyesters such as polyalkylene terephthalates (such as polyethylene terephthalate) and polycarbonates, polyamides such as 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, copolymers of styrene with maleic anhydride, polymethyl methacrylate, or polyvinyl alcoholic compositions polymers. This list is by no means limiting.

Optionally, additives can be added to the mixture of the inventive dendritic macromolecules and the thermoplastic polymer or polymer composition. Examples of such additives are impact modifiers, stabilizers, antioxidants, lubricants, fillers, flame retardants, colorants, pigments, reinforcing fibers and conductive fibers.

The invention is further elucidated with reference to the following examples. The symbols used in these examples mean:

N - the number of reasons; OAK - 1 H - vuaminobutane; ACN - tayl acrylonitrile; PA - l-pbopyloaminai EDA - εΙ-Έηοόννίΐίΐιηίης; ETAM - ethanolemrine; PEG - ghkolkol ethylene; AC - amino0ypeone acid; THF - tetrahydrofuran; MEL - melamine; HMA - hexamethylmethylamine; Jeff - Jeffamine D-2000 (modified polyoxypropylene, Mw = 2000, product of Texaco Chemical Company); EAC - acrylic-atrii; EA - ethanolb; n;

Example I. Production of DAB (ACN) 4 (step a, N 1)

1200 ml of methanol and 150 g (1.7 mol) of 1,4-diaminobutane (DAB, substrate) were introduced into a 2-liter three-neck flask equipped with a stirrer, condenser, thermometer and dropping funnel. The mixture was then cooled to 10 ° C, and a solution of 400 g (7.6 mol) of acrylonitrile in 100 ml of methanol was added dropwise thereto over 2 hours. The reaction mixture thus obtained was heated for 16 hours (temperature 40 ° C).

After the mixture was cooled back 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, whereupon, after crystallization and isolation, the desired product, i.e. tetranitrile, was obtained in pure form with the appearance of white needles; the product was found to have a melting point of 52.8 ° C. The yield was 92%.

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Analysis of the isolated product by 1 H NMR spectroscopy and mass spectrometry indicated that the product obtained was DAB (ACN) ⁴

^L3 C NMR spectrum (50 MHz, D2O): 119 ppm, CN; 53.1 ppm, NCH2 (CH2) 3; 49.4 ppm; NCH2CH2CN; 24.9 ppm NCH2CH2CN; 16.9 ppm CH2CN.

1 H nMr spectrum (200 MHz, CDCl ₃ ): 2.85 ppm, t, 2H, NCH 2 CH 2 CN; 2.55 ppm, m, 1H, NCH2 (CH2) ₃ ; 2.48 ppm, t, 2H, CH2CN; 1.55 ppm, m, 1H, CH2CH2N.

Example EL Production of DAB (pA) 4 (step b, N 1.5)

8.0 g of Raney slanowuclide catalyst (BLM 11L W from Degyssa; delivery by supplier: 85% by weight Ni, 2.0% by weight Fe, 2.5% by weight Cr 1, 9.7% by weight Al) 0.8 g of KOH dissolved in 10 ml of demiBeralysis water was pretreated. The catalyst was then sprinkled three times with 50 ml of ethylenediamine (EDA). The temperature during the pretreatment was 20 ° C.

The catalyst and 100 ml of EDA were introduced into a 160 ml autoclave. The autoclave was closed, rinsed several times with H 2 gas and heated to 40 ° C under a pressure of 58.8-10 ⁵ Pa, while stirring the contents of the reactor.

Then, 4 g of DAB (ACN) 4 dissolved in 10 g of EDA were forced into the autoclave using a so-called dosing vessel, purged several times with H2 gas and pressurized to 68.1-1 [mu] l. The reduction reaction took place under the pressure of 68.1 10 Pa. Complete reduction took 120 minutes. Analysis of the isolated product by ^13C NMR spectroscopy showed that the product obtained was 1,4-diaminobutyl-B, n'-four (1-propylamine) as defined by the formula DAB (PA) 4 Spectrum ^{, 3} C NMR (50 MHz, D ₂ O): 53.4 ppm, NCH 2 CH 2 CH 2 CH 2 (2x); 51.1 ppm, NCH 2 CH 2 CH 2 NH 2 (4x); 39.5 ppm, CH2NH2 (4x); 28.8 ppm, CH 2 CH 2 NH 2 (4x); 23.9 ppm, NCH2CH2CH2CH2N (2x).

Example III. Production of DAB (PA). ₁ (ACN) s (step c, N 2).

Example 1 was repeated with the difference that 5.0 g DAB (PA) 4 was used as the substrate instead of 1 A-diaminobutane.

Analysis of the isolated product by ^13C NMR spectroscopy indicated that the product obtained was DAB (PA) 4 (ACN) g. The yield was 91%.

13 C NMR spectrum (50 MHz, D ₂ O): 118.9 ppm, CN (8 ×); 53.9 ppm, NCH 2 CH 2 CH 2 CH 2 (2x); 51.5 and 51.4 ppm, NCH2CH2CH2NH2 (8x); 49.6 ppm, NCH2CH2CN (8x); 25.0 and 24.9 ppm, NCH2CH2CH2 CH2 and NCH2 CH2CH2N (6x); 16.9 ppm CH ₂ CN (8x).

Example IV. Preparation of DAB (PA) 4 (PA) ₈ (step b, N 2.5). Example 2 was repeated with the difference that 2.0 g of DAB (PA) 4 (ACN) _{8 was} reduced in 1200 minutes to give DAB (PA) 4 (PA) ₈ as shown by analysis of the isolated product by spectroscopy ^{, 3} C NMR.

¹³ C NMR spectrum (50 MHz, D ₂ O): 53.6 ppm NCH 2 CH 2 CH 2 CH 2 (2x); 51.7 NCH2CH2CH2N (8x); 51.2 ppm, NCH2CH2CH2NH2 (8x); 39.6 ppm CH2NH2 (8x); 28.9 ppm CH2CH2NH2 (8x); 24.1 ppm, NCH 2 CH 2 CH 2 CH 2 N (2x); 22.3 ppm NCH ₂ CH ₂ CH ₂ N (4x).

Example 5 Preparation of DAB (PA) 4 (PA) ₈ (ACN) 1 (step c, N 3).

Example III was repeated with the difference that 2.0 g DAB (PA) 4 (PA) s was used as substrate instead of DAB (PA) 4.

Analysis of the isolated product by means of ^13C NMR spectroscopy showed that the product obtained was a DAB (PA) 4 (PA) 8 (ACN) i6.

^L3 C NMR spectrum (50 MHz, D ₂ O): 119.0 ppm, CN (16x); 54.1 ppm, NCH ₂ CH ₂ CH 2 CH 2 (2x); 52.2 ppm, NC H 2 CH ₂ CH 2 (8x); 51.5 and 51.4 ppm, NCH ₂ CH ₂ CH 2 (16x); 49.5 ppm, NCH2CH2CN (16x); 25.0 and 24.9 ppm, NCH2CH2CH ₂ CH ₂ and NCH ₂ CH2CH2N (10x); 24.3 ppm, NCH ₂ CH ₂ CH ₂ N (4x); 16.9 ppm CH ₂ CN (16x).

Example VI. Preparation of DAB (PA) 4 (PA) 8 (PA) and 6 (step b, N 3.5).

Example IV was repeated with the difference that 2.0 g of DAB (PA) 4 (PA) 8 (ACN) was not reduced at 40 ° C in 4200 minutes to give DAB (PA) 4 (PA) 8 (PA) i6, as results from analysis of isolated product by ^13C NMR spectroscopy.

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^L3 C NMR spectrum (50 MHz, D ₂ O): 53.6 ppm, NCH2CH2CH2CH2 (2x); 51.7 NCH2CH2CH2N (24x); 51.2 ppm, NCH2CH2CH2NH2 (16x); 39.6 ppm CH2NH2 (16x); 28.9 ppm, CH2CH2NH2 (16x); 24.1 ppm, NCH 2 CH 2 CH 2 CH 2 N (2x); 22.3 ppm NCH2CH2CH2N (12x).

Example VII. Preparation of DAB (PA) a (PA) s (PA) i6 (ACN) 32 (step c, N 4).

Example 5 was repeated with the difference that 3.0 g DAB (PA) 4 (PA) s (PA) 6 was used as the substrate instead of DaB (PA) ą (PA) g.

The isolated product was analyzed by ^13C NMR spectroscopy which showed that the product obtained was DAB (PA) 4 (PA) 8 (PA) 6 (ACN) ₂ .

Spectrum 1 ³ C NMR (50 MHz, D2O): 119.0 ppm, CN (32x); 54.2 ppm, NCH 2 CH 2 CH 2 CH 2 (2x); 52.2 ppm, NCH2CH2CH2 (24x); 51.4 ppm, NCH2CH2CH2 (32x); 49.4 ppm, NCH2CH2CN (32x); 24.9 ppm, NCH ₂ CH ₂ CH ₂ CH 2 and NCH 2 CH 2 CH 2 N (18x); 24.4 ppm, NCH2CH2CH2N (12x); 16.8 ppm CH ₂ CN (32x).

Example VIII. Preparation of DAB (PA) (PA) (PA) i6 (PA) 32 (step b, N 4.5).

Example Vi was repeated with the difference that 2.0 g of DAB (PA) (PA) (PA) i6 (ACN) 2 was reduced at 60 ° C in 4200 minutes to give DAB (PA) (PA) (PA) 6 (PA) 2, as seen from the analysis of results obtained using NMR spectroscopy ^I3 C.

¹³ C NMR spectrum (50 MHz, D ₂ O): 51.7 NCH 2 CH 2 CH 2 N (56x); 51.2 ppm, NCH2CH2CH2NH2 (32x); 39.6 ppm CH2NH2 (32x); 28.8 ppm, CH ₂ CH ₂ NH ₂ (32x); 22.3 ppm NCH ₂ CH ₂ CH ₂ N (28x).

Example IX. Preparation of DAB (PA) (PA) (PA) 6 (PA) 2 (ACN) 64 (step c, N 5).

Example VII was repeated with the difference that 2.0 g of DAB (PA) (PA) (PA) 16 (PA) 32 was used instead of DAB (PA) (PA) (PA) 6 as the substrate.

The resulting product was analyzed by ^13C NMR spectroscopy which showed it to be DAB (PA) (PA) (PA) ₆ (PA) ₂ (ACN) 64.

^L3 C NMR spectrum (50 MHz, D2O): 119.0 ppm, CN (64x); 54.2 ppm. NCH2CH2CH2CH2 (2x); 52.2 ppm, NCH2CH2CH2 (56x); 51.4 ppm, NCH2CH2CH2 (64x); 49.5 ppm, NCH ₂ CH ₂ CN (64x); 25.0 ppm, NCH ₂ CH ₂ CH ₂ CH 2 and NCH 2 CH 2 CH 2 (34x); 24.2 ppm, NCH ₂ CH ₂ CH ₂ N (28x); 16.9 ppm CH ₂ CN (64x).

Example 10 Preparation of DAB (PA) (PA) (PA) 6 (PA) 32 (PA) 64 (step b, N 5.5).

Example 8 was repeated with the difference that 2.0 g of dAb (PA) (PA) (PA) 6 (PA) 32 (ACN) 64 was reduced at 80 ° C in 4,200 minutes to give DAB (PA) (PA) (PA) 6 (PA) 32 (PA) 64 as evidenced by the analysis of the results obtained by ¹³ C NMR spectroscopy.

13 C NMR spectrum (50 MHz, D2O): 51.7 ppm, NCH2CH2CH2N (1206x); 51.2 ppm, NCH2CH2NH2 (64x); 39.6 ppm, CH2NH2 (64x); 28.8 ppm, CH2CH2NH2 (64x); 22.3 ppm NCH2CH2CH2N (60x).

Example XI. Production of ETAM (ACN) (step a, N 1).

20 g of acrylonitrile were dissolved in 10 ml of methanol. This solution was added dropwise at 10 ° C to a solution of 5.0 g of ethanolamine (ETAM) in methanol. The reaction mixture was then heated for 16 hours (at 40 ° C). After evaporation of the solvent and washing of the residue with ether, analysis of the results using spectroscopy H NMR and ¹³ C NMR showed that the reaction product obtained was a dwunitryloetanol (ETAM (ACN)).

¹³ C NMR spectrum (50 MHz, D2O): 119.0 ppm, CN; 59.5 ppm, CH2OH; 55.5 ppm, CH2CH2OH; 49.7 ppm, NCH2CH2CN; 17.4 ppm CH ₂ CN.

1 H NMR spectrum (200 MHz, CDCl 2): 3.66 ppm, t, 1 H, CH ₂ OH; 2.91 ppm, t, 2H, CH2CH2CN; 2.72 ppm, 1H, t, NCH ₂ CH ₂ OH; 2.53 ppm, 2H, t, CH2CN.

Example XII. Preparation of ETAM (PA) (step b, N 1.5).

Example 2 was repeated with the difference that 2.0 g ETAM (ACN) was used as the substrate. dissolved in methanol. After 60 minutes at 40 ° C, complete selective reduction had taken place in methanol and analysis of the obtained product by ¹³ C NMR spectroscopy showed that the desired ETAM (PA) was obtained.

¹³ C NMR spectrum (50 MHz, D2O): 59.1 ppm, CH2OH; 55.0 ppm, NCH ₂ CH ₂ OH; 51.8 ppm, NCH 2 CH 2 CH 2 NH 2 (2x); 39.5 ppm, CH2NH2 (2x); 28.9 ppm, CH2CH2NH2 (2x).

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Example XIII. Production of PEG (ACN) 2 (step a, N 1).

At 5 ° C, 10 g of acrylonitrile (189 mmol) and 2.0 g of acrylonitrile (189 mmol) and 2.0 g of acrylonitrile (189 mmol) were added dropwise to 0.5 g of anionic ion exchange resin (Lewatit MP 500 MB, adjusted to the hydroxide configuration with 3% NaOH solutions). polyethylene glycol (PEG, Mn = 455, 4.4 mmol). The resulting mixture was stirred for 12 hours at 20 ° C. The product obtained is filtered off and sprinkled with dichloromethane. After evaporating off the dichloromethane and the excess acrylonitrile, the product was washed with diethyl ether (three times). Analysis of the results obtained by ^13C NMR spectroscopy showed that the oil isolated was PEG (ACN) 2.

¹³ C NMR spectrum (50 MHz, CDCl 2): 70.5 ppm, OCH ₂ -CH ₂ O; 65.9 ppm, OCH ₂ -CH ₂ CN;

18.8 ppm, CH ₂ CN; 118.2 ppm, CN.

Example XIV. Production of PEG (PA) ₂ (step b, N 1.5).

Example 2 was repeated with the difference that 2.0 g PEG (ACN) _{2 was} used as the starting material and methanol was used as the reaction solvent. After 300 minutes at 37 ° C, complete and selective reduction had taken place and analysis of the results obtained by ¹³ C NMR spectroscopy showed that the desired PEG (PA) _{2 was} obtained.

¹³ C NMR spectrum (50 MHz, D2O): 70.0 ppm, OCH2-CH2O; 69.3 ppm, OCH ₂ CH ₂ CH ₂ NH 2;

38.2 ppm, CH2NH2; 32.0 ppm, CH ₂ CH 2 NH 2.

Example XV. Generation of ε-AC (ACN) 2 (step a, N 1).

1.0 g of ε-aminocaproic acid (ε-AC, 8.0 mmol) was dissolved in 10 ml of water and deprotonated with 0.5 equivalents of K2CO3. An excess amount of acrylonitrile (4 molar equivalents) was then added at 0 ° C. The mixture was heated for 12 hours (at 40 ° C). Analysis of the results of the C NMR spectrum showed that the colorless oil obtained after evaporation of the solvents and excess acrylonitrile was ε-AC (ACN ) ₂ .

^I3 C NMR spectrum (50 MHz, CDCl): 184.0 ppm, CO; 121.4 ppm, CN; 53.0 ppm, NCH ₂ CH ₂ CH 2 CH 2; 48.8 ppm, NCH ₂ CH ₂ CN; 38.1 ppm, CH ₂ CO; 27.0 ppm, NCH ₂ CH ₂ CH 2; 26.2 / 26.1 ppm, CH ₂ CH ₂ CH ₂ CH ₂ CO; 15.6 ppm, CH ₂ CN.

Example XVI. Preparation of ε-AC (PA) ₂ (step b, N 1.5).

Example 2 was repeated with the difference that 2.0 g of ε-AC (ACN) _{2 was} dissolved in water and used as the substrate. After 120 minutes at 40 ° C has occurred and the selective reduction of the total, and the analysis results obtained by the spectroscopy ^l3 C NMR showed that the desired ε-AC (PA) _2.

Spectrum 1 ^? C NMR (50 MHz, CDCl 2): 182.6 ppm, CO; 53.9 ppm, NCH ₂ CH ₂ CH ₂ CH 2;

51.6 ppm, NCH ₂ CH ₂ CH 2 NH 2 (2x); 40.0 ppm, CH2NH2 (2x); 38.8 ppm, CH ₂ CO; 29.5 ppm, CH ₂ CH ₂ NH ₂ (2x); 27.8 ppm, NCH2CH2; 26.5 ppm / 25.8 ppm NCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ .

Example XVII. Production of DAB (Pa) 4 (step b, N 1.5).

Example 2 was repeated with the difference that n-butanol was used as catalyst spray and as substrate and reaction solvent. Reaction for 180 minutes at 40 ° C was complete and selective reduction to the desired DAB (PA) 4.

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

Example XVIII. Preparation of DAB (PA) 4 (step b, N 1.5).

Example 2 was repeated with the difference that the catalyst was sprayed with tetrahydrofuran (THF). Then 2.0 g of DAB (ACN) 4 was dissolved in THF and THF was also used as a reaction solvent. An H 2 pressure of 29.4 · 1 (0 Pa and a temperature of 80 ° C.) was used. After 120 minutes of reaction, complete and selective reduction to the desired DAB (PA) 4 had occurred.

12 NMR spectrum (50 MHz, D ₂ O): 53.4 ppm, NCH ₂ CH ₂ CH ₂ CH 2 (2x); 51.1 ppm, NCH ₂ CH ₂ CH ₂ NH ₂ (4x); 39.5 ppm, CH ₂ NH 2 (4x); 28.8 ppm, ClbClbNIb (4x); 23.9 ppm, NCH ₂ CH ₂ CH ₂ CH 2 N (2x).

Example XIX. Production of DAB (PA) 4 (step b, N 2).

Example 18 was repeated, except that a reaction temperature of 40 ° C was used. After 240 minutes of reaction, there was complete and selective reduction to the desired DAB (PA) 4.

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¹³ C NMR spectrum (50 MHz, D2O): 53.4 ppm, NCH ₂ CH ₂ CH ₂ CH 2 (2x); 51.1 ppm, NCH ₂ CH ₂ CH ₂ NH ₂ (4x); 39.5 ppm, CH ₂ NH ₂ (4x); 28.8 ppm, CH ₂ CH ₂ NH ₂ (4x); 23.9 ppm, NCH ₂ CH 2 CH 2 CH 2 N (2x).

Example XX. Preparation of DAB (PA) a (step b, N 1.5).

8.0 Raney nickel catalyst (bLm 112 W from Degussa; with a composition of 85 wt.% Ni, 2.0 wt.% Fe, 2.5 wt.% Cr and 9.7 wt.% A1) was pretreated with KOH such as the same way as in example II. After this pretreatment, the catalyst was sprinkled once with 50 ml of demineralized water. The catalyst was then transferred to the autoclave along with 100 ml of demineralized water, and the autoclave was purged with H ₂ gas and heated to 60 ° C. Then 4.0 g of DAB (ACN) a was dissolved in 5.0 ml of methanol and poured into the aauoclave. Over a period of 90 µm and 2 ° C under a pressure of 66.60-10 ⁵ Pa H 2, complete and selective reduction to DAB (PA) 4 took place.

¹³ C NMR spectrum (50 MHz, D ₂ O): 53.4 ppm, NCH ₂ CH ₂ CH ₂ CH ₂ (2x); 51.1 ppm, NCH ₂ CH 2 CH 2 NH 2 (4x); 39.5 ppm, CH2NH2 (4x); 28.8 ppm, CH 2 CH 2 NH 2 (4x); 23.9 ppm, NCH2CH2CH2CH2N (2x).

Example XXI. Preparation of DAB (PA) a (step b, N 1.5).

Example XX was repeated except that the catalyst was Raney Cobalt (Raney cobalt catalyst) (Grace type 2724, promoted with Cr). After 15 minutes of reaction, there was complete and selective reduction to the desired DAB (PA) A.

^{Spectrum, 3} C NMR (50 MHz, D2O): 53.4 ppm, NCH2CH2CH ₂ CH ₂ (2x); 51.1 ppm, NCH ₂ CH ₂ CH 2 NH 2 (4x); 39.5 ppm, CH2NH2 (4x); 28.8 ppm, CH ₂ CH 2 NH 2 (4x); 23.9 ppm, NCH ₂ CH ₂ CH ₂ CH 2 N (2x).

Example XXII. Preparation of MEL (HMA) 3 (ACN) 6 (step a, N 1).

10 g of melamino (3,3,5-tris-sheenomethyleneamine) (23.0 mmol of MEL (HMA) 3) were dissolved in 150 ml of methanol. The resulting solution was added, at 0 ° C, to 15 g of acrylonitrile (283 mmol). The mixture thus obtained was stirred for 1 hour at 20 ° C and then for 12 hours at 45 ° C. The solvent and excess acrylonitrile were removed under reduced pressure with a Rotavapor at 40 ° C. The results of spectrum ^{analysis, 3} C NMR showed that the product obtained after precipitation in diethylether and isolation, a viscous red oil, was a pure MEL (HMA) 3 (ACN) 6.

¹³ C NMR spectrum (50 MHz, CDCl 2): 165.8 ppm, NCN (3x); 118.7 ppm, CN (6x); 53.4 ppm, NCH ₂ CH ₂ CH 2 CH 2 (3x); 49.6 ppm, NCH ₂ Cl 2 CN (6x); 40.5 ppm, NHCH ₂ (3x); 29.7 pprrii NHCH ₂ CHC (3x); 27.3 ppm, 26.8 ppma, 26.7 ppm, NCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ NH (9x); 17.0 ppm, CH ₂ CN (6x).

Example XXIII. Preparation of MEL (HMA) 3 (PA) 6 (step b, N 1.5).

Example XX was repeated, except that 2.3 g of MEL (HMA) 3 (ACN) 6 was dissolved as the starting material. The reduction reaction was carried out at a temperature of 60 ° C. The results of spectral analysis by 1 ³ C NMR Ή NMR showed that after 1020 minutes of reaction there was a complete and selective reduction to the desired melamine (HMA) 3 (PA) 6.

^N C NMR spectrum (50 MHz, D2O): 165.7 ppm, NCN (3x); 53.7 ppm, NCH ₂ CH ₂ CH 2 CH 2 (3x); 51.3 ppm, NCH ₂ CH ₂ NH ₂ (6x); 40.8 ppm, NHCH ₂ (3x); 39.7 ppm, CH 2 NH ₂ (6x); 29.8 ppm, NHCH2CH (3x); 29.1 ppm, CH ₂ CH 2 NH ₂ (6x); 27.6 ppm, 26.9 ppm, 25.6 ppm, NCH ₂ CH ₂ CH ₂ CH 2 CH 2 CH 2 NH (9x).

Example XXIV. Preparation of Jeff (ACN) A (step a, N 1).

25 g of Jeffamine D-2000 (modified polyoxypropylene, Mw = 2000, Texaco Chemical Company) was dissolved in 50 ml of methanol. The resulting solution was added, at 0 ° C, to 6.0 g of acrylonitrile (283 mmol). The mixture thus obtained was stirred for 1 hour at 40 ° C and then for 12 hours at 40 ° C. The resulting product was dissolved in a mixture of 100 ml of pentane and 5 ml of diethyl ether. The results of spectrum analysis ^l3 C NMR showed that the product obtained after isolation was a Jeff (ACN) ± (colorless liquid; yield 94%).

¹³ C NMR spectrum (50 MHz, CDCl 2): 118.7 ppm, CN; 75.1-75.7 ppm OCH2; 73.073.6 ppm, 52.2 - 52.5 ppm, NCH ₂ CH ₂ CN, 17.2 - 17.5 ppm, CCH 3; 19.1 ppm, CH2CN.

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Example XXV. Preparation of Jeff (PA) 4 (step b, N 1.5).

8.0 of the catalyst, it was added Raney nickel (BLM 112 Wz from Degy ssa: osseous a z 85% by weight of Ni, 2.0% by weight of Fe, 2.5% by weight of Cr and 9.7% by weight of A1) pretreated 0, 8 g of KOH dissolved in 10 ml of demineralised water. After the catalyst thus obtained had precipitated, the aqueous layer was deceptively decomposed and 50 ml of ethyl diamine was added while the mixture was stirred. The washed catalyst was then filtered off and added to 100 ml of ethylenediamine in a 160 ml autoclave. The autoclave was closed and purged with H2 gas several times. Gaseous H 2 was introduced into the autoclave at 38 ° C at a pressure of 68.6-10 ⁵ Pa and the contents were vigorously mixed.

2.0 g of Jeff (ACN) 4, dissolved in 10 g of ethylenediamine, were then introduced into the autoclave. After 3 hours, complete reduction was found. Analysis of the ³ C NMR spectra showed that the product obtained was pure Jeff (PA) 4. ^13C NMR spectrum (50 MHz, D2O):

74.8-75.9 ppm OCH2; 72.4-73.3 ppm, NCH; 53.0 - 52.7 ppm, NCH2CH2NH2; 39.1 ppm, CH2NH2; 32.2 ppm, CH2CH2NH2; 16.5 - 17.3 ppm, CCH3.

Example XXVI. Preparation of DAB (PA) 4 (Steps a, b N 1.5).

900 ml of water and 75 g (0.85 mol) of 1,4-diaminobutane (substrate) were introduced into a 2-liter three-neck flask equipped with a stirrer, condenser, thermometer and dropping funnel. The mixture was then cooled to 10 ° C, and a solution of 200 g (3.8 mol) of acrylonitrile was added dropwise thereto over 2 hours. The reaction mixture thus obtained was then heated for 9 hours (temperature 65 ° C).

After cooling the mixture to room temperature, the water and excess acrylonitrile were azeotropically evaporated. The residue thus obtained, containing DAB (ACN) 4 and water, was then reduced with a Raney cobalt catalyst which had not been pretreated. The reaction was stopped after 1 hour to obtain the desired product as a colorless oil. Analysis of the product by ^13C NMR showed that pure DAB was established (PA) 4. The yield was 98%.

¹³ C NMR spectrum (50 MHz, D ₂ O): 53.4 ppm, NCH 2 CH 2 CH 2 CH 2 (2x); 51.1 ppm, NCH 2 CH 2 CH 2 NH 2 (4x); 39.5 ppm, CH2NH2 (4x); 28.8 ppm, CH 2 CH 2 NH 2 (4x); 23.9 ppm, NCH2CH2CH2CH2N (2x).

Example XXVII. Thermal stability of the compounds prepared in Examples 1-7.

The heat stability of the dendritic macromolecules obtained in Examples 1 to 7 was measured by thermographic analysis (TGA). This was done by heating about 2.5 mg of the test product with a Perkin Elmer apparatus (7 runs) under a neon atmosphere from 30 ° C to 900 ° C, at a rate of 20 ° C / mmut. Table 1 lists the temperatures at which maximum product decomposition occurs.

Table 1

TGA results of the products obtained in Examples 1-7

Product Temperature (° C) DAB (ACN) 4 330.1 DAB (PA) 4 330.0 DAB (ACN) 4 (ACN) 6 331.8 DAB (PA) 4 (PA) 8 378.0 DAB (PA) 4 (PA) 8 (ACN) 16 332.0 DAB (PA) 4 (PA) 8 (PA) 16 424.0 DAB (PA) 4 (PA) 8 (PA) 16 (ACN) 32 331.5

Example XXVIII. Production of DAB (ACN) 4 (step a, N 1).

900 ml of water and 75 g (0.85 mol) of diamicobutac were introduced into a 2-liter three-neck flask equipped with a stirrer, condenser, thermometer and dropping funnel. After the mixture had cooled to 10 ° C, a solution of 200 g of acrylonitrile was sprayed onto it

171,776 ml of methanol at such a rate that the temperature of the reaction mixture remained below 15 ° C. After all the addition was made, the reaction mixture was kept for two hours at room temperature and then heated for 9 hours at 65 ° C. The reaction mixture was then cooled to room temperature and the obtained product was isolated.

The results of 1 H NMR and ¹³ C NMR spectroscopy and mass spectrometry indicated that the product isolated was DAB (ACN) a.

^N C NMR spectrum (50 MHz, D 2 O): 119.0 ppm, CN; 53.1 ppm, NCH2 (CH2) 3; 49.4 ppm, NCH2CH2CN; 24.9 ppm, NCH2CH2CN; 16.9 ppm, CH2CN.

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

Example XXIX. Preparation of DAB (PA) a (PA) s (PA) i6 (steps a, b, c, N 3.5).

A 250 ml three-necked flask equipped with a stirrer, condenser, thermometer and dropping funnel was charged with 30 ml of water and 5.0 g (58 mmol) of diaminobutane. After cooling the mixture to 10 ° C, a solution of 15 g (280 mmol) of acrylonitrile was added dropwise thereto at such a rate that the temperature was kept below 15 ° C. After all the solution had been added, the mixture was kept for two hours at room temperature, then the reaction mixture was heated for 16 hours at 45 ° C.

After cooling the reaction mixture to room temperature, water and excess acrylonitrile were evaporated. 2.5 g of the obtained product, which is (DAB (ACN) A), was dissolved in 4 ml of methanol. This solution was introduced into a 160 ml autoclave with 8.0 g of Raney cobalt catalyst (Grace type 2724, promoted Cr). The autoclave was then closed, purged several times with H 2 gas and heated to 80 ° C under a pressure of 29.4-10 ⁵ Pa while stirring the contents of the reactor. These reaction conditions were maintained for one hour. After removing the catalyst by filtration and evaporation of the water, 2.0 g of the residue (DAB (PA) a) was dissolved in 20 ml of water, to which solution was added 5.4 g of acrylonitrile dropwise at 10 ° C. The mixture is kept for two hours at room temperature and then heated for 16 hours at 40 ° C. After cooling, the water and excess acrylonitrile were evaporated under reduced pressure. The colorless residue thus obtained (pure DAB (PA) A (ACN) g) was then reduced in the same manner as DAB (ACN) A as described in this example. Complete and selective reduction was achieved within 90 minutes.

The DAB (PA) a (PA) g thus formed was dissolved in 30 ml of water, and then 5.0 g of acrylonitrile was added dropwise at 10 ° C. The reaction mixture was then kept for two hours at room temperature and then heated for 16 hours at 40 ° C. After cooling, the water and excess acrylonitrile were evaporated off under reduced pressure, whereupon the colorless residue, i.e. DAB (PA) ą (PA) g (ACN) i6, was completely and selectively reduced over two hours to DAB (PA) ą (PA) g ( PA) i6 as described in this example for the reduction of DAB (ACN) a.

The examples show that different generations of dendritic macromolecules according to the invention can be synthesized. The synthesized macromolecules according to the invention are not susceptible to degradation by the hydrolysis reaction. The synthesis can be carried out in various solvents, using different catalysts and different reaction conditions. It has also been shown that it is possible to carry out the various reaction steps one after the other without the need to isolate the (intermediate) product obtained after each step, which means that it is very easy to scale up the process. The outermost generation of dendritic macromolecules can be modified with a number of functional groups. Finally, it has been shown that the dendritic macromolecules according to the invention have very good heat resistance.

Claims (15)

Patent claims A method for producing a dendritic macromolecule having a core and branches extending from the core, characterized in that, when producing a macromolecule with a molecular weight of at least 1600, or in which the generation number N is 3-10, the reaction steps a) to c) are carried out: a) reacting substantially each core functional group with a monomeric vinyl cyanide unit; b) reducing substantially each attached nitrile unit to the amino group, optionally in the presence of a reduction catalyst; c) reacting substantially any amino group with monomeric vinyl cyanide units; wherein steps b) and c) are carried out alternately. 2. The method according to p. The process of claim 1, wherein the core comprises functional groups selected from hydroxyl groups, primary and secondary amino groups, thiol groups and groups formed by carbon compounds with electronegative substituents. 3. The method according to p. The process of claim 2, wherein the core is functionalised with a hydroxyl group, a primary amino group and / or a secondary amino group. 4. The method according to p. The process of claim 3, wherein the core is selected from the group consisting of polymethylene diamines and ammonia. 5. The method according to p. The process of claim 4, wherein the 1,4-diaminobutane core is used. 6. The method according to p. The process of claim 1, wherein acrylonitrile or methacrylonitrile is used as the monomeric vinyl cyanide mer. 7. The method according to p. A process as claimed in claim 1, characterized in that during steps a) and / or c) a ratio of the number of vinyl cyanide monomeric units to the number of reactive sites is at least 1. 8. The method according to p. 1, characterized in that: a) at least 95% of the core functional groups are caused to react with the monomeric vinyl cyanide unit, b) reduced from at least 95% of attached nitrile units to the amino group, and (c) at least 95% of the amine groups are reacted with monomeric vinyl cyanide units. 9. The method according to p. 8, characterized in that: a) at least 99% of the core functional groups are made to react with the monomeric vinyl cyanide unit, b) reducing at least 99% of the attached nitrile units to an amino group, and (c) at least 99% of the amine groups are reacted with vinyl cyanide monomeric units. 10. The method according to p. The process of claim 1, wherein step b) of the reaction is carried out in the presence of a reducing catalyst containing at least a metal from the group consisting of nickel, cobalt, platinum, palladium and rhodium. 11. The method according to p. The process of claim 10, wherein the catalyst is selected from the group consisting of Raney Nickel and Raney Cobalt. 12. The method according to p. The process of claim 11, characterized in that 1-35% by weight of catalyst is used, based on the total weight of the reaction mixture. 16. The method of claim 1, characterized in that: stepb) of the reaction is carried out in a H ₂ sphere under hydrogen pressure of 1 · 10Spa - 500 · 10spa and at a temperature of 20 - 200 ° C. 171 776 17. The method according to p. The process of claim 1, characterized in that the individual reaction steps are carried out in water, methanol or a mixture thereof. 18. A method for producing a dendritic macromolecule containing a core and branches protruding from the core, characterized in that in the case of producing a macromolecule with the desired N 2-10 generation, the reaction steps a) to c) are carried out: a) reacting substantially each core functional group with a monomeric vinyl cyanide unit; b) reducing substantially each attached nitrile unit to an amino group in the presence of a reducing catalyst containing at least a metal from Group VIII of the Periodic Table of the Elements and H2 gas, and c) reacting substantially any amino group with monomeric vinyl cyanide units; wherein steps b) and c) are carried out alternately (N-1) times.