Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
  • C09D201/005—Dendritic macromolecules
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/02—Aliphatic polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/02—Aliphatic polycarbonates
  • C08G64/0208—Aliphatic polycarbonates saturated
  • C08G64/0216—Aliphatic polycarbonates saturated containing a chain-terminating or -crosslinking agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/04—Aromatic polycarbonates
  • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
  • C08G64/14—Aromatic polycarbonates not containing aliphatic unsaturation containing a chain-terminating or -crosslinking agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/42—Chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/005—Dendritic macromolecules
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D169/00—Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates

Definitions

• the present invention relates to highly functional highly or hyperbranched polycarbonates based on dialkyl or diaryl carbonates or phosgene, diphosgene or triphosgene and aliphatic aliphatic / aromatic and aromatic di- or polyols, a process for their preparation and their use for the production of printing inks.
• the highly functional highly branched or hyperbranched polycarbonates according to the invention can i.a. technically advantageously used as adhesion promoters, thixotropic agents or as building blocks for the production of polyaddition or polycondensation polymers, for example paints, coatings, adhesives, sealants, cast elastomers or foams.
• Polycarbonates are usually obtained from the reaction of alcohols or phenols with phosgene or from the transesterification of alcohols or phenols with dialkyl or diaryl carbonates.
• aromatic polycarbonates which are made from bisphenols, for example, aliphatic polycarbonates have so far played a subordinate role in terms of market volume. See also Becker / Braun, Kunststoff-Handbuch Vol. 3/1, polycarbonates, polyacetals, polyester, cellulose esters, Carl-Hanser-Verlag, Kunststoff 992, pages 118-119, and "Ullmann 's Encyclopedia of Industrial Chemistr", 6th Edition, 2000 Electronic Release, published by Wiley-VCH.
• aromatic or aliphatic polycarbonates described in the literature are generally linear or have a low degree of branching.
• No. 3,305,605 describes the use of solid linear aliphatic polycarbonates with a molecular weight above 15,000 Da as plasticizers for polyvinyl polymers.
• Linear aliphatic polycarbonates are also preferably used for the production of thermoplastic materials, for example for polyesters or for polyurethane or polyurea urethane elastomers, see also EP 364052, EP 292772, EP 1018504 or DE 10130882. Characteristic of these linear polycarbonates is general their high inherent viscosity.
• EP-A 896 013 discloses crosslinked polycarbonates which can be obtained by reacting mixtures of diols and polyols having at least 3 OH groups with organic carbonates, phosgenes or derivatives thereof. At least 40% of the diol is preferably used. The document contains no information as to how one can also produce uncrosslinked, hyperbranched polycarbonates based on the starting materials mentioned.
• Hyperbranched polycarbonates can also be produced according to WO 98/50453. According to the process described there, triols are in turn reacted with carbonylbisimidazole. Imidazolides initially form, which then react intermolecularly to the polycarbonates. According to the method mentioned, the polycarbonates are obtained as a colorless or pale yellow, rubber-like product.
• the hyperbranched products are either high-melting or rubber-like, which significantly limits later processability.
• Imidazole liberated during the reaction has to be removed from the reaction mixture in a complex manner.
• the reaction products always contain terminal imidazolide groups. These groups are unstable and have to be taken through a subsequent step, e.g. be converted into hydroxyl groups.
• Carbonyldiimidazole is a comparatively expensive chemical that greatly increases the cost of feed.
• the invention was therefore based on the object of using a technically simple and inexpensive process to prepare aromatic, preferably aromatic / aliphatic and particularly preferably aliphatic, highly functional and highly branched polycarbonates.
• represent whose structures can be easily adapted to the requirements of the application and which, due to their defined structure, can combine advantageous properties such as high functionality, high reactivity, low viscosity and good solubility, and a process for the preparation of these highly functional high or hyperbranched polycarbonates.
• the object was achieved according to the invention by reacting dialkyl or diaryl carbonates with di- or polyfunctional aliphatic or aromatic alcohols.
• phosgene, diphosgene or triphosgene are used instead of the carbonates as the starting material.
• the invention thus relates to a process for producing highly functional, highly branched or hyperbranched polycarbonates, at least comprising the steps:
• condensation products (K) b) intermolecular conversion of the condensation products (K) to a highly functional, highly branched or hyperbranched polycarbonate, the quantitative ratio of the OH groups to the phosgenes or the carbonates in the reaction mixture being chosen such that the condensation products (K) either have an average Carbonate or carbamoyl chloride group and more have as one OH group or one OH group and more than one carbonate or carbamoyl chloride group.
• the invention further relates to the highly functional, highly branched or hyperbranched polycarbonates produced by this process.
• hyperbranched polycarbonates are understood to mean uncrosslinked macromolecules with hydroxyl and carbonate or carbamoyl chloride groups, which are structurally and molecularly nonuniform.
• they can be based on a central molecule analogous to dendrimers, but with a non-uniform chain length of the branches.
• they can also be linear, with functional side groups, or, as a combination of the two extremes, they can have linear and branched parts of the molecule.
• dendrimeric and hyperbranched polymers see also P.J. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, No. 14, 2499.
• hypobranched is understood to mean that the degree of branching (DB), that is to say the average number of dendritic linkages plus average number of end groups per molecule, is 10 to 99.9%, preferably 20 to 99 %, particularly preferably 20-95%.
• DB degree of branching
• dendrimer means that the degree of branching is 99.9-100%.
• the invention further relates to the use of the highly functional, highly branched polycarbonates according to the invention as adhesion promoters, thixotropic agents or as building blocks for the production of polyaddition or polycondensation polymers, for example paints, coatings, adhesives, sealants, cast elastomers or foams.
• Phosgene, diphosgene or triphosgene can be used as the starting material, but organic carbonates (A) are preferably used.
• the radicals R of the organic carbonates (A) of the general formula RO [(CO) O] n R used as the starting material are each independently a straight-chain or branched aliphatic, aromatic / aliphatic or aromatic hydrocarbon radical with 1 to 20 carbon atoms. Atoms.
• the two radicals R can also be connected to one another to form a ring. It is preferably an aliphatic hydrocarbon residue and particularly preferred added to a straight-chain or branched alkyl radical having 1 to 5 carbon atoms, or to a substituted or unsubstituted phenyl radical.
• the carbonates can preferably be simple carbonates of the general formula RO (CO) OR, i.e. in this case n stands for 1.
• n is an integer between 1 and 5, preferably between 1 and 3.
• Dialkyl or diaryl carbonates can be prepared, for example, from the reaction of aliphatic, araiiphatic or aromatic alcohols, preferably monoalcohols with phosgene. Furthermore, they can also be produced via oxidative carbonylation of the alcohols or phenols by means of CO in the presence of noble metals, oxygen or NO x .
• aliphatic, araiiphatic or aromatic alcohols preferably monoalcohols with phosgene.
• they can also be produced via oxidative carbonylation of the alcohols or phenols by means of CO in the presence of noble metals, oxygen or NO x .
• For methods of producing diaryl or dialkyl carbonates see also "Ullmann's Encyclopedia of Industrial Chemistry", 6th Edition, 2000 Electronic Release, Verlag Wiley-VCH.
• suitable carbonates include aliphatic, aromatic / aliphatic or aromatic carbonates such as ethylene carbonate, 1, 2- or 1, 3-propylene carbonate, diphenyl carbonate, ditolyl carbonate, dixylyl carbonate, dinaphthyl carbonate, ethylphenyl carbonate, dibenzyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate carbonate, diisobutyl carbonate, dipentyl carbonate, dihexyl carbonate, dicyclohexyl carbonate, diheptyl carbonate, dioctyl carbonate, didecyl carbonate or didodecyl carbonate.
• aliphatic, aromatic / aliphatic or aromatic carbonates such as ethylene carbonate, 1, 2- or 1, 3-propylene carbonate, diphenyl carbonate, ditolyl carbonate, dixylyl carbonate, dinaphthyl carbonate, ethy
• Examples of carbonates in which n is greater than 1 include dialkyl carbonates such as di (tert-butyl) dicarbonate or dialkyl tricarbonates such as di (tert-butyl) tricarbonate.
• Aliphatic carbonates are preferably used, in particular those in which the radicals comprise 1 to 5 carbon atoms, such as, for example, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate or diisobutyl carbonate or diphenyl carbonate as aromatic carbonate.
• the organic carbonates are reacted with at least one aliphatic or aromatic alcohol (B) which has at least 3 OH groups or mixtures of two or more different alcohols.
• Examples of compounds with at least three OH groups include glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, 1,2,4-butanetriol, tris (hydroxymethyl) amine, tris (hydroxyethyl) amine, tris (hydroxypropyl) amine, pentaerythritol, Diglycerin, triglycerol, polyglycerols, bis (tri-methylolpropane), tris (hydroxymethyl) isocyanurate, tris (hydroxyethyl) isocyanurate, phloroglucinol, trihydroxytoluene, trihydroxydimethylbenzene, phloroglucide, hexahydroxybenzene, 1, 3.5 , 1-tris (4'-hydroxy- phenyl) methane, 1,1,1-tris (4'-hydroxyphenyl) ethane, sugars such as, for example, glucose, sugar derivatives, trifunctional or higher-functional poly
• polyfunctional alcohols can also be used in a mixture with difunctional alcohols (B " ), provided that the average OH functionality of all alcohols used is greater than 2.
• suitable compounds with two OH groups include ethylene glycol, diethylene glycol, triethylene glycol , 1,2- and 1,3-propanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1,2-, 1,3- and 1,4-butanediol, 1,2-, 1,3- and 1,5-pentanediol, Hexanediol, cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, bis (4-hydroxycyclohexyl) methane, bis (4-hydroxycyclohexyl) ethane, 2,2-bis (4-hydroxycyclohexyl) propane, 1,1 'bis (4-hydroxyphenyl ) -3,3-5-tri- methylcyclohexan
• the diols are used to fine-tune the properties of the polycarbonate. If difunctional alcohols are used, the ratio of difunctional alcohols (B ') to the at least trifunctional alcohols (B) is determined by the person skilled in the art depending on the desired properties of the polycarbonate. As a rule, the amount of the alcohol (s) (B ') is 0 to 39.9 mol% based on the total amount of all alcohols (B) and (B') together. The amount is preferably 0 to 35 mol%, particularly preferably 0 to 25 mol% and very particularly preferably 0 to 10 mol%.
• reaction of phosgene, diphosgene or triphosgene with the alcohol or alcohol mixture generally takes place with the elimination of hydrogen chloride
• reaction of the carbonates with the alcohol or alcohol mixture to give the highly functional highly branched polycarbonate according to the invention takes place with the elimination of the monofunctional alcohol or phenol from the carbonate molecule.
• the highly functional, highly branched polycarbonates formed by the process according to the invention are terminated with hydroxyl groups and / or with carbonate groups or carbamoyl chloride groups after the reaction, that is to say without further modification. They dissolve well in various solvents, for example in water, alcohols such as methanol, ethanol, butanol, alcohol / water mixtures, ac clay, 2-butanone, ethyl acetate, butyl acetate, methoxypropylacetate, methoxyethyl acetate, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene carbonate or propylene carbonate.
• alcohols such as methanol, ethanol, butanol, alcohol / water mixtures, ac clay, 2-butanone, ethyl acetate, butyl acetate, methoxypropylacetate, methoxyethyl acetate, tetrahydrofur
• a highly functional polycarbonate is to be understood as a product which, in addition to the carbonate groups which form the polymer structure, furthermore has at least three, preferably at least six, more preferably at least ten functional groups at the end or at the side.
• the functional groups are carbonate groups or carbamoyl chloride groups and / or OH groups.
• there is no upper limit on the number of terminal or pendant functional groups but products with a very large number of functional groups may have undesirable properties, such as high viscosity or poor solubility.
• the highly functional polycarbonates of the present invention mostly have no more than 500 terminal or pendant functional groups, preferably no more than 100 terminal or pendant functional groups.
• condensation product (K) the resultant simplest condensation product
• the reactive group which results as a single group is generally referred to below as the "focal group”.
• the production of the condensation product (K) from a carbonate and a trihydric alcohol with a conversion ratio of 1: 1 results in an average Molecule of the type XY 2 , illustrated by the general formula 2.
• the focal group here is a carbonate group.
• condensation product (K) is prepared from a carbonate and a tetravalent alcohol, likewise with the conversion ratio 1: 1, an average molecule of the type XY 3 results, illustrated by the general formula 3.
• the focal group here is a carbonate group.
• R has the meaning defined at the outset and R 1 represents an aliphatic or aromatic radical.
• condensation product (K) can also be prepared, for example, from a carbonate and a trihydric alcohol, illustrated by the general formula 4, the conversion ratio being 2: 1 molar.
• the result is an average molecule of the type X 2 Y, the focal group here is an OH group.
• R and R 1 have the same meaning as in formulas 1 to 3.
• difunctional compounds for example a dicarbonate or a diol
• this causes the chains to be lengthened, as illustrated, for example, in general formula 5.
• An average molecule of type XY 2 results again, focal group is a carbonate group.
• R 2 represents an aliphatic or aromatic radical
• R and R 1 are defined as described above.
• condensation products can also be used for the synthesis.
• several alcohols or several carbonates can be used.
• mixtures of different condensation products of different structures can be obtained. This is illustrated by the example of the implementation of a carbonate with a trihydric alcohol. If the starting products are used in a ratio of 1: 1, as shown in (II), a molecule XY 2 is obtained . If the starting products are used in a ratio of 2.1, as shown in (IV), a molecule X 2 Y is obtained. With a ratio between 1: 1 and 2: 1, a mixture of molecules XY 2 and X 2 Y is obtained.
• the simple condensation products (K) described by way of example in the formulas 1-5 preferably react intermolecularly to form highly functional polycondensation products, hereinafter referred to as polycondensation products (P).
• the reaction to give the condensate (K) and the polycondensation product (P) is usually carried out at a temperature from 0 to 300 C C, preferably 0 to 250 C C, particularly preferably at 60 to 200 ° C and most preferably from 60 to 160 ° C in substance or in solution.
• all solvents can be used which are inert to the respective starting materials.
• Organic solvents such as decane, dodecane, benzene, toluene, chlorobenzene, xylene, dimethylformamide, dimethylacetamide or solvent naphtha are preferably used.
• the condensation reaction is carried out in bulk.
• the monofunctional alcohol liberated in the reaction or the phenol ROH can be removed from the reaction equilibrium in order to accelerate the reaction, for example by distillation, if appropriate under reduced pressure.
• distillation it is regularly advisable to use carbonates which, in the course of the reaction, release alcohols or phenols ROH with a boiling point of less than 140 ° C. at the present pressure.
• Suitable catalysts are compounds which catalyze esterification or transesterification reactions, for example alkali metal hydroxides, alkali metal carbonates, alkali hydrogen carbonates, preferably sodium, potassium or cesium, tertiary amines, guanidines, ammonium compounds, phosphonium compounds, aluminum, tin, zinc, titanium, zirconium or bismuth organic compounds, furthermore so-called double metal cyanide (DMC) catalysts, such as described for example in DE 10138216 or in DE 10147712.
• DMC double metal cyanide
• the catalyst is generally added in an amount of from 50 to 10,000, preferably from 100 to 5000, ppm by weight, based on the amount of the alcohol or alcohol mixture used.
• the intermolecular polycondensation reaction both by adding the suitable catalyst and by selecting a suitable temperature.
• the average molecular weight of the polymer (P) can be set via the composition of the starting components and via the residence time.
• condensation products (K) or the polycondensation products (P), which were produced at elevated temperature, are usually stable over a longer period at room temperature.
• condensation products (K) Due to the nature of the condensation products (K), it is possible that the condensation reaction can result in polycondensation products (P) with different structures that have branches but no crosslinks.
• the polycondensation products (P) ideally have either a carbonate or carbamoyl chloride group as the focal group and more than two OH groups, or else an OH group as the focal group and more than two carbonate or carbamoyl chloride groups.
• the number of reactive groups results from the nature of the condensation products (K) used and the degree of polycondensation.
• a condensation product (K) according to general formula 2 can react by triple intermolecular condensation to give two different polycondensation products (P), which are represented in general formulas 6 and 7.
• R and R 1 are as defined above.
• the temperature can be reduced to a range in which the reaction comes to a standstill and the product (K) or the polycondensation product (P) is stable in storage.
• the catalyst can be deactivated, in the case of basic catalysts, for example by adding an acidic component, for example a Lewis acid or an organic or inorganic protonic acid.
• an acidic component for example a Lewis acid or an organic or inorganic protonic acid.
• a product with groups reactive toward the focal group of (P) can be added to the product (P) to terminate the reaction become.
• a mono-, di- or polyamine can be added to a carbonate group as a focal group.
• the product (P) can be added, for example, to a mono-, di- or polyisocyanate, a compound containing epoxy groups or an acid derivative which is reactive with OH groups.
• the highly functional polycarbonates according to the invention are usually produced in a pressure range from 0.1 mbar to 20 bar, preferably at 1 mbar to 5 bar, in reactors or reactor cascades that are operated in batch mode, semi-continuously or continuously.
• the products according to the invention can be processed further without further purification after production.
• the product is stripped, i.e. freed from low molecular weight, volatile compounds.
• the catalyst can optionally be deactivated and the low molecular weight volatile constituents, for example monoalcohols, phenols, carbonates, hydrogen chloride or volatile oligomeric or cyclic compounds, by distillation, if appropriate with introduction of a gas, preferably nitrogen, carbon dioxide or air, if appropriate with reduced Pressure to be removed.
• the polycarbonates according to the invention can contain further functional groups in addition to the functional groups already obtained by the reaction.
• the functionalization can take place during the molecular weight build-up or also subsequently, i.e. after the actual polycondensation has ended.
• Such effects can be achieved, for example, by adding compounds during polycondensation which, in addition to hydroxyl groups, carbonate groups or carbamoyl chloride groups, contain further functional groups or functional elements, such as mercapto groups, primary, secondary or tertiary amino groups, ether groups, carboxylic acid groups or their derivatives, sulfonic acid groups or their derivatives , Phosphonic acid groups or their derivatives, silane groups, siloxane groups, aryl groups or long-chain alkyl groups.
• further functional groups or functional elements such as mercapto groups, primary, secondary or tertiary amino groups, ether groups, carboxylic acid groups or their derivatives, sulfonic acid groups or their derivatives , Phosphonic acid groups or their derivatives, silane groups, siloxane groups, aryl groups or long-chain alkyl groups.
• carbamate groups for example ethanolamine, propanolamine, isopropanolamine, 2- (butylamino) ethanol, 2- (cyclohexylamino) ethanol, 2-amino-1-butanol, 2- (2'-amino-ethoxy) ethanol or higher alkoxylation products of ammonia, 4-hydroxypiperidine, 1-hydroxyethylpiperazine, diethanolamine, dipropanolamine, diisopropanolamine, tris (hydroxymethyl) aminomethane, tris (hydroxyethyl) aminomethane, ethylenediamine, propylenediamine, hexamethylenediamine or isophoronediamine.
• carbamate groups for example ethanolamine, propanolamine, isopropanolamine, 2- (butylamino) ethanol, 2- (cyclohexylamino) ethanol, 2-amino-1-butanol, 2- (2'-amino-ethoxy) ethanol or higher
• mercaptoethanol can be used for the modification with mercapto groups.
• Tertiary amino groups can be generated, for example, by incorporating triethanolamin, tripropanolamine, N-methyldiethanolamine, N-methyldipropanolamine or N, N-dimethylethanolamine.
• ether groups can be generated by the condensation of di- or higher-functional polyetherols.
• Ester groups can be produced by adding dicarboxylic acids, tricarboxylic acids, dicarboxylic esters, such as dimethyl terephthalate or tricarboxylic esters.
• Long-chain alkyl residues can be introduced by reaction with long-chain alkanols or alkanediols. The reaction with alkyl or aryl diisocyanates generates alkyl, aryl and urethane groups containing polycarbonates, the addition of primary or secondary amines leads to the introduction of urethane or urea groups.
• a subsequent functionalization can be obtained by the highly functional, highly or hyperbranched polycarbonate obtained in an additional process step (step c)) with a suitable functionalizing reagent which reacts with the OH and / or carbonate or carbamoyl chloride groups of the polycarbonate can implement.
• Highly functional, highly or hyperbranched polycarbonates containing hydroxyl groups can be modified, for example, by adding molecules containing acid groups or isocyanate groups.
• polycarbonates containing acid groups can be obtained by reaction with compounds containing anhydride groups.
• Highly functional polycarbonates containing hydroxyl groups can also be converted into highly functional polycarbonate polyether polyols by reaction with alkylene oxides, for example ethylene oxide, propylene oxide or butylene oxide.
• alkylene oxides for example ethylene oxide, propylene oxide or butylene oxide.
• a great advantage of the method according to the invention is its economy. Both the conversion to a condensation product (K) or polycondensation product (P) and the reaction of (K) or (P) to polycarbonates with other functional groups or elements can take place in one reaction device, which is technically and economically advantageous.
• the highly functional, highly branched or hyperbranched polycarbonates obtained by the process according to the invention can be used, for example, as adhesion promoters, thixotropic agents or as building blocks for the production of polyaddition or polycondensation polymers, for example as components for the production of lacquers, coatings, adhesives, sealants, Cast elastomers or foams. They are particularly suitable for the production of printing inks, such as flexographic, deep, offset or screen printing inks, and for the production of printing varnishes.
• the polycarbonates according to the invention are particularly suitable for the production of low-viscosity printing inks, such as flexographic or gravure printing inks, for packaging printing. They can be used in printing inks for various purposes, but in particular as binders, possibly also in a mixture with other binders.
• the polycarbonates according to the invention are formulated with suitable solvents, colorants, optionally further binders and additives typical of printing inks.
• suitable solvents colorants
• optionally further binders and additives typical of printing inks.
• WO 02/36695 and WO 02/26697 in particular to the statements in WO 02/36695, page 10, line 19 to page 15, line 14 and WO 02 / 36697, page 7, line 14 to page 10, line 18 as well as the examples given in the said documents.
• Printing inks which contain the polycarbonates according to the invention have a particularly good, hitherto unknown adhesion to the substrates, in particular to metal and / or polymer films.
• the printing inks are therefore also particularly suitable for producing laminates from two or more polymer and / or metal foils, in which one foil is printed with one or more layers of a printing ink and a second foil is laminated onto the printed layer.
• Composites of this type are used, for example, for the production of packaging.
• the polyfunctional alcohol or the alcohol mixture, the carbonate, and possibly other monomers, and catalyst 250 ppm based on the mass of alcohol
• the polyfunctional alcohol or the alcohol mixture, the carbonate, and possibly other monomers, and catalyst 250 ppm based on the mass of alcohol
• the temperature of the reaction mixture decreased due to the onset of evaporative cooling of the monoalcohol released.
• the reflux condenser was then exchanged for a descending condenser, optionally (based on **), based on the equivalent amount of catalyst, one equivalent of phosphoric acid was added, the monoalcohol was distilled off and the temperature of the reaction mixture was slowly increased to 160 ° C. In the test marked ***, the pressure was additionally reduced to 8 mbar.
• the distilled alcohol was collected in a cooled round-bottomed flask, weighed, and the conversion was thus determined as a percentage compared to the theoretically possible full conversion (see Table 1).
• reaction products were then analyzed by gel permeation chromatography, eluent was dimethylacetamide, and polymethyl methacrylate (PMMA) was used as the standard.
• PMMA polymethyl methacrylate
• TMP trimethylolpropane
• PO propylene oxide
• CHD 1,4-cyclohexanediol
• THEA tris (hydroxyethyl) amine
• CHDM 1,4-cyclohexanedimethanol
• TDME dimethyl terephthalate
• DMC dimethyl carbonate
• DEC diethyl carbonate
• a viscosity measurement was 90% in butyl acetate
• b viscosity measurement was 90% in ethyl acetate
• nb not determined
• the quality of the printing inks according to the invention was determined on the basis of the adhesive strength on various substrates.
• Measuring method tesa strength
• Test procedure "Tesafestmaschine" serves to determine the adhesion of an ink film on the substrate.
• the ink which has been thinned to the printing viscosity, is printed on the prescribed printing material or applied with a 6 ⁇ m squeegee.
• a tape of tape (tape with a width of 19 mm (Article BDF 4104, Beiersdorf AG) is attached to the ink film, pressed evenly and torn off after 10 seconds. This process is repeated 4 times with a new tape at the same place on the test object.
• Each strip of tape is glued to white paper one after the other, or black paper for white colors, and is checked immediately after the color is applied.
• the surface of the test object is visually checked for damage.
• the grading is from 1 (very bad) to 5 (very good).
• Table 2 Stencfard binders compared to polymer from Example 5 (Table 1)
• printed polymer films for example polyamide, polyethylene or polypropylene films
• other film types such as metal films or else plastic films
• Important application properties of laminates of this type for use as composite packaging are, in addition to the strength of the composite in normal storage, the strength of the composite under more stringent conditions, for example when heating or sterilizing.
• the quality of the printing inks according to the invention was assessed by determining the bond strength. Bond strength refers to the determination of the bond between two films or metal foils connected by lamination or extrusion. Measuring and testing devices;
• At least 2 strips (width: 15mm) of the material to be tested must be cut lengthways and crossways to the film web.
• the ends of the punched strips can be dipped in an appropriate solvent (e.g. 2-butanone) until the materials separate. Then the pattern must be carefully dried again.
• an appropriate solvent e.g. 2-butanone
• the delaminated ends of the test specimens are clamped in the tensile tester.
• the less stretchable film should be placed in the upper clamp.
• the end of the pattern should be held at right angles to the direction of pull, which ensures a constant pull.
• the take-off speed is 100 mm / min, the take-off angle of the separated films to the non-separated complex is 90 °.
• the bond value is read as the mean value, specified in N / 15mm.
• the ink, thinned to the printing viscosity, is printed on the specified printing material polyamide (emblem 1500) or applied with a 6 ⁇ m squeegee.
• the polyethylene laminating film is coated with the adhesive-hardener mixture Morfree A415 (adhesive) and C90 (hardener, Rohm & Haas), weight mixing ratio 100:40, so that a film thickness of approximately 6 ⁇ m (corresponds to approximately 2 , 5 g / m 2 ) results. Both foils are then pressed in such a way that the printing ink and the adhesive come into contact. After pressing, the composite films are stored at 60 ° C for 5 days.
• the following recipes (parts by weight) were chosen for the examples:
• pigment heliogen blue D 7080 (BASF AG) 15.0 binder (polyvinyl butyral) 3.0 additive (polyethylenimine, BASF AG) 69.0 ethanol
• Example 30 Compound values for the laminate made of polyamide and polyethylene:

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