EP1646675A1

EP1646675A1 - Method for producing hyperbranched polymers

Info

Publication number: EP1646675A1
Application number: EP04740320A
Authority: EP
Inventors: Jean-François STUMBE; Bernd Bruchmann; Joelle Bedat
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2003-07-11
Filing date: 2004-06-25
Publication date: 2006-04-19
Also published as: CN1823118A; US20060199913A1; CN100447180C; WO2005007726A1; DE10331770A1

Abstract

The invention relates to a method for producing hyperbranched polymers, said method being characterised in that compounds of general formula (1), wherein the variables are defined as follows, are reacted in the presence of a catalyst, optionally with at least one compound of general formula (1a) wherein the variables are also defined as follows: x represents sulphur or oxygen; R<1> and R<3> are the same or different and are selected from hydrogen, C1-C6 alkyl, C3-C12 cycloalkyl, C6-C14 aryl; R<2> and R<4> are the same or different and are selected from hydrogen, C1-C6 alkyl, C3-C12 cycloalkyl, C6-C14 aryl; Z<1> and Z<2> are the same or different and are selected from COOH and COOR<6>, the radicals R<6> being the same or different and selected from C1-C6 alkyl, formyl, CO-C1-C6 alkyl; R<5> is respectively the same or different and selected from C1-C6 alkyl and hydrogen; and n is a whole number between 2 and 10.

Description

Process for the preparation of hyperbranched polymers

description

The present invention relates to a process for the preparation of hyperbranched polymers, characterized in that compounds of the general formula 1

in which the variables are defined as follows:

X sulfur or oxygen,

R ¹ , R ³ different or identical and selected from hydrogen, -CC ₆ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₆ -C ₄ aryl,

R ² , R ⁴ different or identical and selected from hydrogen, CrC ₆ alkyl, C ₃ -C ₂ -cycloalkyl, C ₆ -C ₁₄ aryl,

ZZ ² different or identical and selected from COOH and COOR ⁶ , the radicals R ^{6 being} different or identical and selected from CrC ₆ alkyl, formyl, CO-C C ₆ alkyl,

R ⁵ each different or the same and selected from CC ₆ alkyl and hydrogen.

n is an integer in the range from 2 to 10,

optionally with at least one compound of the general formula I a

in which the variables are defined as above,

in the presence of a catalyst to react with each other. Dendrimers, arborols, starburst polymers and hyperbranched polymers are names for polymer structures which are distinguished by a branched structure and high functionality. Dendrimers are molecular and structurally uniform macromolecules with a highly symmetrical structure. They are built in multi-step syntheses, in most cases require the use of protective group chemistry and are accordingly expensive. US 4,507,466 may be mentioned as an example.

In contrast, so-called hyperbranched polymers are both molecularly and structurally inconsistent. For a definition and overview of hyperbranched polymers, see, for example, News from Chemistry, Technology and Laboratory, 2002, 50, 1218 and as well as Dendrimers and Dendrons, Concepts, Syntheses, Applications from GR Newkome, CN Moorefield, F. Vögtle, Wiley-VCH, 2001. So-called AB _X molecules are particularly suitable for the synthesis of hyperbranched polymers. AB _x molecules have two different functional groups A and B, which can react with one another to form a link. The functional group A is only present once in the molecule, the group B at least twice, ie x is an integer greater than or equal to 2. The reaction of the AB _x molecules with one another produces uncrosslinked hyperbranched polymers with regularly arranged branching sites. Hyperbranched polymers then almost exclusively have B end groups at the chain ends. Further details are, for example, in JMS - Rev. Marcromol. Chem. 1997, C37 (3), 555.

From WO 02/36697 it is known that hyperbranched polymers with functional groups are suitable as an additive for liquid printing inks, for example for flexographic printing.

Modified, highly functional hyperbranched polyesters and polyester-based dendrimers are known as such, see for example WO 96/19537, and are already used in some applications, for example as an impact modifier. However, dendrimers are too expensive for general use because the syntheses place high demands on the yields of the building reactions and purity of the intermediate and end products and require reagents that are too expensive for large-scale use. The production of hyperbranched, highly functional polyesters produced by conventional esterification reactions usually requires very drastic conditions, cf. WO 96/19537, for example high temperatures and / or strong acids. This can lead to side reactions such as dehydration reactions, decarboxylations and, as a result of the side reactions, to undesirable resinification and discoloration. I. Mievis and Y. Geerts presented a poster at the Belgium Polymer Group Meeting 2002, on which they produced the production of hyperbranched polyesters based on

AB ₂ monomers indicated by a Michael addition of N, N-diethanolamine

Methyl acrylate were synthesized. Precise data on the polymer obtained have not been disclosed.

Lu Yin et al. disclose in Acta Polym. Sinica 2000, volume 4, p. 411 and volume 5, p. 554 the synthesis of hyperbranched polyamine esters with an extremely broad molecular weight distribution (volume 4, page 412, table 2, lines 1 and 2). Furthermore, Lu Yin et al. Polyamine esters with extremely narrow molecular weight distribution (same table, lines 3-5), which were produced by a so-called pseudo-one-step process. The pseudo-one-step process consists in reacting 1, 1, 1-trimethylol-propane as a so-called core molecule with several portions of N, N-diethylol-3-a-aminomethyl-propionate. N, N-diethylol-3-amino-methyl propionate is obtained from methacrylic acid and N, N-diethanolamine, a molar ratio of methacrylic acid and N, N-diethanolamine of 1: 1 being chosen. H. Wei et al. disclose in J. Appl. Polym. Be. 2003, 87, 168 that the dendrimers and hyperbranched polymers obtainable in this way can be photopolymerized after modification with acrylic end groups.

The properties of those described by H. Wei et al. However, published hyperbranched polymers are not sufficient for some technical applications. In particular, the molecular weight and functionality of the hyperbranched polymers described are not sufficient for many technical applications.

The object was therefore to provide hyperbranched polymers which have improved application properties. There was also the task of providing a process by means of which new hyper-twisted polymers can be produced.

It has now been found that the object can be achieved by the hyperbranched polymers defined at the outset.

The present invention therefore relates to a process for producing the hyperbranched polymers according to the invention, also referred to below as the process according to the invention.

In one embodiment of the present invention, compounds of the general formula I are used to carry out the process according to the invention

in which the variables are defined as follows:

X sulfur or preferably oxygen;

R ¹ , R ³ are different or preferably the same and selected from hydrogen,

C Ce-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, iso-pentyl, sec.-pentyl, neo- Pentyl, 1, 2-dimethyl-propyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably CτC ₄ -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl;

C ₃ -C ₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred.

C ₆ -C ₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl.

R ¹ and R ³ are very particularly preferably in each case the same and selected from hydrogen and methyl.

R ² , R ⁴ are different or preferably the same and selected from

Hydrogen, ^~ CC ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl , neo-pentyl, 1,2-dimethyl-propyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, particularly preferably CC ₄ - alkyl such as methyl, ethyl, n-propyl, iso-propyl, n -Butyl, iso-butyl, sec-butyl and tert-butyl; C ₃ -C ₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyK ^_ C ₆ -C ₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl. R ² and R ^{4 are} each very particularly preferably hydrogen.

ZZ ² are different or preferably the same and selected from COOH and preferably COOR ⁶ , the radicals R ^{6 being} different or preferably the same and selected from d-Ce-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl , iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, iso-pentyl, sec.-pentyl, neo-pentyl, 1, 2-dimethyl propyl, iso-amyl, n-hexyl, iso- Hexyl, sec-hexyl, particularly preferably CC ₄ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl;

formyl,

CO-CrCe-alkyl such as CO-CH ₃ (acetyl), n-propionyl, isopropionyl, n-butyryl, sec-butyryl, pivaloyl, n-valeroyl, n-caproyl.

R ⁵ are in each case different or preferably identical and selected from CC ₆ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, iso-pentyl, sec.-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, particularly preferably C _r C ₄ - alkyl such as methyl, ethyl , n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl and in particular hydrogen.

n is an integer in the range from 2 to 10, preferably up to 4 and particularly preferably up to 3.

By adding catalyst, compound with the general formula I is reacted. The process according to the invention can be carried out in the presence of a compound I a

in which the variables are defined as above. If the process according to the invention is carried out in the presence of compound I and I a, it is preferred if the variables correspond to one another, ie R ¹ from compound I and compound I a are in each case identical, R ² from compound I and compound I a always the same etc.

0 to 1000% by weight of compound I a, based on compound I, can be used, preferably 0 to 100% by weight, particularly preferably 10 to 50% by weight.

The process according to the invention can be carried out in the presence or absence of at least one polyfunctional compound which can serve as a core or "core molecule". Polyfunctional compounds for the purposes of the present invention are compounds with 2 or more identical or different functional groups, such as, for example, acids or their derivatives, such as esters, acid halides or anhydrides.

Examples include:

Dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, azelaic acid, phthalic acid, isophthalic acid, terephthalic acid, and mono- and diesters, in particular mono- and di-C 1-4 alkyl esters, halides and anhydrides the aforementioned dicarboxylic acids; where dC ₄ alkyl is selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl;

Tricarboxylic acids, such as trimellitic acid (1, 2,4-benzenetricarboxylic acid), 1, 3,5-benzenetricarboxylic acid, and mono-, di- and triesters, in particular mono-, di- and tri-Ci-Cralkyl esters, halides and anhydrides the aforementioned tricarboxylic acids; where C 1 -C ₄ alkyl is selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl; Tetracarboxylic acids, such as ethylenediaminetetraacetic acid (EDTA), pyromellitic acid (benzene-1, 2,4,5-tetracarboxylic acid), and mono-, di- and triesters, in particular mono-, di- tri- and tetra-C 1 -C ₄ -alkyl esters , Halides and anhydrides of the aforementioned tetracarboxylic acids; where CC ₄ alkyl is selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl. Mixtures of the di-, tri- and tetracarboxylic acids mentioned or their derivatives can of course also be used.

Furthermore, for example, di- or polyisocyanates can also be used as core molecules. Suitable di- and polyisocyanates are the aliphatic, cycloaliphatic and aromatic isocyanates known from the prior art. Preferred di- or polyisocyanates are 4,4 ^{'-Diphenylmethandüsocyanat,} the mixtures of monomeric diphenylmethane diisocyanates and oligomeric diphenylmethane diisocyanates (polymer-MD I), tetramethylene diisocyanate, tetramethylene diisocyanate trimers, hexamethylene diisocyanate, hexamethylene diisocyanate trimers, isophorone diisocyanate

Trimer, 4,4'-methylenebis (cyclohexyl) diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dodecyl diisocyanate, lysine alkyl ester diisocyanate, where alkyl is d to C ₁₀ , 2,2,4- or 2,4,4- Trimethyl-1, 6-hexamethylene diisocyanate, 1, 4-diisocyanatocyclohexane or 4-isocyanatomethyl-1, 8-octamethylene diisocyanate, 2,4-tolylene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate ( 2,4 ^' -MDI), triisocyanatotoluene,

Isophorone diisocyanate (IPDI), 2-butyl-2-ethylpentamethylene diisocyanate, 2-isocyanato-propylcyclohexyl isocyanate, 3 (4) -isocyanatomethyl-1-methylcyclo-hexyl-isocyanate, 1, 4-diisocyanato-4-methylpentane, 2,4'-methylene bis (cyclohexyl) diisocyanate and 4-methyl-cyclohexane-1,3-diisocyanate (H-TDI), 1,3- and 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenyl diisocyanate, tolidinediisocyanate or 2,6 -Toluenedi-isocyanate.

Furthermore, it is possible, for example, to use oligo- or polyisocyanates which are composed of the di- or polyisocyanates mentioned or their mixtures by being linked by means of urethane, allophanate, urea, biuret, uretdione, amide, isocyanate, Have carbodiimide, uretonimine, oxadiazinetrione or iminooxadiazinedione structures produced.

Mixtures of the isocyanates mentioned can of course also be used.

If it is desired to use at least one “core molecule”, an excess of compound of the formula I is usually used. Suitable molar excesses of the compound of the formula I are, for example, 1: 1 to 1000: 1, based in each case on the number of functional groups of the "core molecules". A catalyst is preferably used to carry out the process according to the invention. Enzymes are suitable, for example. If one wishes to use enzymes, the use of lipases and esterases is preferred. Well-suited lipases and esterases are from Candida cylindracea, Candida lipolytica, Candida rugosa, Candida antarctica, Candida utilis, Chromobacterium viscosum, Geotrichum viscosum, Geotrichum candidum, Mucorjavanicus, Mucor miehei, pig pancreas, pseu-domonas sppcens, pseudomonas , Rhizopus arrhizus, Rhizopus delemar, Rhizopus niveus, Rhizopus oryzae, Aspergillus niger, Penicillium roquefortii, Penicillium camembertii or Esterase from Bacillus spp. and Bacillus thermoglucosidasius. Candida antarctica lipase B is particularly preferred. The enzymes listed are commercially available, for example from Novozymes Biotech Inc., Denmark.

Enzyme is preferably used in immobilized form, for example on silica gel or Lewatit®. Methods for immobilizing enzymes are known per se, for example from Kurt Faber, "Biotransformations in organic chemistry", 3rd edition 1997, Springer Verlag, chapter 3.2 "Immobilization", pages 345-356. Immobilized enzymes are commercially available, for example from Novozymes Biotech Inc., Denmark.

The amount of enzyme used is usually 1 to 20% by weight, in particular 10-15% by weight, based on the mass of the compound I used overall.

In one embodiment of the present invention, non-enzymatic catalysts are used.

The process is preferably carried out in the presence of an acidic inorganic, organometallic or organic catalyst or mixtures of two or more acidic inorganic, organometallic or organic catalysts.

Acidic inorganic catalysts for the purposes of the present invention include, for example, sulfuric acid, phosphoric acid, phosphonic acid, hypophosphorous acid, aluminum sulfate hydrate, alum, acidic silica gel (pH <6, in particular <5) and acidic aluminum oxide. Furthermore, for example, aluminum compounds of the general formula AI (OR) ₃ and titanates of the general formula Ti (OR) ₄ can be used as acidic inorganic catalysts, where the radicals R can in each case be the same or different and are selected independently of one another C Cιo-alkyl radicals, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo -Pentyl, 1, 2-dimethyl-propyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, 2-ethyl-hexyl, n-nonyl or n-decyl,

C ₃ -Ci ₂ cycloalkyl radicals, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred.

The radicals R in Al (OR) ₃ or Ti (OR) ₄ are preferably the same and selected from isopropyl or 2-ethylhexyl.

Preferred acidic organometallic catalysts are selected, for example, from dialkyltin oxides R ₂ SnO, where R is defined as above. A particularly preferred representative of acidic organometallic catalysts is di-n-butyltin oxide, which is commercially available as so-called oxo-tin or as Fascat® brands.

Preferred acidic organic catalysts are acidic organic compounds with, for example, phosphate groups, sulfonic acid groups, sulfate groups or phosphonic acid groups. Sulfonic acids such as para-toluenesulfonic acid are particularly preferred. It is also possible to use acidic ion exchangers as acidic organic catalysts, for example polystyrene resins containing sulfonic acid groups, which are crosslinked with about 2 mol% of divinylbenzene.

Combinations of two or more of the aforementioned catalysts can also be used. It is also possible to use such organic or organometallic or else inorganic catalysts which are in the form of discrete molecules in immobilized form.

If it is desired to use acidic inorganic, organometallic or organic catalysts, 0.01 to 10% by weight, preferably 0.02 to 2% by weight, of catalyst is used according to the invention.

If it is desired to use enzyme-based catalysts, the process according to the invention is preferably carried out at temperatures in the range from 0 ° C. to 120 ° C. It is preferred to work at temperatures below 100 ° C. Temperatures in the range from 40 ° C. to 80 ° C. are preferred, very particularly preferably from 60 to 80 ° C.

If one wishes to use acidic inorganic, organometallic or organic catalysts, the process according to the invention is preferably carried out at temperature ren from 80 to 200 ° C. Preferably one works at temperatures from 100 to 180, in particular up to 150 ° C or below.

In one embodiment of the present invention, the process according to the invention is carried out in the presence of a solvent. For example, hydrocarbons such as paraffins or aromatics are suitable. Particularly suitable paraffins are n-heptane and cyclohexane. Particularly suitable aromatics are toluene, ortho-xylene, meta-xylene, para-xylene, xylene as a mixture of isomers, ethylbenzene, chlorobenzene and ortho- and meta-dichlorobenzene. Furthermore, very particularly suitable are: ethers such as dioxane or tetrahydrofuran and ketones such as methyl ethyl ketone and methyl isobutyl ketone.

However, the use of solvents can be dispensed with if compound I or if all the compounds are liquid under the reaction conditions. In the event that compound I is liquid under the reaction conditions, the use of solvents is preferably dispensed with.

In one embodiment of the present invention, the method according to the invention is carried out under an inert gas atmosphere, that is to say, for example, under carbon dioxide, nitrogen or noble gas, argon and nitrogen in particular being mentioned.

The printing conditions of the method according to the invention are not critical per se. You can work at a significantly reduced pressure, for example at 0.1 to 500 mbar. The method according to the invention can also be used for prints above

500 mbar can be carried out. For reasons of simplicity, the reaction at from 500 mbar to atmospheric pressure is preferred; however, it is also possible to carry out the process at a slightly elevated pressure, for example up to 1200 mbar. You can work under significantly increased pressure, for example at pressures up to 10 bar. The conversion is preferred at 0.1 mbar to atmospheric pressure.

In one embodiment of the present invention, the process is carried out in the presence of a dehydrating agent as an additive which can be added at the start of the reaction. This embodiment is preferred if one or more enzymes are used as the catalyst. For example, weakly acidic silica gels, weakly acidic aluminum oxides, molecular sieves, in particular 4Ä molecular sieve, MgSO and Na ₂ SO _{4 are} suitable. Additional dehydrating agents can be added during the reaction, or dehydrating agents can be replaced by fresh dehydrating agents. In one embodiment of the present invention, a water separator and entrainer are used to separate water or alcohol or carboxylic acid formed during the reaction.

The reaction time can usually be in the range from 2 to 48 hours, 8 to 36 hours being preferred.

The hyperbranched polymers produced by the process according to the invention can be worked up by generally customary operations. The catalyst can be separated off, for example by filtration or other methods customary in the laboratory. If you have used a solvent, the reaction mixture is usually concentrated, the concentration usually being carried out under reduced pressure. Other well-suited processing methods are precipitation after the addition of suitable agents, for example water, and subsequent washing and drying.

Compounds of the general formula I and I a are known per se. Compounds of the general formula I can be obtained, for example, by reacting compounds of the general formula II with olefins of the general formulas III a and III b in accordance with a Michael addition.

lil a III b

If, in compounds of the general formula I, the radicals R ¹ and R ³ , R ² and R ⁴ , Z ¹ and Z ² are each identical in pairs and n and the corresponding radicals R ^{5 are} each identical, compounds of the general formula are shown Formula I by reacting compound of general formula II with two equivalents lil a.

Compounds of general formula I a can be prepared by reacting compounds of general formula II with one equivalent of olefin of formula III a.

Mixtures of compounds of the general formula I and I a are particularly easy to prepare if the radicals R ¹ and R ³ , R ² and R ⁴ , Z ¹ and Z ^{2 are} each in pairs. are the same and n and the corresponding radicals R ^{5 are} each identical. It is then possible to react compound II with about 1.1 equivalents of olefin III a and to use the resulting mixture for the process according to the invention without further working up.

Another object of the present invention are hyperbranched polymers obtainable by the process according to the invention.

The hyperbranched polymers according to the invention have a molecular weight M _w of 500 to 100,000 g / mol, preferably 3000 to 20,000 g / mol, particularly preferably 3000 to 7000 g / mol and very particularly preferably 4000 g / mol. The polydispersity Pd is 1.2 to 50, preferably 1.4 to 40, particularly preferably 1.5 to 30 and very particularly preferably up to 10. They are usually very readily soluble, ie clear solutions with up to 50% by weight can be obtained. %, in some cases even up to 80% by weight, of the polymers according to the invention in tetrahydrofuran (THF), n-butyl acetate, ethanol and numerous other solvents without gel particles being detectable with the naked eye.

The hyperbranched polymers according to the invention are generally carboxyl-terminated, where the carboxyl groups can be esterified, and can be used, for example, for the preparation. B. of adhesives, coatings, foams, coatings, printing inks and varnishes can be used advantageously.

Another aspect of the present invention is a method for the hydrophilic modification of the hyperbranched polymers according to the invention and hydrophilically modified hyperbranched polymers according to the invention. To produce hydrophilically modified polymers according to the invention, one can start from hyperbranched polymers according to the invention and react them with a hydrophilic compound, for example with at least one polyhydric alcohol or with at least one alkanolamine.

Examples of preferred polyhydric alcohols are: alcohols with at least 2 hydroxyl groups, such as: ethylene glycol, 1,2-propanediol, 1,4-butanediol, 1,3-propanediol, 1,2-butanediol, glycerol, butane-1, 2,4-triol, n-pentane-1, 2,5-triol, n-pentane-1, 3,5-triol, n-hexane-1, 2,6-triol, n-hexane-1, 2, 5-triol, n-hexane-1, 3,6-triol, trimethylolbutane, trimethylolpropane or di-trimethylolpropane, trimethylolethane, pentaerythritol or dipentaerythritol; Sugar alcohols such as mesoerythritol, threitol, sorbitol, mannitol or mixtures of the above-mentioned alcohols. Glycerol, trimethylolpropane, trimethylolethane and pentaerythritol can preferably be used. Examples of alkanolamines used with preference are: monoalkanolamines, N, N-dialkylalkanolamines, N-alkylalkanolamines, dialkanolamines, N-alkylalkanolamines and trialkanolamines each having 2 to 18 carbon atoms in the hydroxyalkyl radical and optionally 1 to 6 carbon atoms in the alkyl radical, preferably 2 to 6 carbon atoms in the alkanol radical and optionally 1 or 2 carbon atoms in the alkyl radical. Ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, n-butyldiethanolamine, N, N-dimethylethanolamine and 2-amino-2-methylpropanol-1 are very particularly preferred. Ammonia and N, N-dimethylethanolamine are very particularly preferred.

Another aspect of the present invention is a method for producing hydrophobically modified hyperbranched polymers using the hyperbranched polymers according to the invention, and a further aspect of the present invention is hydrophobically modified hyperbranched polymers, produced by the inventive hydrophobic modification of hyperbranched polymers according to the invention.

For the production of hydrophobically modified hyperbranched polymers according to the invention, for example, hyperbranched polymers according to the invention are used and reacted with at least one hydrophobic alcohol. Hydrophobic alcohols are, for example, fatty alcohols, that is, in the sine of the present invention, alcohols with saturated or unsaturated C ₁₀ -C ₄₀ alcohols, or glycerol esterified with one or two equivalents of the same or different fatty acids, for example with oleic acid. Oleic acid, linoleic acid, linolenic acid, myristic acid, palmitic acid, castor acid. A preferred example is glycerol monostearate.

Another aspect of the present invention are hyperbranched polymers modified with at least one ethylenically unsaturated compound and a method for modifying the hyperbranched polymers according to the invention with ethylenically unsaturated compound.

To produce hyperbranched polymers according to the invention modified with at least one ethylenically unsaturated compound, for example, one starts from at least one hyperbranched polymer according to the invention and reacts this with at least one alcohol or an amine which in turn contains an ethylenic double bond. Examples of alcohols, which in turn have at least one ethylenic double bond, are 2-hydroxyethyl (meth) acrylate), 3-hydroxypropyl (meth) acrylate, ω-hydroxy-n-butyl (meth) acrylate and others with (meth ) - acrylic acid esterified diols and polyols in which at least one hydroxyl group is not esterified. Examples include: trimethylolpropane monoacrylate, trimethylolpropane diacrylate, pentaerythritol tri (meth) acrylate, pentaerythritol triallyl ether, pentaerythritol di (meth) acryiatmonostrearat. Unsaturated ethers of diols and polyols in which at least one hydroxyl group is not etherified are also suitable, for example trimethylolpropane diallyl ether, trimethylolpropane monoallyl ether, 1,6-hexanediol mono vinyl ether. Unsaturated alcohols such as hex-1-en-3-ol and hex-2-en-1-ol may also be mentioned.

Examples of suitable amines include allylamine and hex-1-en-3-amine.

Hypbranched polymers modified according to the invention with at least one ethylenically unsaturated compound are particularly suitable for the production of printing varnishes.

Another aspect of the present invention is the use of the hyperbranched polymers according to the invention for the production of polyaddition or polycondensation products, for example polycarbonates, polyurethanes and polyethers. The use of the hydroxyl group-terminated hyperbranched polymers according to the invention is preferred for the production of polyaddition or polycondensation products such as polycarbonates or polyurethanes.

Another aspect of the present invention is the use of the hyperbranched polymers according to the invention and the polyaddition or polycondensation products produced from hyperbranched polymers according to the invention as a component of adhesives, coatings, foams, coatings and lacquers. Another aspect of the present invention are adhesives, coatings, foams, coatings and lacquers containing the hyperbranched polymers according to the invention. They are characterized by excellent technical properties.

Another preferred aspect of the present invention is printing inks, in particular packaging printing inks for flexographic and / or gravure printing, which comprises at least one solvent or a mixture of different solvents, at least one colorant, at least one polymeric binder and optionally further additives, where it is at least one of the polymeric binders is a hyperbranched polymer according to the invention.

Hyperbranched polymers according to the invention can be used in the context of the present invention in a mixture with other binders. Examples of other binders for printing inks according to the invention include polyvinyl butyral, nitrocellulose, polyamides, polyacrylates or polyacrylate copolymers. The combination of at least one hyperbranched poly- proven with nitrocellulose. The total amount of all binders in the printing ink according to the invention is usually 5-35% by weight, preferably 6-30% by weight and particularly preferably 10-25% by weight, based on the sum of all components. The ratio of hyperbranched polymers according to the invention to the total amount of all binders is usually in the range from

30% by weight to 100% by weight, preferably at least 40% by weight, but the amount of hyperbranched polymer generally being 3% by weight, preferably 4% by weight and particularly preferably 5% by weight, based on the sum of all Components of the printing ink should not be less.

A single solvent or a mixture of several solvents can be used. In principle, the usual solvents for printing inks, in particular packaging printing inks, are suitable as solvents. Particularly suitable as solvents for the printing ink according to the invention are alcohols such as ethanol, 1-propanol, 2-propanol, ethylene glycol, propylene glycol, diethylene glycol, substituted alcohols such as ethoxypropanol, esters such as ethyl acetate, isopropyl acetate, n-propyl or n butyl acetate. Water is also suitable in principle as a solvent. Particularly preferred as the solvent is ethanol or mixtures which consist predominantly of ethanol. The person skilled in the art makes a suitable selection from the solvents which are possible in principle, depending on the solubility properties of the polymer and the desired properties of the printing ink. Usually 40 to 80% by weight of solvent are used in relation to the sum of all components of the printing ink.

Conventional dyes, in particular conventional pigments, can be used as colorants. Examples are inorganic pigments such as titanium dioxide pigments or iron oxide pigments, interference pigments, carbon blacks, metal powders such as in particular aluminum, brass or copper powder, and organic pigments such as azo, phthalocyanine or isoindoline pigments. Mixtures of different dyes or colorants can of course also be used, as can soluble organic dyes. Usually 5 to 25% by weight of colorant is used in relation to the sum of all components.

Printing inks according to the invention and in particular packaging printing inks according to the invention can optionally comprise further additives and auxiliary substances. Examples of additives and auxiliaries are fillers such as calcium carbonate, aluminum oxide hydrate or aluminum or magnesium silicate. Waxes increase the abrasion resistance and serve to increase the lubricity. Examples are, in particular, polyethylene waxes, oxidized polyethylene waxes with an M _w in the range from 1500 to 20,000 g / mol, petroleum waxes or ceresin waxes. Fatty acid amides can be used to increase the surface Chen smoothness can be used. Plasticizers serve to increase the elasticity of the dried film. Examples are phthalic acid esters such as dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, citric acid ester or esters of adipic acid. Dispersing aids can be used to disperse the pigments. Adhesion promoters can advantageously be dispensed with in the printing ink according to the invention, without the use of adhesion promoters thereby being excluded. The total amount of all additives and auxiliary substances usually does not exceed 20% by weight with respect to the sum of all components of the printing ink and is preferably 0-10% by weight.

Packaging printing inks according to the invention can be produced in a manner known in principle by intensive mixing or dispersing of the constituents in conventional apparatus, such as, for example, one or more dissolvers, one or more stirred ball mills or one or more three-roll mills. First of all, a concentrated pigment dispersion with one part is advantageous of the components and a part of solvent, which is then processed further with the inventive hyperbranched polymer, optionally further constituents and further solvent to give the finished printing ink.

Another preferred aspect of the present invention is printing varnishes which comprise at least one solvent or a mixture of different solvents, at least one polymeric binder and optionally further additives, where at least one of the polymeric binders is a hyperbranched polymer according to the invention, and the use of Printing varnishes according to the invention for priming, as a protective varnish and for producing multilayer materials.

Printing varnishes according to the invention contain no colorants, but apart from that they have the same constituents as the printing inks according to the invention described above. The amounts of the other components increase accordingly.

It has been found that by using printing inks according to the invention, in particular packaging printing inks, or printing varnishes with binders based on hyperbranched polymers, multilayer materials with excellent adhesion between the individual layers can be obtained. The addition of adhesion promoters is not necessary. In many cases, even better results can be achieved without using a bonding agent than when adding a bonding agent. Adhesion could be significantly improved, especially on polar foils. working examples

1. Preparation of hyperbranched polymer 1

In a four-necked flask equipped with a stirrer and nitrogen inlet tube, 33.4 g (0.55 mol) of ethanolamine were placed under a nitrogen atmosphere at room temperature and 141 g (1.1 mol) of tert-butyl acrylate were added dropwise. After the addition was complete, the mixture was stirred at room temperature until the Michael addition had ended (control by thin-layer chromatography), which was the case after about 2 hours. N, N- (di-tert-butylpropionato) aminoethan-2-ol (1.1) was obtained.

0.17 g (1000 ppm) of di-n-butyltin oxide, commercially available as Fascat® 4201 (E-Coat, ELF Atochem), was added and the mixture was heated to 130.degree. A pressure of 200 mbar was set in order to separate off the tert-butanol formed during the reaction. After 10 hours the pressure was reduced to 50 and then further to 0.1 mbar. After 15 hours, the mixture was cooled to room temperature. A tough, oily resin was obtained.

Molecular mass determination (GPC): M _n 4800 g / mol; M _w 7600 g / mol. Column: stationary phase: polystyrene-hexafluoroisopropane gel. Mobile phase: 0.05% by weight potassium trifluoroacetate in hexafluoroisopropanol; Standard: polymethyl methacrylate.

2. Preparation of hyperbranched polymer 2

In a four-necked flask equipped with a stirrer and nitrogen inlet tube, 50 g (0.82 mol) of ethanolamine were placed under a nitrogen atmosphere at room temperature and 141 g (1.6 mol) of methyl acrylate were added dropwise. After the addition was complete, the mixture was stirred at room temperature until the Michael addition had ended (control by thin layer chromatography), which was the case after about 2 hours. N, N-Di- (methylpropionato) aminoethan-2-ol (I.2) was obtained.

0.19 g (1000 ppm) of di-n-butyltin oxide, commercially available as Fascat® 4201 (E-Coat, ELF Atochem), was added and the mixture was then heated to 130.degree. A pressure of 200 mbar was set in order to separate off the methanol formed during the reaction. After 10 hours the pressure was reduced to 50 mbar and then further to 0.1 mbar.

After 4 hours, the mixture was cooled to room temperature. A tough, oily, pale yellow resin was obtained.

Molecular mass determination (GPC): M _n 3700 g / mol; M _w 6000 g / mol, conditions: as in Example 1.

3. Preparation of hyperbranched polymer 3

0.17 g (1000 ppm) of di-n-butyltin oxide were added, commercially available as Fascat® 4201 (E-Coat, ELF Atochem), and heated to 130 ° C. A pressure of 200 mbar was set in order to separate off the tert-butanol formed during the reaction. After 10 hours the pressure was reduced to 50 mbar and then further to 0.1 mbar and the temperature was kept at 130 ° C.

After 210 minutes, the mixture was cooled to room temperature and a pressure of 1 bar was set with nitrogen. Then 33.4 g (0.55 mol) of ethanolamine were added. The reaction mixture was then heated to 140 ° C. for half an hour. The pressure was then reduced to 25 mbar and heated at 140 ° C. and 25 mbar for a further hour in order to distill off tert-butanol.

After 5 hours, the mixture was cooled to room temperature and a pressure of 1 bar was set with nitrogen. A viscous, oily resin was obtained which could be easily dissolved in water.

Application examples: Production of printing inks

Flexographic printing inks F1.1 and F1.2 were produced by intensively mixing the following components, whereby flexographic printing inks are to be understood as printing inks for flexo printing.

70.0 g blue pigment preparation based on pigment blue 15: 4 (BASF Drucksys teme GmbH) 6.0 g hyperbranched polymer 1 (only for flexographic printing ink F1.1) 6.0 g hyperbranched polymer 2 (only for flexographic printing ink F1.2 ) 8.0 g nitrocellulose (Wolf) 1.0 g oleamide (Croda) 0.5 g polyethylene wax with an M _w of 3500 g (BASF Aktiengesellschaft), produced by polymerizing ethylene at 1700 bar and 210 ° C in a high pressure autoclave, described by M. Buback er al., Chem. Ing. Tech. 1994, 66, 510; 10.5 g ethanol 2.0 g coupling agent Ti (acac) ₃ ; acac: acetylacetonate

In a second series, flexographic inks F 2.1 and F 2.2 were produced by intensively mixing the following components:

70.0 g blue pigment preparation based on pigment blue 15: 3 (BASF Drucksysteme) 6.0 g hyperbranched polymer 1 (only for flexographic printing ink F2.1) 6.0 g hyperbranched polymer 2 (only for flexographic printing ink F2.2) 8 , 0 g nitrocellulose (Wolf) 1.0 g oleamide (Croda) 0.5 g polyethylene wax with an M _w of 3500 g (BASF Aktiengesellschaft), produced by polymerizing ethylene at 1700 bar and 210 ° C in a high pressure autoclave, described by M. Buback et al., Chem. Ing. Tech. 1994, 66, 510; 10.5 g ethanol

For comparison purposes, flexographic printing inks were also produced using conventional polyurethane binders (PUR 7313 (BASF). The formulations are listed in Table 1:

Table 1: Composition of the printing inks tested

Adhesion to substrates

The adhesion of the flexographic printing inks according to the invention to polar films made of polyamide and PET and to a non-polar film made of polypropylene was determined.

Measurement Method:

The test procedure "Tesafestigkeit" serves to determine the adhesion of an ink film on the substrate.

Carrying out the test

The ink, diluted to the printing viscosity, was printed on the respective film or applied using a 6 μm doctor blade. A tape strip (adhesive tape with a width of 19 mm (item BDF 4104), Beiersdorf AG) was stuck onto the ink film, evenly printed and torn off after 10 seconds. This process was carried out four times at the same place on the test specimen, each time with new tape strips. Each tape was stuck on white paper one after the other, on white paper on black paper. The test was carried out immediately after application of the flexographic printing ink.

evaluation

There was a visual inspection of the surface of the printed film for damage. The grading was from 1 (very bad) to 5 (very good). Tables 2 and 3 summarize the results of the tests.

Table 2: Test results with flexographic printing inks that contain adhesion promoters

Manufacture of composite materials

Multi-layer materials with various foils were produced with printing inks 1.1 to V5. The quality of the composites is determined by determining the bond strength between two foils connected by lamination.

Application examples 4 - 9

General working instructions

The flexographic printing ink, thinned to printing viscosity, was printed on film 1 as printing material. In parallel, the lamination film (film 2) is coated with an adhesive-hardener mixture (R&H MOR-FREE A 4123 / hardener C88)) in such a way that a film thickness of approximately 6 μm resulted. Both foils were then pressed in such a way that the printing ink and the adhesive came into contact. After pressing, the composite films obtainable in this way were stored at 60 ° C. for 3 days and the composite value was then determined. The results of the tests are summarized in Table 4. Test Method:

Measuring and testing equipment: tensile strength tester from Zwick punching tool (width: 15 mm)

At least 2 strips (width 15 mm) of the composite material to be tested were cut along and across the film web. To facilitate the separation (delamination) of the composite, the ends of the punched strips were immersed in a suitable solvent (e.g. 2-butanone) until the materials came apart. The pattern was then dried carefully. The delaminated ends of the test specimens were clamped in the tensile strength tester. The less stretchable film was placed in the upper clamp. When the machine started up, the end of the pattern was held at right angles to the direction of pull, ensuring a constant pull. The take-off speed was 100 mm / min, the take-off angle of the separated films to the non-separated complex was 90 °.

Evaluation:

The bond value was read off as the mean, given in N / 15 mm.

Table 4: Results for the composite films

Polyamide film: Walomid XXL, PET film: Melinex 800, PP film MB 400.

The test results show that the adhesion of the flexographic printing inks according to the invention, even on chemically different film types, has been significantly improved by the use of the hyper-dilated polyester amines in comparison to conventional binders. You can do without adhesion promoters and still achieve very good results. Composite films according to the invention, produced using flexographic printing inks which soften hyperbranched polyester amines, show excellent adhesion, in particular when using polar films. This result is all the more surprising since the tests with tape treads did not lead to this result.

Claims

claims

1. A process for the preparation of hyperbranched polymers, characterized in that compounds of the general formula I

in which the variables are defined as follows:

X selected from sulfur or oxygen,

R \ R ³ different or the same and selected from hydrogen, CC ₆ alkyl, C ₃ -C ₁₂ cycloalkyl, C ₆ -C ₄ aryl,

R ² , R ⁴ different or the same and selected from hydrogen, -CC ₆ alkyl, C ₃ -Ci ₂ cycloalkyl, C ₆ -C ₁₄ aryl,

Z ¹ , Z ² different or identical and selected from COOH and COOR ⁶ , where the radicals R _6 are different or identical and selected from CrC ₆ alkyl, formyl, CO-C C ₆ alkyl,

R each different or the same and selected from d-Ce alkyl and hydrogen. n is an integer in the range from 2 to 10, optionally with at least one compound of the general formula I a

in which the variables are as defined above, reacting with each other in the presence of a catalyst.

2. The method according to claim 1, characterized in that in formula I the radicals R ¹ and R ^{3 are the} same.

3. The method according to claim 1 or 2, characterized in that in formula I the radicals R ² and R ^{4 are the} same.

4. The method according to any one of claims 1 to 3, characterized in that in formula I the radicals Z ¹ and Z ² each represent COOH.

5. The method according to any one of claims 1 to 3, characterized in that in formula I the radicals Z ¹ and Z ² each represent COOR ⁶ .

6. The method according to any one of claims 1 to 3 or 5, characterized in that in formula I the radicals R ^{6 are} each the same.

7. The method according to any one of claims 1 to 4, characterized in that in formula IR ¹ and R ^{3 are} each the same and are selected from methyl and hydrogen, the radicals R ² and R ^{4 are} each hydrogen and the radicals Z ¹ and Z ² each mean COOR ⁶ .

8. The method according to any one of claims 1 to 7, characterized in that 0 to 1000 wt .-% compound of general formula I a, based on compound of general formula I, is used.

9. The method according to any one of claims 1 to 8, characterized in that one carries out the reaction in the presence of at least one polyfunctional compound.

10. The method according to any one of claims 1 to 9, characterized in that one carries out the reaction in the presence of at least one enzyme.

11. The method according to any one of claims 1 to 9, characterized in that one carries out the reaction in the presence of an acidic inorganic, organometallic or organic catalyst or a mixture of several acidic inorganic, organometallic or organic catalysts.

12. Hyperbranched polymers obtainable by a process according to one of claims 1 to 11.

13. A process for the preparation of hydrophilically modified hyperbranched polymers, characterized in that hyperbranched polymers according to claim 12 are reacted with a hydrophilic compound.

14. Hydrophilically modified hyperbranched polymers, obtainable by a process according to claim 13.

15. A process for the preparation of hydrophobically modified hyperbranched polymers, characterized in that hyperbranched polymers according to claim 12 are reacted with at least one hydrophobic alcohol.

16. Hydrophobically modified hyperbranched polymers, obtainable by a process according to claim 15. 7. Process for the preparation of hyperbranched polymers modified with at least one ethylenically unsaturated compound, characterized in that hyperbranched polymers according to claim 12 are reacted with at least one alcohol or an amine, which in turn has an ethylenically unsaturated double bond.

18. Hyperbranched polymers modified with at least one ethylenically unsaturated compound, obtainable by a process according to claim 17.

19. Use of hyperbranched polymers according to claim 12 for the production of adhesives, coatings, foams, coatings, printing inks and varnishes, in particular printing varnishes.

20. Printing inks produced using hyperbranched polymers according to claim 12.

21. Printing varnishes produced using hyperbranched polymers according to claim 12 or of hyperbranched polymers modified with at least one ethylenically unsaturated compound according to claim 18.