NL1006097C2 - A method of making a branched macromolecule, the branched macromolecule and uses of the branched macromolecule. - Google Patents

Description

- 1 -

METHOD FOR MANUFACTURING A BRANCHED MACROMOLECULE THE BRANCHED MACROMOLECULE AND

APPLICATIONS OF THE BRANCHED MACROMOLECULE

The invention relates to a process for preparing a branched macromolecule of the order N.

A method of preparing a second order branched macromolecule is known from US-A-5,418,301. US-A-5,418,301 discloses a method in which a core molecule containing one or more hydroxy groups is contacted with a compound containing one carboxyl and at least two hydroxy groups, the amount of this compound being chosen such that it number of carboxyl groups is equal to the number of hydroxy groups of the core molecule. After the esterification, an amount of the compound with one carboxyl and at least two hydroxy groups is added again, the amount of this compound being chosen such that the number of carboxyl groups is equal to the number of free hydroxy groups (hydroxy groups after the first esterification) of the first order). This last step can optionally be repeated one or more times. In this way, a branched polymer diverges. This process can be performed in one reactor. It is recommended that the water generated during the esterification is continuously distilled off. A drawback of this process is that the carboxyl groups do not only react with the hydroxyl groups of the last-formed order present on the macromolecule, but also with hydroxyl groups of the newly-formed order and with 100609 in the reaction mixture. - 2 - present hydroxyl groups of molecules not yet bound to the macromolecule. This results in irregularities in the build-up of the subsequent orders, which is shown, among other things, by a molecular weight distribution.

The object of the invention is to provide a method in which this drawback does not occur or occurs to a lesser extent.

This object is achieved according to the invention by a method comprising the following steps: a) Contacting a core molecule containing one or more end groups, consisting of a hydroxy, a thiol, or an amino group, with a, molar amount of a compound of a first type, which contains a primary and a tertiary isocyanate group, relative to end groups; b) contacting the product obtained in the previous step with a compound of a second type containing a first reactive group which is reactable with a tertiary isocyanate and one or more groups which are reactive with a primary isocyanate and are less reactive with a tertiary isocyanate than the first reactive group, the amount of the compound of the second kind being selected to be molar equivalent to an amount of the compound of the first kind added in the previous step followed by alternately performing steps (c) and (b) such that the total number of steps is N and N is £ 2.

c) contacting the product obtained in step (b) with a compound of the first kind, wherein the amount of the compound of the first kind is chosen to be molar equivalent to that in step (b) added 1006097-3 - number of less reactive groups, wherein steps (a), (b) and (c) are performed in the presence of an ionic metal complex containing a metallic element of groups III, IV or VII of the Periodic Table of elements and an interchangeable counterion.

The process according to the invention achieves that a branched polymer is formed in one reactor, which has a regular build-up of successive 10 orders. It has been found that the branched polymer prepared by the process of the invention has a very low molecular weight distribution.

An advantage of the method according to the invention is that no water or other reaction products need to be removed between the different steps.

Another method of preparing a branched polymer with a regular build-up of the successive orders is described by Zeng and Zimmerman in J.Am.Chem.Soc. 1996, 118, 5326-5327.

It describes how two molecules (4-tert-butylphenoxy) ethanol are coupled to 1-iodobenzyl, 3,5-25 dicarboxylic acid under Mitsunobu conditions (in the presence of PPh3, diethyl azodicarboxylate (DEAD) in THF), whereby a branched molecule of the first order is formed. The center of this molecule is an aryliodide, which is coupled via a Sonogashira reaction in the presence of Pd (Pph3) 2Cl2, Cul and triethylamine to the acetylene groups of 3.5-30 diethynylbenzyl alcohol to form a second order branched macromolecule. A drawback of the method described by Zeng and Zimmerman is that the environments in which the two different reaction steps must be carried out are incompatible with each other, so that the subsequent steps cannot be carried out in one reactor and in one and the same medium. Another drawback of this 1006097-4 convergent build-up of a branched macromolecule is that the reaction takes place in the center of the macromolecule, decreasing the yield as the number of orders increases. An advantage of the diverging method according to the invention is that the reaction takes place on the outer shell of the macromolecule, so that the yield is independent of the number of orders.

In this description, a branched macromolecule of the order N 10 is understood to mean a macromolecule that counts shells from the core molecule N, each reaction step adding one shell and N 2. The macromolecule therefore contains at least two shells formed in the first two steps. (a) and (b). If the macromolecule 3 contains shells, they are formed in steps (a), (b) and (c). A four shell macromolecule is formed by sequentially performing steps (a), (b), (c) and (b).

In the method according to the invention, a core molecule containing one or more end groups, consisting of a hydroxy, a thiol, or an amino group, is contacted with a compound of a first kind. Suitable core molecules may include: a) an aliphatic, cycloaliphatic or aromatic diol, b) an aliphatic, cycloaliphatic or aromatic triol, c) an aliphatic, cycloaliphatic or aromatic tetrol, d) a sugar alcohol, e) di (trismethylolpropane) or dipentaerythriol, f) an α-alkylglucoside, or, h) a monofunctional alcohol, with 1-10,000 carbon atoms.

i) an alcohol with a functional group that does not react with isocyanate having 1-10,000 100,609 7-5 carbon atoms.

Suitable core molecules are trimethylolpropane (TMP), pentaerythritol, bis (trimethylolpropane), tris (aminoethyl) amine, 5 bis (aminoethyl) amine, tris (aminopropyl) amine, bis (aminopropyl) amine, bis (hexamethylene) triamine, tertrakis (aminopropyl) 1,4-butanediamine, trisaminononane, 1,4-butanediamine, 1,6-hexanediamine, ethylenediamine, pentaerythrinolatrakis (2-10 mercaptoacetate), pentaerythriol tatrakis (2-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropananthropin (3-mercapto-acetate) 1,6-hexanedithiol, 1,4-butanedithiol and 1,2-ethanedithiol.

Preferably, the core molecule contains 2,3 or 4 chemically equivalent end groups. This has the advantage that the reactivity with the compound of the first kind is the same for all end groups, thereby promoting a regular build-up of the macromolecule. Examples include: trimethylolpropane, pentaerythritol, tris (trimethylolpropane), tris (aminoethyl) amine, tr is (aminopropyl) amine, tertrakis (aminopropyl) 1,4-butanediamine, trisaminononane, 1,4-butanediamine, 1.6 Hexanediamine, ethylenediamine, pentaerythriolatatrakis (2-mercaptoacetate), pentaerythrioltatrakis (2-mercapto propionate), trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tr (3-mercaptopropionate), 1,6-30-hexanedithiol 1,2 ethanedithiol.

The compound of the first kind contains a primary and a tertiary isocyanate group and preferably contains 4-20 carbon atoms. By this is meant that the compound of the first kind is an aliphatic diisocyanate with one isocyanate group attached to a primary carbon atom and one isocyanate group attached to a tertiary carbon atom. The advantage of such a compound of the first kind is that the isocyanate group attached to the primary carbon atom is more sterically accessible than the isocyanate group bound to the tertiary carbon atom, so that the two isocyanate groups have different reactivity. Such compounds can be represented by the formula (1):

NCO

R1-C-R3-CH2-NCO

I (1) R2 wherein R 1 and R 2 have the same or different (C 1 -C 4) alkyl groups and R 3 contains a divalent, optionally branched saturated aliphatic hydrocarbon radical.

Cycloaliphatic diisocyanates can also be used with one sterically more accessible isocyanate group attached to a primary carbon atom and one sterically less accessible isocyanate group connected to a tertiary carbon atom. These compounds can be represented by formula (2)

25 R / NCO

o c / \

30 R7 r8-CH2-NCO

where: - R4 = (C 1 -C 4) alkyl group 35 - R 5 and R 6 = equal or different bivalent, optionally branched saturated aliphatic (C1-C3) hydrocarbon radical, 1006097 - 7 - - R 7 = hydrogen or (¢ ^ -04) alkyl group - R® = bivalent, optionally branched, saturated aliphatic (C 1 -C 6) hydrocarbon residue and - n = 0 or n = 1 5 Examples of suitable diisocyanates are 1,4-diisocyanato-4-methyl-pentane, 1,5-diisocyanato- 5-methylhexane, 3 (4) -isocyanatomethyl-1-methylcyclohexyl isocyanate, 1,6-diisocyanato-6-methyl-heptane, 1,5-diisocyanato-2,2,5-trimethylhexane and 1,7-10 diisocyanato-3 7-dimethyloctane and 1-isocyanato-1-methyl-4- (4-isocyanatobut-2-yl) -cyclohexane, 1-isocyanato-1,2,2-trimethyl-3- (2-isocyanatoethyl) -cyclopentane, 1-isocyanato-1,4-dimethyl-4-isocyanatomethyl-cyclohexane, 1-isocyanato-1,3-dimethyl-3-isocyanatomethyl-cyclohexane, 1-isocyanato-1-butyl-3- (4-isocyanatobut -1-yl) -cyclopentane, 1-isocyanato-1,2-dimethyl-3-ethyl-3-isocyanatomethyl-cyclopentane. The method of preparation of such diisocyanates is described in, for example, DE-A-3608354, DE-A-3620821 and EP-A-153561.

Preferably the compound of the first kind is 3 (4) -isocyanatomethyl-1-methylcyclohexyl isocyanate, (IMCI) or 1,4 diisocyanato-4-methylpentane.

In the method according to the invention, the core molecule is contacted with an molar amount of the compound of the first kind equivalent to the end groups of the core molecule. This achieves that only the most reactive isocyanate group reacts with the end groups of the core molecule and the reaction proceeds stoichiometrically.

The uncatalyzed reaction between the core molecule and a compound of the first kind shows a sharply decreasing selectivity at higher temperatures when the end groups of the core molecule consist of hydroxy or thiol groups. The selectivity of this reaction is understood to mean the ratio between the primary isocyanate groups reacted with the end groups and the total number of primary isocyanate groups. Generally, at room temperature, the selectivity of the reaction is high, but the reaction rate is relatively slow. Therefore, the reaction is carried out in the presence of a catalyst containing an ionic metal complex based on a metallic element of groups III, IV or VII of the Periodic Table of the Elements and at least one exchangeable counterion. This ensures that the reaction proceeds quickly at a temperature between room temperature and 100 ° C and that a high selectivity is also obtained. The reaction is preferably carried out in a solvent with a boiling point between room temperature and 100 ° C under reflux of the solvent. The catalyzed reaction proceeds almost quantitatively in 0.5 to 8 hours.

The coupling of the diisocyanate to the hydroxy, amino, or thiol group of the core molecule 20 takes place exclusively or almost exclusively via the most reactive isocyanate group by using the catalyst. Surprisingly, the reactivity difference between the isocyanate groups having a hydroxy group present in these compounds was found to be more than a factor of 100.

Suitable metallic elements in the appropriate valency are aluminum (III), tin (IV), manganese (III), titanium (HI), titanium (IV) and zirconium (IV).

Preferably tin (IV), titanium (IV), manganese (III) and zirconium (IV) are used.

The number of counterions is between 1 and 4.

For tetravalent metals, it is possible, for example, to use 4 monovalent counterions, 2 divalent 35 counterions, 1 divalent counterion in combination with 2 monovalent counterions or to use 1 trivalent in combination with 1 monovalent counterion. Preferably 10 6 U97-9, 4 monovalent counterions are used.

For trivalent metals, the number of counterions is between 1 and 3 and preferably 3 monovalent counterions are used.

Examples of suitable counterions are halides, preferably chloride, (C 1 -C 20) alkoxides, preferably (C 1 -C 20) alkoxide, (C 2 -C 20) carboxylates, preferably (C 2 -C 20) carboxylates, enolates, preferably 2,4-pentanedione (acetylacetonates) and alkyl esters of malonic acid and acetylacetic acid, phenolates, naphthenates, cresylates and mixtures of said counterions.

Suitable catalysts are, for example, aluminum (III) acetate, aluminum (III) acetylacetonate, aluminum (III) 2,2,6,6-tetramethyl-3,5-heptanedionate, aluminum (III) ethoxide, aluminum (III) isopropoxide, aluminum (III) sec-butoxide, aluminum (III) tert-butoxide, tin (IV) chloride, tin (IV) bromide, tin (IV) iodide, tin (IV) acetate, tin (IV) 20 bis (acetylacetonate) dichloride, tin (IV) bis (acetylacetonate) dibromide, manganese (III) acetate, manganese (III) acetylacetonate, manganese (III) fluoride, titanium (IV) chloride, titanium (IV) bromide, titanium (IV) methoxide, titanium (IV) ethoxide, 25 titanium (IV) isopropoxide (TYZOR TPT ™), titanium (IV) propoxide, titanium (IV) butoxide (TYZOR TBT ™), titanium (IV) 2-ethylhexoxide (TYZOR TOT ™), titanium (IV) acetylacetonate, titanium (IV) bis (acetylacetonate) diisopropoxide (TYZOR AA ™), titanium (IV) 30 bis (ethyl acetoacetato) diisopropoxide, titanium (IV) (triethanolaminato) isopropoxide (TYZOR TE ™), zirconium (IV) chloride, zirconium (IV) bromide, zirco nium (IV) acetate, zirconium (IV) 2-ethylhexanoate, zirconium (IV) ethoxide, zirconium (IV) butoxide, 35 zirconium (IV) tert-butoxide, zirconium (IV) citrate ammonium complex, zirconium (IV) isopropoxide, zirconium (IV) propoxide, zirconium (IV) acetylacetonate t006097-10 - and zirconium (IV) trifluoroacetylacetonate.

Preferably, titanium (IV) butoxide, zirconium (IV) acetylacetonate, zirconium (IV) butoxide, tin (IV) acetate, manganese (III) 5 acetylacetonate, titanium (IV) isopropoxide, zirconium (IV) 2-ethylhexanoate and tin ( IV) chloride.

The catalyst complex can also contain one or more neutral elements such as, for example, alkyl cyanide, crown ether, (poly-) ether, such as, for example, polytetrahydrofuran, polyethylene glycol or tetrahydrofuran, dialkyl sulfide or tertiary amine.

The amount of catalyst is usually between 0.01 and 3% by weight (relative to the compound which can react with 15 isocyanate groups and the compound which contains isocyanate groups).

In step (b), the product obtained in the previous step is contacted with a compound of a second kind containing a first reactive group reactable with a tertiary isocyanate and one or more groups reactive with a primary isocyanate and are less reactive with the tertiary isocyanate than the first reactive group. This ensures that the groups reactive with the tertiary isocyanate fully react with it. The "previous step" means reaction step (a) when step (b) is performed for the first time. For all subsequent times (b) is performed, step 30 (c) is the preceding step.

Suitable compounds of the second kind are compounds containing from 4 to 40 carbon atoms and belonging to the group of the amino alcohols, or aminothiols, which contain one primary or secondary amino group as the reactive group and at least one hydroxy or thiol group as the less reactive group. Polyols with one 1006097-11-reactive hydroxy group and at least one less reactive hydroxy group are also suitable compounds of the second type. Preferably, the compound of the second kind is tris (methylol) methylamine (TRIS) or mono- or 5 bis-alkanolamines of the formula 3: R '10 "hH ^ c- ^ oh], (3) H] Where x = 0 or 1, y = 2-x, n = 1 or 2, m = 0 or 1, R -H or alkyl C 1 -C 1 R '= alkyl C 1 -C 1 and R "= alkyl Examples of these are (N-alkyl) ethanolamine, (N-alkyl) isopropanolamine, diethanolamine or diisopropanolamine The advantage of using 20 amines is that they react substantially quantitatively with the tertiary reactive isocyanate groups of the diisocyanate without this reaction causing the presence of requires a catalyst, or is adversely affected by the presence of the catalyst, thereby ensuring that no catalyst needs to be removed between the various steps The amount of the compound of the second type is selected to be molar equivalent to the amount of the compound of the first kind added in the previous step.

In step (c), the product obtained in step (b) is contacted with a compound of the first kind. The reaction between the primary isocyanate group of the compound of the first type 35 and one or more groups, of the compound of the second type, which are reactive with a primary isocyanate (the hydroxy or thiol groups) is carried out in 1006097-12 - in presence of the aforementioned catalyst. The temperature at which this reaction is carried out generally ranges from room temperature to 100 ° C. The amount of the compound of the first kind is selected to be molar equivalent to the number of less reactive groups added in step (b).

Steps (a), (b) and (c) are carried out in the presence of the above-mentioned ionic metal complex 10 which contains a metallic element of groups III, IV or VII of the Periodic Table of the Elements and an exchangeable counterion. Preferably the (metallic) element in the method according to the invention is zirconium (IV). Preferably the counter ion is acetylacetonate, butoxide, or 2-ethylhexanoate.

In the method of the invention, the compounds of the second type used in steps (b) may be the same or different. According to a preferred embodiment of the method according to the invention, the compound of the second type is different in at least two steps (b). In this way it can be achieved that a cavity is formed within the macromolecule. For this purpose, the compounds of the second type can deviate from each other in at least two steps (b) in different ways.

A first method of creating a cavity within the macromolecule is by using a compound of the second type at least once with only one less reactive group. In order to obtain a highly branched macromolecule, a compound of the second type is generally used in which at least two groups which are reactable with a primary isocyanate group are present. However, by carrying out step (b) one or more times in succession with a compound of the second type in which only one group reactable with a primary isocyanate group is present 10 0 6 ü 9 7 - 13 - one or more shells with less branches formed. This creates a cavity in the macromolecule.

The size of this cavity can be selected by the number of times in succession in step (b) a compound of the second type is used with only one group reactable with a primary isocyanate.

A second method of creating a cavity within the highly branched macromolecule is to use a compound of the second type at least once in step (b), the distance between the groups reactable with primary and tertiary isocyanate being greater then said distance in the connections of the second type which is used in the other steps (b).

A combination of the first and second methods can also be used to create a custom cavity within the macromolecule. The advantage of custom cavities is that certain compounds can be selectively included therein and that this can also influence diffusion to and from the cavity.

In a preferred embodiment of the method according to the invention, the compound of the second kind contains in at least one of the steps (b) at least one functional group, which does not react with isocyanate, or which interferes with the reaction between isocyanate and the isocyanate-reactable groups. The functional group which does not react with isocyanate is preferably selected from the series of compounds having an ethylenic or ethynic unsaturation, a crown ether, or from trisalkylphosphine, trisarylphosphine, pyridine, bipyridine, phenanthroline, trisalkylamine, dialkyl sulfide, guanidine, alkylimidazoline benzoquinone, anthraquinone, hydroxybenzophenone, ketones and aldehydes, or checkered amines, alcohols thiols and acids. This achieves that additional? 0 0 8 U 9 7 - 14 - functional groups are incorporated, which can interact with guest molecules in an internal cavity, if necessary after the release, in the macromolecule. Guest molecules can be metal ions or complexes, dyes, peroxides, light-active organic or inorganic compounds, organic bases or acids, or compounds with a catalytic or pharmaceutical action.

In a preferred embodiment of the method according to the embodiment, the compound of the first kind in the last step (c) to be carried out is replaced by a compound containing only one primary isocyanate group. This achieves that the isocyanate groups react with the end groups of the product obtained in the last step (b) and that the product thus obtained no longer contains isocyanate groups. Examples of such monoisocyanates are: alkyl isocyanates (C2-C20), optionally substituted, branched or unsaturated, and 3-isocyanato-20-propyltri (m) ethoxysilane. For example, if the macromolecule contains 3 shells, they are formed in steps (a), (b) and step (c), as described above.

In another preferred embodiment of the method of the embodiment, the compound of the second kind is replaced in the last time that step (b) is performed by a derivatizing agent: a compound containing one reactive group reactable with a tertiary isocyanate. For example, if the macromolecule contains 2 shells, they are formed in step (a) and in step (b) as described above. This prevents, for example, an increase in molecular weight after the reaction, for example by hydrolysis of the isocyanate groups, or by urea formation. The end groups of the macromolecule also determine its character. For example, by suitable choice of the end groups, the 10ϋ6υ9 (- 15 - solubility of the macromolecule can be influenced. Suitable derivatizing agents for carrying out the final step (b) reaction are, for example, diethylamine, mono- and bisalkylamines (C2-C40), 5 optionally substituted or unsaturated, 3-amino-propyl silane derivatives, amino acids (natural and synthetic), and amino acid derivatives, alcohols (C 1 -C 10) optionally substituted or unsaturated.

The reactions (b) and (c) are preferably carried out under nitrogen.

All reactions are preferably carried out in a solvent in which all components dissolve well. Suitable solvents are low viscosity solvents which do not themselves react with isocyanate groups. In order to prevent an uncontrolled build-up of the branched macromolecule by hydrolysis of isocyanates and urea formation, it is recommended to pre-dry the solvent with, for example, a type 3A mole screen.

The invention also relates to a branched macromolecule obtainable by the method according to the invention. Branched macromolecules based on isocyanates are known from DE-A-195 240 045.

Described herein are dendritic macromolecules which are formed by coupling a molecule ABn to each functional group B1 to a core molecule with at least 2 functional groups B1 and to coupling a subsequent ABn group to each group B and so on, wherein n is at least 2 and A is a 30 is isocyanate group. Nowhere in DE-A-195 240 045 is it stated that A is a diisocyanate with a primary and a tertiary isocyanate.

The advantage of the branched macromolecule according to the invention (with primary and tertiary isocyanate) is the lower polydispersity.

Preferably, the polydispersity of the macromolecule according to the invention is less than 1.5.

10060S.

- 16 -

More preferably less than 1.1. Even more preferably, the polydispersity is less than 1.05.

A drawback of the method described in DE-A-195 240 045 is that a lower polydispersity can only be obtained by applying protection and deprotection steps.

A further advantage of the method according to the invention is that the preparation can be stopped after step (b) or after step (c), while the method described in DE-A-195 10 240 045 always ends on isocyanate-reactable groups .

The invention also relates to the use of this macromolecule as a crosslinking agent, as a lubricant, as a catalyst or catalyst support, as a photosensitizer, as a colorant carrier and in pharmaceuticals.

Example I

A second order 20 branched macromolecule was prepared in the following manner: To 25.00 ml of a 0.200 M solution of trismethylolpropane (TMP, 99 +%, Aldrich) in THF was added 2 ml of a 0.075 M solution of zirconium (IV) acetyl acetate in THF added.

Then 25.00 ml of a 0.600 M solution of IMCI (99 +%, Bayer) was slowly added at room temperature. While stirring, the mixture was quickly heated to reflux temperature (58 ° C). After stirring at reflux temperature for 4 hours, the mixture was cooled, after which slowly 10.00 ml of a 1.500 M solution of diethylamine (DA) in THF was added. After 30 minutes, a sample was taken from this mixture, which was diluted with HPCL-grade THF (1: 5) and injected immediately afterwards into a Gel Permeation Chromatography column. The result is shown in bottom line 35 of Figure 1. The sharp peak at 32 min.

corresponds to the ideal “trimer” structure. There is no visible signal from 1006097 - 17 - unreacted IMCI (35.5 min.). The peak at 30.5 min. with an area smaller than 2% of the peak at 35.5 min. can be attributed to a "pentameric" structure consisting of 2 TMP units and 5 IMCI / DA 5 units. In this error structure, one of the five IMCI units has reacted via both the primary and tertiary isocyanate groups. The equally small peaks at 32.5 and 34 min come from incomplete structures, consisting of one TMP unit and only 2 or 1 IMCI units, respectively. The molecular weight spread expressed in the polydispersity (= Mw / Mn) of the whole is 1.03, which means that almost all molecules have an ideally branched structure. The polydispersity was determined from the GPC measurement using polystyrene as the standard.

The reaction mixture was further evaporated to obtain a colorless glassy material.

20

Example II

A fourth order branched macromolecule was prepared in the following manner: The same procedure was followed as for the preparation of a first order branched macromolecule except that instead of 10 ml diethylamine 50.00 ml of a 0.6 M solution of diethanolamine in THF was added. After stirring for 16 hours, 11.652 g of IMCI and 4.0 ml of the 0.075 M 30 solution of zirconium (IV) acetylacetate in THF were added and warmed to reflux temperature (58 ° C). After stirring at the reflux temperature for 4 hours, the mixture was cooled and 20 ml of a 1,500 M solution of diethylamine (2.2 g) in THF was slowly added. After 30 minutes a sample was taken from this mixture, which was diluted with HPCL-grade THF (1: 5) and injected immediately afterwards in a Gel 1006U97 - 18 -

Permeation Chromatography column. The result is shown in the middle line of Figure 1. Around the sharp peak of about 30 minutes from the ideally branched macromolecule, small shoulders 5 of higher and lower molecular weight material are visible. The polydispersity of the macromolecule formed was 1.06.

After evaporation of the reaction mixture, a colorless glassy material was again obtained. This fourth order macromolecule.

Example III

A sixth order branched macromolecule (G3) was prepared in the following manner: The same procedure was followed as for the preparation of a second order branched macromolecule except that instead of 20 ml of diethylamine, 25.00 ml of a 0, 6M solution of diethanolamine in THF was added.

This mixture was stirred at room temperature for 16 hours.

Then 5.827 g of IMCI and 2.0 ml of the 0.075 M solution of zirconium (IV) acetyl acetate in THF were added and heated to reflux temperature (58 ° C). After stirring at reflux temperature for 4 hours, the mixture was cooled and 40 ml of a 1,500 M solution of diethylamine (4.4 g) in THF was slowly added. After 30 minutes, a sample was taken from this mixture, which was diluted with HPCL-grade THF (1: 5) and injected immediately afterwards into a Gel Permeation Chromatography column. The result is shown in the top line of Figure 1. In addition to the sharp peak at about 28 min from the ideally branched macromolecule shown in Figure 2, a small peak is visible at 27 min from material with a higher molecular weight. The polydispersity of the whole was 1.07. After evaporation, a colorless glassy material was obtained.

1006097

Claims (19)

A method for preparing a branched macromolecule of the order N, comprising the following 5 steps: a) Contacting a core molecule comprising one or more end groups consisting of a hydroxy, a thiol, or an amino group containing with a molar amount equivalent to 10 end groups of a compound of a first kind containing a primary and a tertiary isocyanate group; b) contacting the product obtained in the previous step with a compound of a second type containing a first reactive group which is reactable with a tertiary isocyanate and one or more groups which are reactive with a primary isocyanate and are less reactive with a tertiary isocyanate than the first reactive group, the amount of the compound of the second species being selected to be molar equivalent to an amount of the compound of the first added in the previous step type followed by alternately performing steps (c) and (b) such that the total number of steps N is N and N £ 2.30 c) contacting the product obtained in step (b) with a compound of the first kind, wherein the amount of the compound of the first kind is selected to be molar equivalent to the number of less reactive groups added in step 35 (b), the sta ppen (a), (b) and (c) are carried out in the presence of an ionic metal complex containing a metallic element of groups III, IV or VII of the Periodic Table of the Elements and an exchangeable counterion. The method of claim 1, wherein the core molecule contains 2,3 or 4 chemically equivalent end groups. The method of claim 2, wherein the core molecule is trimethylol propane, pentaerythritol, 10 bis (trimethylol propane), tris (aminoethyl) amine, tr (aminopropyl) amine, tertrakis (aminopropyl) 1,4-butanediamine, tr isaminononane-1,4- butanediamine, 1,6-hexanediamine or ethylenediamine. 4. The method of claim 3, wherein the compound of the first kind is 3 (4) - isocyanatomethyl-1-methylcyclohexyl isocyanate, or 1,4-diisocyanato-4-methylpentane. A method according to any one of claims 1-4, wherein the compound of the second kind is 20 (N-alkyl-) ethanolamine, (N-alkyl) isopropanolamine, diethanolamine, diisopropanolamine, or trismethylolmethylamine, the alkyl group of which contains 1-20 carbon atoms . 6. A method according to any one of claims 1-5, wherein the (metallic) element is zirconium (IV). A method according to any one of claims 1-6, wherein the counterion is chloride acetate, acetylacetonate, butoxide, or 2-ethylhexanoate. 8. A method according to any one of claims 1-7, wherein the compound of the second kind is different in at least two steps (b). 9. A method according to any one of claims 1-8, wherein the compound of the second kind in at least one of steps (b) contains at least one functional group that does not react with isocyanate. 10. A method according to claim 9, wherein the functional group which does not react with isocyanate 1005097-21 - is selected from the series of compounds carbon black an ethylenic or ethynic unsaturation, a crown ether, or from trisalkylphosphine, trisarylphosphine, pyridine, bipyridine, phenanthroline, trisalkylamine , dialkyl sulfide, guanidine, alkyl imidazoline benzoquinone, anthraquinone, hydroxybenzophenone, ketones and aldehydes, or blocked amines, alcohols, thiols and acids. 11. A method according to any one of claims 1-10, wherein the compound of the first kind in the last step (c) to be carried out is replaced by a compound containing only one reactive group which is reactable with the end groups of the product obtained in step (b). 12. A method according to any one of claims 1-11, wherein the compound of the second kind in the last time that step (b) is performed is replaced by a compound containing one reactive group reactable with a tertiary isocyanate. Branched macromolecule obtainable from the method according to any one of claims 1-12. 14. Use of the macromolecule according to claim 13 in a coating, as a crosslinking agent, 15. Use of the macromolecule according to claim 13 as a lubricant. Use of the macromolecule of claim 13 as a catalyst or catalyst support. Use of the macromolecule of claim 13 in pharmaceuticals. 18. Use of the macromolecule of claim 13 as a photosensitizer. 19. Use of the macromolecule according to claim 14 as a dye carrier. 1006097