Classifications

• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/78—Preparation processes
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
• • 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
  • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
  • C08G83/002—Dendritic macromolecules
  • C08G83/005—Hyperbranched macromolecules

Definitions

• the present invention relates to specifically constructed high or hyperbranched polyesters based on mono-, di-, tri- or polycarboxylic acids or their derivatives and mono-, di-, tri-, tetra- or polyols, processes for their preparation and their use.
• the high or hyperbranched polyesters of the invention may i.a. used as adhesion promoters, for example in printing inks, as rheology modifiers, as surface or interface modifiers, as functional polymer additives, as building blocks for the preparation of polyaddition or polycondensation polymers, for example of paints, coatings, adhesives, sealants, cast elastomers or foams, in a technically advantageous manner be as well as a component of binders, optionally with other components such as Isocyanates, epoxy group-containing binders or Al kyd resins, in adhesives, printing inks, coatings, foams, coatings and paints, dispersions, as surface-active amphoteric and in thermoplastic molding compositions.
• adhesion promoters for example in printing inks, as rheology modifiers, as surface or interface modifiers, as functional polymer additives, as building blocks for the preparation of polyaddition or polycondensation polymers, for example of paints, coatings
• Polyesters are usually obtained from the reaction of carboxylic acids or their derivatives with alcohols.
• aromatic polyesters i. Polymers containing ester groups, wherein the molecular units are derived primarily to one of aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid or terephthalic acid, and on the other of dialcohols, such as 1, 2-ethanediol, 1, 2 or 1, 3-propanediol or 1,4-butanediol.
• aromatic dicarboxylic acids such as phthalic acid, isophthalic acid or terephthalic acid
• dialcohols such as 1, 2-ethanediol, 1, 2 or 1, 3-propanediol or 1,4-butanediol.
• aliphatic polyesters i. Polymers comprising ester groups, wherein the molecular units are derived primarily to one of aliphatic or cycloaliphatic dicarboxylic acids, such as succinic acid, glutaric acid or adipic acid, and on the other of dialcohols, such as 1, 2-ethanediol, 1, 2 or 1, 3-propanediol, 1, 2-, 1, 3- or 1, 4-butanediol, 1, 5-pentanediol or 1, 6-hexanediol.
• aliphatic polyesters i. Polymers comprising ester groups, wherein the molecular units are derived primarily to one of aliphatic or cycloaliphatic dicarboxylic acids, such as succinic acid, glutaric acid or adipic acid, and on the other of dialcohols, such as 1, 2-ethanediol, 1, 2 or 1, 3-propanediol, 1, 2-, 1, 3- or 1, 4-
• the aromatic or aliphatic polyesters made up of these building blocks are generally linear or have a low degree of branching. Polyesters based on carboxylic acids or derivatives or alcohols having a functionality greater than two are also known.
• WO 02/34814 describes a process for the preparation of polyesters in which up to 3 mol% of a trifunctional alcohol or a trifunctional carboxylic acid are used. Due to the low content of trifunctional alcohol, however, only a small degree of branching is achieved here.
• No. 4,749,728 describes a process for preparing a polyester from trimethylolpropane and adipic acid. The process is carried out in the absence of solvents and catalysts. The water formed in the reaction is removed by simple distillation. The products thus obtained can be reacted, for example, with epoxides and processed to form thermosetting coating systems.
• WO 02/34814 describes the preparation of low branched polyesterols for powder coatings by reacting aromatic dicarboxylic acids together with aliphatic dicarboxylic acids and diols, as well as with small amounts of a branching agent, for example a triol or a tricarboxylic acid.
• EP-A 776 920 describes binders of polyacrylates and polyesters, the latter being able to comprise, as structural component, hexahydrophthalic acid and / or methylhexahydrophthalic acid and, optionally, neopentyl glycol, trimethylolpropane, other alkanediols, other dicarboxylic acids and monocarboxylic and / or hydroxycarboxylic acids in certain ratios.
• EP 1 334 989 describes the preparation of branched, low-viscosity polyesterols for coating applications for increasing the nonvolatile content.
• mixtures of di- and higher-functional carboxylic acids (functionality of the mixture at least 2.1) are reacted with trifunctional alcohols and aliphatic branched monocarboxylic acids.
• the described polyesters are to be regarded as branched, but the use of branched monocarboxylic acids which greatly reduce the viscosity of the system but also increase the unreactive proportion of the polyester is to be regarded as essential here.
• WO 93/17060 EP 630 389
• the synthesis is very inflexible, as it depends on AB2 building blocks such as dimethylolpropionic acid as the sole starting material.
• dendrimers are too expensive for general use, because even the AB2 building blocks as starting materials usually expensive and the syntheses are multi-stage and high demands are placed on the purity of the intermediate and end products.
• WO 01/46296 describes the preparation of dendritic polyesters in a multistage synthesis starting from a central molecule, such as trimethylolpropane, dimethylolpropionic acid as AB2 building block, as well as a dicarboxylic acid or a glycidyl ester as functionalizing agents. This synthesis also depends on the presence of the AB2 building block.
• WO 03/070843 and WO 03/070844 describe hyperbranched copolyester polyols based on AB 2 or also AB 3 building blocks and a chain extender, which are used in coatings systems. For example, dimethylolpropionic acid and caprolactone are used as starting materials. Again, one is dependent on an AB2 device.
• EP 1109775 describes the preparation of hyperbranched polyesters having a tetrafunctional central group.
• unsymmetrical tetrols such as homopentaerythritol
• a dendrimer-like product is used as the central molecule, which is used in paints.
• asymmetric tetrols are expensive specialty chemicals that are not commercially available in large quantities.
• EP 1070748 describes the preparation of hyperbranched polyesters and their use in powder coatings.
• the esters again based on self-condensable monomers such as dimethylolpropionic acid as AB 2 building block, are tenverinrung, the paint system in amounts of 0.2 to 5 wt.% Added as a flow improver.
• DE 101 63 163 and DE 10219508 describe the preparation of hyperbranched polyesters based on an A2 + B3 approach. This principle is based on the use of dicarboxylic acids and triols or based on tricarboxylic acids and diols. The flexibility of these syntheses is significantly higher, since one does not depend on the use of an AB2 building block.
• R. A. Gross and coworkers describe syntheses of branched polyesters by reacting dicarboxylic acids with glycerol or sorbitol and aliphatic diols. These syntheses are carried out by enzymatic catalysis and lead to "soft" products, which have a glass transition temperature between -28 ° C and 7 ° C. See Polym. Prep. 2003, 44 (2), 635, Macromolecules 2003, 36, 8219 and Macromolecules 2003, 36, 9804. The reactions under enzyme catalysis generally have long reaction times, which significantly reduces the space-time yield of the reaction and the costs for the production of Polyesters increased.
• WO 2005/118677 discloses hyperbranched polyesters which have an acid number of at least 18 mg KOH / g
• a disadvantage of the highly branched or hyperbranched polyesters disclosed in the prior art is that they are based either on expensive special monomers of the type AB y or A x B (with x or y> 1), which entails commercial disadvantages and the variability of the Properties, or that they are intrinsically always in danger of gelling and crosslinking under the significant use of A2 + By or A x + B2 monomers.
• the inherent potential for gelation and cross-linking limits both the attractiveness of their production and the field of their possible applications.
• WO 2005/1 18677 describes hyperbranched polyesters which have a low degree of crosslinking and avoid a large part of the disadvantages known from the prior art. However, gelling or cross-linking can not be ruled out even with the production method described here.
• polyester composition that is to say the molecular basic units which are derived essentially from di-, tri- or polycarboxylic acids and di-, tri-, tetra- or polyols and monocarboxylic acids, monoalcohols and hydroxycarboxylic acids. It is possible to prepare highly branched or hyperbranched polyesters which do not gel under reaction conditions if the stoichiometric ratios of the underlying monomers and / or the maximum permissible conversion are set in a specific manner.
• the selection according to the invention has proven to be non-trivial and does not become apparent to the person skilled in the art from the prior art either.
• polyesters according to the invention make it possible to adapt molecular structures, degrees of branching, end group functionalities, glassy character, softening temperatures, solubilities and dispersibilities, melt and dissolving viscosities, optical properties to the requirements of the application in a wide range and at the same time the advantageous properties of polymers to obtain finite molecular weights and expansions.
• the stoichiometric ratios of the molecular basic units found in the polyester are shown in this document on the basis that the polyester hydrolytically in the constituent monomers, ie mono-, di-, tri- or polycarboxylic acids, mono-, di-, tri-, Tetra- or polyols and optionally decomposed hydroxycarboxylic acids is thought.
• the polyester hydrolytically in the constituent monomers ie mono-, di-, tri- or polycarboxylic acids, mono-, di-, tri-, Tetra- or polyols and optionally decomposed hydroxycarboxylic acids is thought.
• a and for those derived from hydroxyl groups, B is used for molecular units of the polyester derived from carboxyl groups.
• Ai denotes units derived from monocarboxylic acids or their derivatives;
• Bi is analogous to units derived from monofunctional alcohols; B2 of diols, of triols B3, B 4 of tetraalcohols, By + of polyols having a hydroxyl functionality of five or greater.
• AB, A x B, AB y , A x By stands for structures derived from the corresponding hydroxycarboxylic acids.
• the conversion given in this document always refers to the functionality (carboxyl or hydroxyl functionality) which is present in the product or in the reaction mixture in the deficit. If the conversion approaches 100%, the polyester according to the invention by definition no longer has any free end groups of the deficiency functionality. At 0% conversion, the polyester is hydrolytically completely decomposed into its constituent monomers, ie mono-, di-, tri- or polycarboxylic acids, mono-, di-, tri-, tetra- or polyols (and optionally hydroxycarboxylic acids).
• the selection according to the invention with regard to the stoichiometry and / or the conversion is based on the average functionality fA of the molecular units A derived from carboxylic acids and on the basis of the average functionality fB of the molecular units B derived from alcohols Mole fraction xA of the groups derived from carboxylic acids. Selection criteria are the following definitions and limits:
• the selection criteria fA + fB> 4, preferably fA + fB> 4.5, particularly preferably fA + fB> 5 with fA> 2 and fB> 2 or with fA> 2 apply to the middle functionalities fA and fB and fB> fA / (fA-1) or with fA ⁇ fB / (fB-1) and fB> 2 where mean functionality of the carboxylic acids fA ⁇ ( ⁇ , nA, fA,) / ( ⁇ , nA,) average functionality of the Alcohols fB ⁇ ( ⁇ k nB k fB k ) / ( ⁇ k nB k ) with nA, as a molar amount of carboxylic acids i in mol with fA, as carboxylic acid functionality per molecule A, where fA, a positive number, for example from 1 to 8 , preferably 1 to 4, particularly preferably 2, with
• the degree of conversion U used here in each case differs from the usual conversion of a reaction mixture in such a way that only the ester, hydroxyl and carboxylic acid groups present in the product are considered and not the original reaction mixture from which this polyester is formed, is used. In many cases, typically when the composition of the reaction mixture does not change except by the withdrawal of water of reaction, the degree of conversion U of this document can be equated with the conventional concept of turnover.
• the polyester is considered hydrolyzed and the total content of the carboxyl groups results from the number of free carboxyl end groups of the product plus the carboxyl groups from the ester groups.
• the total content of the hydroxyl groups results from the number of free hydroxyl end groups of the product plus the hydroxyl groups from the ester groups.
• the degree of conversion U used here refers in each case to the functionality present in the deficit, ie to the smaller of the two values, if one compares the total content of the carboxyl groups with the total content of the hydroxyl groups.
• a non-remunerated, non-crosslinked, branched polyester of finite molecular weight is obtained when the following conversion limitation is maintained in the composition fA / [f.A + (fA-1) * fB] ⁇ xA ⁇ 0.5 (case 2b): U ⁇ [2 / f.max + (0.5
• a non-remunerated, non-crosslinked, branched polyester of finite molecular weight is obtained when the composition 0.5 ⁇ xA ⁇ [(fB-1) * fA] / [fB + (fB-1) * fA] satisfies the following limitation on sales becomes (case 2c): U ⁇
• polyesters according to the invention demonstrate the material design of the polyesters according to the invention and additionally serve to illustrate the complicated appearing, but in practice simple definition of the selection criteria according to the invention.
• polyesters according to the invention examples are:
• the monocarboxylic acids (Ai) include, for example, acetic acid, propionic acid, n-, iso- or tert. Butyric acid, valeric acid, trimethylacetic acid, caproic acid, caprylic acid, heptanoic acid, capric acid, pelargonic acid, lauric acid, myristic acid, palmitic acid, montanic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, erucic acid, fatty acids from soya, linseed, ricinus and sunflower , isostearic acid, nonanoic acid, isononanoic acid, 2-ethylhexanoic acid, ⁇ , ⁇ -dimethyl octanoic acid, ⁇ , ⁇ - dimethyl propanoic acid, benzoic acid, and unsaturated monocarboxylic acids such as acrylic or methacrylic
• the monocarboxylic acids can be used either as such or in the form of derivatives.
• unsaturated carboxylic acids or their derivatives are used as monocarboxylic acids, it may be useful to work in the presence of commercially available polymerization inhibitors.
• the dicarboxylic acids (A2) include, for example, aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, undecane- ⁇ , ⁇ -dicarboxylic acid, dodecane- ⁇ , ⁇ -dicarboxylic acid, cis- and trans Cyclohexane-1,2-dicarboxylic acid, cis- and trans-cyclohexane-1,3-dicarboxylic acid, cis- and trans-cyclohexane-1,4-dicarboxylic acid, cis- and trans-cyclopentane-1,2-dicarboxylic acid, cis- and trans-cyclopentane-1,3-dicarboxylic acid.
• aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, a
• aromatic dicarboxylic acids such as, for example, phthalic acid, isophthalic acid or terephthalic acid.
• unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid.
• Dicar Bon Textren that carry other functional groups that do not interfere with the esterification, such as 5-sulfoisophthalic acid, its salts and derivatives can be used.
• a preferred example of this is the sodium salt of the 5-sulfoisophthalic acid dimethyl ester.
• the dicarboxylic acids mentioned can also be substituted by one or more radicals selected from C 1 -C 10 -alkyl groups, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert.
• n-pentyl isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, 2-ethylhexyl, trimethylpentyl, n-nonyl or n-decyl,
• C 3 -C 12 -cycloalkyl groups for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl,
• Alkylene groups such as methylene or ethylidene or
• C 6 -C 14 aryl groups such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl Phenyl, 1-naphthyl and 2-naphthyl, more preferably phenyl.
• substituted dicarboxylic acids which may be mentioned are: 2-methyl malonic acid, 2-ethylmalonic acid, 2-phenylmalonic acid, 2-methylsuccinic acid, 2-ethylsuccinic acid, 2-phenylsuccinic acid, itaconic acid, 3,3-dimethylglutaric acid.
• mixtures of two or more of the aforementioned dicarboxylic acids can be used.
• the dicarboxylic acids can be used either as such or in the form of derivatives.
• Mono- or dialkyl esters preferably mono- or di-C 1 -C 4 -alkyl esters, more preferably mono- or dimethyl esters or the corresponding mono- or
• Ci-C4-alkyl in this document means methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, preferably methyl, ethyl and n-butyl, particularly preferably methyl and ethyl, and most preferably methyl.
• malonic acid succinic acid, glutaric acid, adipic acid, 1, 2, 1, 3 or 1, 4-cyclohexanedicarboxylic acid (hexahydrophthalic acids), phthalic acid, isophthalic acid, terephthalic acid or their mono- or dialkyl esters.
• Reactable tricarboxylic acids (A3), tetracarboxylic acids (A 4 ) or polycarboxylic acids (AxA x ) are, for example, aconitic acid, 1, 3,5-cyclohexanetricarboxylic acid, 1, 2,4-benzenetricarboxylic acid, 1, 3,5-benzenetricarboxylic acid, 1, 2,4 , 5-Benzoltetracarboxylic acid (pyromellitic acid) and mellitic acid and low molecular weight polyacrylic acids.
• Tricarboxylic acids (A3), tetracarboxylic acids (A 4 ) or polycarboxylic acids (A x + ) can be used in the process according to the invention either as such or in the form of derivatives.
• Derivatives are preferably understood to mean the relevant anhydrides in monomeric or else polymeric form, "monodi or trialkyl, preferably mono-, di- or tri-C 1 -C 4 -alkyl, particularly preferably mono-, di- or trimethyl esters or corresponding mono-, di- or triethyl ester, furthermore mono-, di- and trivinyl esters and mixed esters, preferably mixed esters with different C 1 -C 4 -alkyl components, particularly preferably mixed methyl ethyl esters.
• a mixture of a tri-, tetra- or polycarboxylic acid and one or more of its derivatives for example a mixture of pyromellitic acid and pyromellitic dianhydride.
• a mixture of several different derivatives of one or more tri- or polycarboxylic acids for example a mixture of 1,3,5-cyclohexanetricarboxylic acid and pyromellitic dianhydride.
• the monoalcohols (Bi) include, for example, methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1,3-propanediol monomethyl ether, n- Hexanol, n-
• diols (B2) examples are ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,2-diol, butane-1,3-diol, butane.
• n is an integer and n> 4 with a molecular weight up to 2000 g / mol, polyethylene-polypropylene glycols, where the sequence of ethylene oxide-propylene oxide units is blockwise or random with a molecular weight of up to 2000 g / mol, polytetramethylene glycols, preferably up to a molecular weight of up to 5000 g / mol, poly-1, 3-propanediols, preferably having a molecular weight of up to 5000 g / mol, polycaprolactones or mixtures of two or more representatives of the above connections.
• diols are ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 2, 1, 3 - And 1, 4-cyclohexanediol, 1, 3- and 1, 4-bis (hydroxymethyl) cyclohexane, and diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol.
• At least trifunctional alcohols include glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, 1, 2,4-butanetriol, tris (hydroxymethyl) amine,
• glycerol diglycerol, triglycerol, trimethylolethane, trimethylolpropane,
• fA that is the carboxylic acid functionality per molecule A 1
• f.Bk ie hydroxyl functionality per molecule Bk
• fA and f.Bk are positive fractional numbers smaller than the nominal positive integers according to the structural formula, which are effective functionalities and, in turn, are functions of temperature, pressure, and other reaction conditions.
• glycerin would have a nominal hydroxy functionality of 3.
• the secondary hydroxy function has lower reactivity than the primary hydroxy function, the secondary hydroxy function will effectively participate less in the reaction, depending on the reaction conditions.
• glycerol has an effective functionality below 3, for example 2.5 to less than 3. The exact effective functionalities can be determined under the reaction conditions used.
• the carboxylic acids A or alcohols B can have, in addition to carboxyl or hydroxyl groups, further functional groups or functional elements, a polyester according to the invention having other functionalities different from carboxyl or hydroxyl groups being obtained.
• Functional groups may, for example, furthermore be ether groups, carbonate groups, urethane groups, urea groups, thiol groups, thioether groups, thioester groups, keto or aldehyde groups, trisubstituted amino groups, nitrile or isonitrile groups, carboxamide groups, sulfonamide groups, silane groups or siloxane groups, sulfonic acid, sulfenic acid groups. or sulfinic acid groups, phosphonic acid groups, vinyl or allyl groups.
• Such effects can be achieved, for example, by addition of functionalized building blocks as compounds during the polycondensation, in addition to hydroxyl groups or carboxyl groups further functional groups or functional elements such as mercapto, tertiary amino, ether, carbonyl, sulfonic or derivatives of sulfonic acids, sulfinic acids or derivatives of Sulfin acids, phosphonic acids or derivatives of phosphonic acids, phosphinic acids or derivatives of phosphinic acids, silane groups, siloxane, wear.
• functionalized building blocks as compounds during the polycondensation, in addition to hydroxyl groups or carboxyl groups further functional groups or functional elements such as mercapto, tertiary amino, ether, carbonyl, sulfonic or derivatives of sulfonic acids, sulfinic acids or derivatives of Sulfin acids, phosphonic acids or derivatives of phosphonic acids, phosphinic acids or derivatives of phosphinic acids
• Mercaptoethanol or thioglycerol can be used for the modification with mercapto groups, for example.
• Tertiary amino groups can be prepared, for example, by incorporation of N-methyldiethanolamine, N-methyldipropanolamine or N, N- Produce dimethylethanolamine.
• Ether groups can be generated, for example, by condensation of di- or higher-functional polyetherols.
• the highly branched or hyperbranched polyesters according to the invention have a glassy character without pronounced crystallinity of the polyester skeleton.
• Highly or hyperbranched polyesters in which side chains crystallize, for example alkane radicals, are also considered to be in accordance with the invention.
• the polyesters of the invention have a number average molecular weight M n of at least 500, preferably at least 750 and more preferably at least 1,000 g / mol.
• the upper limit of the molecular weight M n is preferably 100,000 g / mol, more preferably not more than 50,000 and most preferably not more than 10,000 g / mol.
• the polyesters according to the invention have a weight-average molecular weight M w of at least 750, preferably at least 1500 and more preferably at least 2500 g / mol.
• the upper limit of the molecular weight M w is preferably 500,000 g / mol, more preferably it is not more than 100,000, and most preferably not more than 50,000 g / mol.
• the data on the number average and weight average molecular weights M n and M w and the resulting polydispersity M w / M n relate to gel permeation-chromatographic measurements using polymethyl methacrylate as standard and tetrahydrofuran or hexafluoroisopropanol or dimethylacetamide as eluent. The method is described in the Analyst Taschenbuch Vol. 4, pages 433 to 442, Berlin 1984.
• the polydispersity of the polyesters of the invention is 1, 2 to 50, preferably 2 to 40, more preferably 2.5 to 30 and most preferably to 10.
• the polyesters according to the invention are usually very readily soluble, ie, at 25 ° C., clear solutions having a content of up to 50% by weight, in some cases even more than 80% by weight, of the polyester according to the invention in tetrahydrofuran (THF), ethyl - Acetate, n-butyl acetate, methyl ethyl ketone, acetone, ethanol or other solvents o- represent the solvent mixtures, without the naked eye gel particles are detectable bar. Even in the case of microfiltration, in the case of polyesters according to the invention no degree of recovery is found which is higher than that of a linear polyester of comparable molar mass Mw.
• THF tetrahydrofuran
• optically clear solutions preferably: 5-30% by weight
• a suitable solvent preferably: ethyl acetate, butyl acetate, methyl ethyl ketone, anhydrous acetone, less preferably: acetone-water mixtures, hexafluoroisopropanol, Dichloroacetic acid.
• the dissolution process can take several hours and possibly elevated temperatures.
• a suitable volume preferably: 5 to 50 ml
• the filter is dried and the polymer fraction remaining on the membrane is determined gravimetrically. If the filter locks during filtration of the solution, the non-filterable volumes are used as a measure of the relative degree of gelling.
• the highly branched and hyperbranched polyesters according to the invention can be terminated by carboxyl groups, terminated by carboxyl groups and hydroxyl groups, or terminated by hydroxyl groups.
• Terminal carboxyl groups may be present as free carboxylic acids, as neutralized carboxylic acid salts or as common reaction products (e.g., with epoxides).
• the polyesters are especially hydroxyl-terminated.
• they may be used to make e.g. Of adhesives, inks, coatings, foams, coatings and paints are used advantageously.
• the polyesters are especially carboxyl-terminated. They can be used advantageously, for example, in aqueous and nonaqueous dispersions and surface coatings.
• the invention furthermore relates to processes for the preparation of the polyesters according to the invention within the scope of the boundary conditions according to the invention.
• the processes according to the invention can be carried out in bulk or in the presence of a solvent. In a preferred embodiment, the reaction is carried out free of solvent.
• a water-removing agent which is added at the beginning of the reaction.
• Suitable examples are molecular sieves, in particular molecular sieve 4A, MgSO 4 and Na 2 SO 4 . It is also possible during the reaction to add further de-watering agent or to replace de-watering agent with fresh de-watering agent.
• the process according to the invention can be carried out in the absence of catalysts. However, it is preferable to work in the presence of at least one catalyst. These are the usual catalysts for esterification and transesterification reactions as are familiar to those skilled in the art.
• Such catalysts are used in the usual concentrations. Typical concentrations are from 3 to 1000 ppm of the catalyzing metal based on the carboxylic acid monomers.
• antimony (III) acetate antimony (III) oxide, germanium (IV) oxide, freshly precipitated titanium hydroxide oxides TiO (OH) 2 and similar compositions
• titanium tetrabutoxide Ti [OC 4 Hg] 4 titanium tetraisopropoxide Ti [O-CH (CHs) 2 J 4 , potassium titanyl oxalate hydrate K 2 TiO [C 2 O 4 J 2 x H 2 O, dibutyltin dilaurate Sn [C 4 H 9 ] 2 [OCi 2 H 25 ] 2 , dibutyltin oxide Sn [C 4 Hg] 2 O and similar compositions
• tin (II) n-octanoate tin (II) 2-ethylhexanoate
• tin (II) laurate dibutyltin oxide, diphenyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin di
• acidic organic catalysts such as organic compounds with, for example, carboxyl groups (also autocatalysis), phosphate groups, sulfonic acid groups, sulfate groups or phosphonic acid groups. Particularly preferred are sulfonic acids such as para-toluenesulfonic acid. 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.
• acidic inorganic catalysts examples are sulfuric acid, sulfates and hydrogen sulfates, such as sodium hydrogen sulfate, phosphoric acid, phosphonic acid, hypophosphorous acid, aluminum sulfate hydrate, alum, acidic silica gel (pKs ⁇ 6, especially ⁇ 5) and acidic alumina.
• aluminum compounds of the general formula Al (OR 1 ) 3 and titanates of the general formula Ti (OR 1 ) 4 can be used as acidic inorganic catalysts, where the radicals R 1 can each be identical or different and are selected independently of one another from:
• C 1 -C 20 -alkyl radicals for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec.
• C 3 -C 12 -cycloalkyl radicals for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl.
• radicals R 1 in Al (OR 1 ) 3 or Ti (OR 1 ) 4 are preferably identical and selected from n-butyl, isopropyl or 2-ethylhexyl.
• Preferred acidic organometallic catalysts are, for example, selected from dialkyltin oxides R 1 2 SnO or dialkyltin esters R 1 2 Sn (OR 2) 2 wherein R 1 is as defined above standing and can be identical or different.
• R 2 may have the same meanings as R 1 and additionally C 6 -C 12 aryl, for example phenyl, o-, m- or p-tolyl, xylyl or naphthyl. Each R 2 may be the same or different.
• organotin catalysts examples include tin (II) n-octanoate, tin (II) 2-ethylhexanoate, tin (II) laurate, dibutyltin oxide, diphenyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimaleate or dioctyltin diacetate ,
• acidic organometallic catalysts are dibutyltin oxide, diphenyltin oxide and dibutyltin dilaurate.
• transesterification catalysts such as oxides, carboxylates, organometallic compounds and complexes of manganese, cobalt, zinc, calcium or magnesium, such as acetates, alkoxides, oxalates can be used.
• Such catalysts are used in the usual concentrations. Typical concentrations are 5 to 500 ppm of the catalyzing metal based on the carboxylic acid monomers. Examples of these are manganese (II) acetate and magnesium acetate,
• acidic inorganic, organometallic or organic catalysts 0.1 to 10% by weight, preferably 0.2 to 2% by weight, of catalyst is used. Enzymes or decomposition products of enzymes are also possible organic catalysts in the context of the present invention. Also, the carboxylic acids can act as acidic organic catalysts in the context of the present invention, as long as either the degree of conversion is limited or carboxyl groups are not present as Unterschußkomponente.
• the process according to the invention is preferably carried out under an inert gas atmosphere, i. a gas which is inert under the reaction conditions, for example under carbon dioxide, combustion gases, nitrogen or noble gas, of which in particular argon can be mentioned.
• an inert gas atmosphere i. a gas which is inert under the reaction conditions, for example under carbon dioxide, combustion gases, nitrogen or noble gas, of which in particular argon can be mentioned.
• the inventive method is carried out at temperatures of 60 to 350 0 C.
• the reaction is carried out at the lowest possible temperatures, but above a temperature at which all components of the reaction mixture are in fluid form.
• the reaction is carried out at temperatures above the boiling point of low molecular weight condensation products to be distilled off.
• the pressure conditions of the process according to the invention are generally not critical. They depend on the volatility of the starting materials, intermediates and condensation products at the above reaction temperatures.
• the reaction for producing the polyesters according to the invention preferably takes place in such a way that the condensation product (usually water or methanol) can be easily removed via the gas phase and monomers and oligomers remain in the reaction mixture. It is possible to depress by pressing until e.g. 10 bar, atmospheric pressure, but also work at low pressure. Preference may be given to processes under excess pressure, for example when the desired reaction temperature is above the boiling point of a monomer at atmospheric pressure. Preference may be given to processes under normal pressure, for example if the mass transfer in the gas phase is not limiting or if monomers or oligomers tend to sublime or evaporate.
• processes at reduced pressure may be preferred, for example when mass transfer in the gas phase is limiting or monomers are to be withdrawn for a controlled reaction progress.
• a significantly reduced pressure for example at 3 to 500 mbar, more preferably below 50 mbar and most preferably below 5 mbar.
• the reaction time of the process according to the invention is usually 10 minutes to 48 hours, preferably 30 minutes to 24 hours.
• the solid or liquid starting substances a) and b) are added in bulk or solution or suspended or emulsified in a suitable solvent in a heatable and stirrable reaction volume.
• the catalysts listed can be added to the reaction vessel individually or together, in bulk, in solution or in admixture with suitable starting substances a) or b). The addition of the catalysts can be carried out at the beginning of the reaction or at any suitable time in the course of the reaction.
• the starting materials a) and b) initially introduced in the reaction volume are heated with or without catalyst and, if appropriate, all components are brought into liquid phase.
• reaction mixture is stirred under elevated temperatures in such a way that the surface of the reaction mixture is continually renewed and allows the efficient discharge of low-molecular condensation products, for example water or methanol.
• the pressure and temperature profile are selected such that the boiling point of the low molecular weight condensation products to be discharged is exceeded, but as far as possible no bumping, local overheating, foaming, uncontrolled spraying of the reaction mixture in the reaction volume occur.
• pressure and temperature profiles are selected so that the boiling point of the low molecular weight condensation products to be discharged is exceeded, but as far as possible no boiling or sublimation point of starting substances or oligomers is achieved.
• the composition of the reaction mixture remains constant over the entire reaction time with respect to the di- or higher-functional carboxylic acids and di- or higher-functional alcohol-based molecular units.
• the composition of the reaction mixture with respect to the molecular units based on di- or higher-functional carboxylic acids and di- or higher-functional alcohol-based molecular units does not remain constant throughout the reaction time.
• the Composition can be changed by distillative separation of a diol or based on it cyclic ether.
• the composition of the reaction mixture with respect to the carboxylic acids and alcohol-based molecular units does not remain constant throughout the reaction time.
• the composition can be changed by subsequent addition of an alcohol or a carboxylic acid.
• the course of the reaction is followed by non-continuous or regular quasi-continuous or continuous measuring methods.
• the course of the reaction is measured by random determination of the acid numbers, by random determination of the melt viscosity or by continuous measurement of the torque or the force absorption of a stirrer motor.
• the highly branched and hyperbranched polyesters of the invention can be directly granulated from the melt.
• the polyester according to the invention can be mixed with solvents and converted into a solution or dispersion. The choice of the preferred embodiment depends on how the product can be better handled and stored and which form provides advantages for further use.
• polyesters of the invention When the polyesters of the invention are prepared in solution, they may be directly further-crosslinked or the polymer may be subjected to sequential reactions and / or by stripping off the solvent, usually by depressurising the solvent under reduced pressure, or precipitating the polymer, for example using water as the solvent Be isolated precipitant. Possibly. The polymer can then be washed and dried.
• Subsequent reactions may, for example, be those reactions of the ester, carboxyl or hydroxyl groups which do not significantly change the hyperbranched structure of the polyester.
• free carboxylic acid functions are completely or partially neutralized with bases.
• Suitable bases for this purpose may be secondary and tertiary amines such as, for example, morpholine, diethanolamine, triethanolamine, triethylamine, N, N-diethylethanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine.
• free carboxylic acid functions are completely or partially reacted with epoxides.
• Suitable examples include epoxidized olefins, glycidyl esters (eg glycidyl (meth) acrylate) of saturated or unsaturated carboxylic acids or glycidyl ethers of aliphatic or aromatic polyols and glycidol.
• epoxides are, for example, unsubstituted or substituted alkylene oxides such as ethylene oxide and / or propylene oxide, epichlorohydrin, epibromohydrin, 2,3-epoxy-1-propanol, 1-allyloxy-2,3-epoxypropane, 2,3-epoxy-phenyl ether, 2 , 3-epoxypropyl isopropyl ether, 2,3-epoxypropyl octyl ether or 2,3-epoxypropyltrimethyl ammonium chloride.
• alkylene oxides such as ethylene oxide and / or propylene oxide
• epichlorohydrin epibromohydrin
• 2,3-epoxy-1-propanol 1-allyloxy-2,3-epoxypropane
• 2,3-epoxy-phenyl ether 2,3-epoxy-phenyl ether
• 3-epoxypropyl isopropyl ether 2,3-
• the acid functionalities containing hyperbranched polyester optionally dissolved in a suitable solvent, at temperatures between 0 0 C and 120 0 C, preferably between 10 and 100 0 C and particularly preferably between 20 and 80 0 C, preferably under protective gas, such as nitrogen, submitted.
• the alkylene oxide is dissolved continuously or in portions, optionally at a temperature of -30 0 C to 50 0 C, with thorough mixing so that the temperature of the reaction mixture between 120 and 180 0 C, preferably between 120 and 150 0 C is maintained ,
• the reaction can take place under a pressure of up to 60 bar, preferably up to 30 bar and particularly preferably up to 10 bar.
• a catalyst can be added for acceleration.
• alkylene oxide After complete metered addition of the alkylene oxide is generally 10 to 500 minutes, preferably 20 to 300 minutes, more preferably 30 to 180 minutes at temperatures between 30 and 220 0 C, preferably 80 to 200 0 C and particularly preferably 100 to 180 0 post-reacted let the temperature remain the same or can be raised gradually or continuously.
• the conversion of alkylene oxide is preferably at least 90%, particularly preferably at least 95% and very particularly preferably at least 98%.
• Possible residues of alkylene oxide can be stripped out of the reaction mixture by passing a gas, for example nitrogen, helium, argon or steam.
• free hydroxyl functions are fully or partially reacted with activated carboxylic acid derivatives.
• anhydrides, carboxylic acid halides and esters, preferably methyl esters, and carbonates such as, for example, succinic anhydride, maleic anhydride, phthalic anhydride, hydrophthalic anhydride and dimethyl carbonate, diethyl carbonate, are suitable for this purpose.
• succinic anhydride, maleic anhydride, phthalic anhydride, hydrophthalic anhydride and dimethyl carbonate, diethyl carbonate are suitable for this purpose.
• Particular preference is given to setting mild reaction conditions, in particular lower reaction temperatures.
• azeotrope-forming solvent such as n-pentane, n-hexane, n-heptane, cyclohexane, methylcyclohexane, benzene, toluene or xylene. It may be useful to catalyze the reaction, for example enzymatically.
• free hydroxyl functions are completely or partially reacted with carboxylic acids C.
• carboxylic acids C the monocarboxylic acids A L described above are suitable for this purpose .
• long-chain, branched aliphatic carboxylic acids are used which reduce the polarity and positively influence the dissolution behavior of the polyesters.
• ⁇ , ⁇ -unsaturated carboxylic acids or their derivatives are used. To suppress polymerization in the reaction of ⁇ , ß-unsaturated carboxylic acids or derivatives thereof, it may be useful to work in the presence of commercially available polymerization inhibitors, which are known in the art per se.
• free hydroxyl functions are completely or partially modified by addition of molecules containing isocyanate groups.
• polyesters containing urethane groups can be obtained by reaction with alkyl or aryl isocyanates.
• free hydroxyl functions are fully or partially modified by reaction with lactones (e.g., ⁇ -caprolactone).
• lactones e.g., ⁇ -caprolactone
• the invention further relates to the uses of the polyesters according to the invention.
• the high or hyperbranched polyesters according to the invention or produced according to the invention can i.a. as adhesion promoters, for example in printing inks, as rheology modifiers, as surface or interface modifiers, as functional polymer additives, as building blocks for the preparation of polyaddition or polycondensation onspolymeren, for example, paints, coatings, adhesives, sealants, casting elastomers or foams technically be used advantageously, and as a component of binders, optionally with other components such as Isocyanates, epoxy group-containing binders or alkyd resins, in adhesives, printing inks, coatings, foams, coatings and paints, dispersions, as surface-active amphoteric and in thermoplastic molding compositions.
• adhesion promoters for example in printing inks, as rheology modifiers, as surface or interface modifiers, as functional polymer additives, as building blocks for the preparation of polyaddition or polycondensation onspolymeren,
• a further aspect of the present invention is the use of the highly branched and hyperbranched polyesters according to the invention for the preparation of polyaddition or polycondensation products, for example polycarbonates, polyurethanes, polyesters and polyethers.
• a further aspect of the present invention is the use of the highly branched and hyperbranched polyesters according to the invention and the polyaddition or polycondensation products prepared from highly functional, highly branched and hyperbranched polyesters as a component of printing inks, adhesives, coatings, foams, coatings and paints.
• Another aspect of the present invention are printing inks, adhesives, coatings, foams, coatings and paints containing at least one inventive hyperbranched and hyperbranched polyaddition or polycondensation from the inventive hyperbranched and hyperbranched polyesters, which are characterized by excellent application Characterize properties.
• a further preferred aspect of the present invention is the use of the highly branched or hyperbranched polyesters according to the invention in printing inks, in particular packaging inks for flexographic and / or gravure printing, at least one high or hyperbranched polyester prepared according to the invention, at least one solvent or a Mixture of various solvents, at least one colorant, at least one polymeric binder and optionally further additives.
• the highly branched and hyperbranched polyesters according to the invention can also be used in admixture with other binders in the context of the present invention.
• further binders for such printing inks include polyvinyl butyral, nitrocellulose, polyamides, polyurethanes, polyacrylates or polyacrylate copolymers.
• the combination of high and hyperbranched polyesters with nitrocellulose has proved particularly advantageous.
• the total amount of all binders in printing inks is usually 5 to 35 wt .-%, preferably 6 to 30 wt .-% and particularly preferably 10 to 25 wt .-% based on the sum of all components.
• the ratio of highly branched and hyperbranched polyester to the total amount of all binders is usually in the range of 30 wt .-% to 100 wt .-%, preferably at least 40 wt .-%, but the amount of highly branched and hyperbranched polyester as a rule 3 wt .-%, preferably 4 wt .-% and particularly preferably 5 wt .-% should not fall below the sum of all components of the ink.
• Suitable solvents in principle are the customary solvents for printing inks, in particular packaging printing inks.
• Particularly suitable as solvents for the printing ink according to the invention are alcohols, such as, for example, 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.
• Particularly preferred solvents are ethanol or mixtures, which consist predominantly of ethanol, and ethyl acetate.
• the solvents which are possible in principle the person skilled in the art makes a suitable choice, depending on the solubility properties of the polyester and the desired properties of the printing ink. Usually, 40 to 80% by weight of solvent are used with respect to the sum of all constituents of the printing ink.
• colorants the usual dyes and preferably conventional pigments can be used. Of course, it is also possible to use mixtures of different dyes or colorants, and also soluble organic dyes. Usually, from 5 to 25% by weight of colorants are used with respect to the sum of all constituents.
• Pigments are according to CD Römpp Chemie Lexikon - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995 with reference to DIN 55943 particulate "practically insoluble in the application medium, inorganic or organic, colored or achromatic colorants".
• practically insoluble means a solubility at 25 ° C. of less than 1 g / 1000 g of application medium, preferably less than 0.5, more preferably less than 0.25, very preferably less than 0.1 and in particular less than 0.05 g / 1000 g of application medium.
• pigments include any systems of absorption and / or effect pigments, preferably absorption pigments. Number and selection of the pigment components are not subject to any restrictions. They can be adapted to the particular requirements, for example the desired color impression, as desired. For example, all the pigment components of a standardized mixed-paint system can be based.
• Effect pigments are to be understood as meaning all pigments which have a platelet-like structure and impart special decorative color effects to a surface coating.
• the effect pigments are, for example, all effect pigments which can usually be used in vehicle and industrial coating. Examples of such effect pigments are pure metal pigments; such as aluminum, iron or copper pigments; Interference pigments, such as z, B. titanium dioxide coated mica, iron oxide coated mica, mixed oxide coated mica (eg with titanium dioxide and Fe2O3 or titanium dioxide and C1 -C6), metal oxide coated aluminum, or liquid crystal pigments.
• the coloring absorption pigments are, for example, customary organic or inorganic absorption pigments which can be used in the coatings industry. Examples of organic absorption pigments are azo pigments, phthalocyanine, quinacridone and pyrrolopyrrole pigments. Examples of inorganic absorption pigments are iron oxide pigments, titanium dioxide and carbon black.
• Dyes are also colorants and differ from the pigments by their solubility in the application medium, ie they have at 25 0 C, a solubility above 1 g / 1000 g in the application medium.
• dyes examples include azo, azine, anthraquinone, acridine, cyanine, oxazine, polymethine, thiazine, triarylmethane dyes. These dyes may find application as basic or cationic dyes, mordant, direct, disperse, development, vat, metal complex, reactive, acid, sulfur, coupling or substantive dyes.
• Coloriferous inert fillers are understood as meaning all substances / compounds which on the one hand are coloristically inactive; i.e. which show low intrinsic absorption and whose refractive index is similar to the refractive index of the coating medium, and which, on the other hand, are capable of controlling the orientation (parallel alignment) of the effect pigments in the surface coating, i. in the applied paint film to influence, further properties of the coating or the coating materials, such as hardness or rheology.
• examples of usable inert substances / compounds are mentioned, but without limiting the term coloristically inert topology-influencing fillers to these examples.
• Suitable inert fillers as defined may be, for example, transparent or semi-transparent fillers or pigments, e.g. Silica gels, blancfixe, diatomaceous earth, talc, calcium carbonates, kaolin, barium sulfate, magnesium silicate, aluminum silicate, crystalline silica, amorphous silica, alumina, microspheres or hollow microspheres e.g. made of glass, ceramic or polymers with sizes of for example 0.1-50 microns.
• any solid inert organic particles such as e.g. Urea-formaldehyde condensation products, micronized polyolefin wax and micronized amide wax.
• the inert fillers can also be used in each case in a mixture. Preferably, however, only one filler is used in each case.
• An exemplary ink may optionally include other additives and auxiliaries.
• additives and auxiliaries are fillers such as calcium carbonate, alumina 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, petroleum waxes or ceresin waxes.
• Fatty acid amides can be used to increase the surface smoothness.
• 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 esters or esters of adipic acid.
• Dispersing agents may be used to disperse the pigments.
• the total amount of all additives and auxiliaries usually does not exceed 20% by weight with respect to the sum of all constituents of the printing ink and is preferably 0-10% by weight.
• paints, printing inks or coating compositions can be carried out in a basically known manner by intensive mixing or dispersion of the constituents in customary apparatuses, for example dissolvers, stirred ball mills or a three-roll mill.
• customary apparatuses for example dissolvers, stirred ball mills or a three-roll mill.
• a concentrated pigment dispersion with a portion of the components and a portion of the solvent is first prepared, which is further processed later with other ingredients and further solvent to the finished ink.
• a further preferred aspect of the present invention is printing inks which comprise at least one solvent or a mixture of different solvents, at least one polymeric binder and optionally further additives, at least one of the polymeric binders being a highly branched and hyperbranched high-functionality polyester according to the invention, as well as the use of the printing lacquers according to the invention for priming, or as a protective lacquer and for producing multilayer materials.
• the printing varnishes according to the invention contain no colorants, but apart from that they have the same constituents as the already described printing inks according to the invention.
• the quantities of the other components increase accordingly.
• polyesters according to the invention can be used as binder component, for example in coating compositions, optionally together with other hydroxyl- or amino-containing binders, for example with hydroxy (meth) acrylates (polyacrylatols), hydroxystyryl (meth) acrylates, linear or branched polyesters, polyethers , Polycarbonates, melamine resins or urea-formaldehyde resins, together with compounds which are reactive toward carboxy and / or hydroxyl functions, for example with isocyanates, blocked isocyanates, epoxides, carbonates and / or aminoplasts, preferably isocyanates, epoxides or aminoplasts, particularly preferably with isocyanates or epoxides and very particularly preferably with isocyanates.
• Isocyanates are, for example, aliphatic, aromatic and cycloaliphatic di- and polyisocyanates having an average NCO functionality of at least 1, 8, preferably 1, 8 to 6 and particularly preferably 2 to 4, and their isocyanurates, oxadiazinetriones, iminooxadiazinediones, ureas, biurets, amides , Urethanes, allophanates, carbodiimides, uretonimines and uretdiones.
• the diisocyanates are preferably isocyanates having 4 to 20 C atoms.
• Examples of customary diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, 1,5-diisocyanatopentane, hexamethylene diisocyanate (1, 6
• Diisocyanatohexane Diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1, 4, 1, 3 or 1, 2-diisocyanatocyclohexane, 4,4'- or 2,4 ' Di (isocyanatocyclohexyl) methane, 1-isocyanato-3,3,5-trimethyl-5- (isocyanatomethyl) cyclohexane (isophorone diisocyanate),
• Suitable polyisocyanates are polyisocyanates containing isocyanurate groups, uretdione diisocyanates, biuret-containing polyisocyanates, polyisocyanates containing amide groups, polyisocyanates containing urethane or allophanate groups, oxadiazinetrione groups or polyisocyanates containing iminooxadiazinedione groups, carbodiimide- or uretonimine-modified polyisocyanates of straight-chain or branched C 4 -C 20 -alkylene diisocyanates , Cycloaliphatic diisocyanates having a total of 6 to 20 carbon atoms or aromatic diisocyanates having a total of 8 to 20 carbon atoms or mixtures thereof.
• aliphatic or cycloaliphatic di- and polyisocyanates e.g. the abovementioned aliphatic or cycloaliphatic diisocyanates, or mixtures thereof.
• hexamethylene diisocyanate 1, 3-bis (isocyanatomethyl) - cyclohexane, isophorone diisocyanate and di (isocyanatocyclohexyl) methane
• isophorone diisocyanate and hexamethylene diisocyanate particularly preferred is hexamethylene diisocyanate.
• isocyanurate-containing polyisocyanates of aromatic, aliphatic and / or cycloaliphatic diisocyanates Particular preference is given here to the corresponding aliphatic and / or cycloaliphatic isocyanato-isocyanurates and in particular those based on hexamethylene diisocyanate and isophorone diisocyanate.
• the isocyanurates present are, in particular, trisisocyanatoalkyl or trisisocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologues containing more than one isocyanurate ring.
• the isocyanato-isocyanurates generally have an NCO content of 10 to 30 wt .-%, in particular 15 to 25 wt .-% and an average NCO functionality of 2.6 to 4.5.
• Uretdione diisocyanates having aromatic, aliphatic and / or cycloaliphatic bonded isocyanate groups, preferably aliphatically and / or cycloaliphatically bonded and in particular those derived from hexamethylene diisocyanate or isophorone diisocyanate.
• Uretdione diisocyanates are cyclic dimerization products of diisocyanates.
• uretdione diisocyanates can be used in the preparations according to the invention as the sole component or in a mixture with other polyisocyanates, in particular those mentioned under 1).
• Isocyanate groups in particular tris (6-isocyanatohexyl) biuret or mixtures thereof with its higher homologs.
• These biuret grouped poly- isocyanates generally have an NCO content of 18 to 23 wt .-% and an average NCO functionality of 2.8 to 4.5.
• Allophanate-containing polyisocyanates generally have an NCO content of 12 to 20 wt .-% and an average NCO functionality of 2.5 to 4.5.
• oxadiazinetrione-containing polyisocyanates preferably derived from hexamethylene diisocyanate or isophorone diisocyanate.
• oxadiazinetrione-containing polyisocyanates can be prepared from diisocyanate and carbon dioxide.
• Iminooxadiazindion phenomenon containing polyisocyanates preferably derived from hexamethylene diisocyanate or isophorone diisocyanate.
• polyisocyanates containing iminooxadiazinedione groups can be prepared from diisocyanates by means of special catalysts.
• the polyisocyanates 1) to 7) can be used in a mixture, if appropriate also in a mixture with diisocyanates.
• the isocyanate groups of the di- or polyisocyanates may also be present in capped form.
• Suitable capping agents for NCO groups are, for example, oximes, phenols, imidazoles, pyrazoles, pyrazolinones, triazoles, diketopiperazines, caprolactam, malonic acid esters or compounds as mentioned in the publications by ZW Wicks, Prog. Org. Coat. 1975, 3 73-99 and Prog. Org. Coat 1981, 9, 3-28, by DA Wicks and ZW Wicks, Prog. Org. Coat. 1999, 36, 148-172 and Prog. Org. Coat. 2001, 41, 1-83 and in Houben-Weyl, Methods of Organic Chemistry, Vol.
• blocking or blocking agents are meant compounds which convert isocyanate groups into blocked (capped or protected) isocyanate groups, which then do not exhibit the usual reactions of a free isocyanate group below the so-called deblocking temperature.
• Such compounds having blocked isocyanate groups are commonly used in dual-cure or powder coatings which are finally cured by isocyanate group cure.
• Epoxy compounds are those having at least one, preferably having at least two, particularly preferably two to ten epoxide groups in the molecule.
• glycidyl esters e.g., glycidyl (meth) acrylate
• saturated or unsaturated carboxylic acids or glycidyl ethers aliphatic or aromatic polyols, and glycidol.
• Such products are commercially available in large numbers.
• Particularly preferred are bisphenol A, F or B type polyglycidyl compounds and glycidyl ethers of polyfunctional alcohols, e.g. Butanediol, 1, 6-hexanediol, glycerol and pentaerythritol.
• Examples of such polyepoxide compounds are Epikote® 812 (epoxy value: approx. 0.67 mol / 100g) and Epikote® 828 (epoxy value: approx. 0.53 mol / 100g), Epikote® 1001, Epikote® 1007 and Epikote® 162 0.61 mol / 100g) from Resolution,
• Gertapox® 0162 epoxy value: about 0.58 mol / 100g
• Scotland epoxy value: about 0.53 mol / 100g
• GAtapox® 0165 epoxy value: about 0.48 mol / 100 g
• Araldit® DY 0397 epoxy value: about 0.83 mol / 100 g
• Carbonate compounds are those having at least one, preferably having at least two, preferably two or three carbonate groups in the molecule, which preferably contain terminal C 1 -C 20 -alkyl carbonate groups, particularly preferably terminal C 1 -C 4 -alkyl carbonate groups, very particularly preferably terminal methyl carbonate, ethyl carbonate or n-butyl carbonate ,
• methylalkoxy groups such as etherified reaction products of formaldehyde with amines such as melamine, urea, etc., phenol / formaldehyde adducts, siloxane or silane groups, and anhydrides, e.g. in US 5,770,650 are described.
• preferred aminoplasts are particularly preferably urea resins and melamine resins, such as urea-formaldehyde resins, melamine-formaldehyde resins, melamine-phenol-formaldehyde resins or melamine-urea-formaldehyde resins, usable.
• Suitable resin substances are those which are obtainable by reacting ureas with aldehydes and may be modified if desired.
• urea, N-substituted or N, N'-disubstituted ureas are suitable, e.g. N-methylurea, N-phenylurea, N, N'-dimethylurea, hexamethylenediurea, N, N'-diphenylurea, 1,2-ethylenediurea, 1,3-propylenediurea, diethylenetriurea, dipropylenetriurea, 2-hydroxypropylenediurea, 2- imidazolidinone (ethyleneurea), 2-oxohexahydropyrimidine (propyleneurea) or 2-oxo-5-hydroxyhexahydropyrimidine (5-hydroxypropyleneurea).
• Urea resins may optionally be partially or fully modified, e.g. by reaction with mono- od.
• Polyfunctional alcohols, ammonia or amines (cationically modified urea resins) or with (hydrogen) sulfites (anionic modified urea resins), particularly suitable are the alcohol-modified urea resins.
• Possible alcohols for the modification are C 1 -C 6 -alcohols, preferably C 1 -C 4 -alkyl alcohol and in particular methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol and sec-butanol.
• Suitable melamine resins are those which are obtainable by reacting melamine with aldehydes and which may optionally be partially or completely modified.
• aldehydes are formaldehyde, acetaldehyde, isobutyraldehyde and glyoxal.
• Melamine-formaldehyde resins are reaction products of the reaction of melamine with aldehydes, e.g. the o.g. Aldehydes, especially formaldehyde.
• aldehydes e.g. the o.g. Aldehydes, especially formaldehyde.
• the resulting methylol groups are modified by etherification with the abovementioned monohydric or polyhydric alcohols.
• the melamine-formaldehyde resins can also be modified as described above by reaction with amines, aminocarboxylic acids or sulfites.
• melamine-formaldehyde resins including monomeric or polymeric melamine resins and partially or fully alkylated methylamine resins
• urea resins for example methylolureas such as formaldehyde-urea resins, alkoxyureas such as butylated formaldehyde-urea resins, but also N- Methylol acrylamide emulsions, isobutoxy methyl acrylamide emulsions
• polyanhydrides such as, for example, poly succinic anhydride
• siloxanes or silanes for example dimethyl dimethoxysilanes.
• aminoplast resins such as melamine-formaldehyde resins or formaldehyde-urea resins.
• the paints in which the polyesters according to the invention can be used may be conventional solvent-based paints, water-based paints, essentially solvent-free and water-free liquid paints (100% systems), essentially solvent-free and water-free solid basecoats (powder paints and coatings) pigmented powder coatings) or essentially solvent-free, possibly pigmented powder coating dispersions (slurry basecoats). They can be thermal, radiation or dual-cure, self-crosslinking or externally crosslinking.
• zinc compounds Compounds of the metals of the IV., V. or VI subgroup (in particular of zirconium, vanadium, molybdenum or tungsten), aluminum, or bismuth compounds are used as catalysts.
• the highly branched and hyperbranched polyesters formed by the process according to the invention are terminated after the reaction, ie without further modification, with hydroxyl groups and / or with acid groups. They usually dissolve well or can be well dispersed in various solvents, for example in water, alcohols, such as methanol, ethanol, butanol, alcohol / water mixtures, acetone, 2-butanone, ethyl acetate, butyl acetate, methoxypropyl acetate, methoxyethyl acetate, Tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene carbonate or propylene carbonate.
• alcohols such as methanol, ethanol, butanol, alcohol / water mixtures, acetone, 2-butanone, ethyl acetate, butyl acetate, methoxypropyl acetate, methoxyethyl acetate, Tetrahydrofuran, di
• the turnover of acid functions is usually over 75%, usually over 80% and often over 90%.
• the hyperbranched polyester is reacted with carbodiimides, preferably monomeric carbodiimide, for example those based on TMXDI (tetramethylxylylene diisocyanate), with dicyclohexylcarbodiimide or N, N'-diisopropylcarbodiimide.
• Carbodiimides are sold, for example, under the following brand names: Stabaxol® 1 (Rhein Chemie Rheinau GmbH, Mannheim, Germany); Ucarlnk® XL-29SE (DOW CHEMICAL COMPANY, Midland, Mich.), Elastostab® H 01 (BASF AG; polymer), Carbodilite® grades Nissboffbo; hydrophilic).
• the polyesters obtainable according to the invention generally have a glass transition temperature of -40 to 100 ° C.
• the glass transition temperature T 9 is determined by DSC (Differential Scanning Calorimetry) according to ASTM 3418/82.
• polyesters according to the invention which have a T 9 of -40 to 60 ° C. are used in printing inks, since good adhesion of the printing ink to the substrate, if appropriate in combination with adhesion to a cover layer, is obtained.
• such polyesters according to the invention which have a glass transition temperature T 9 of at least 0 ° C., are used in coating compositions and paints.
• This range of glass transition temperature is advantageous for achieving, for example, sufficient paint hardness and chemical resistance.
• polyesters according to the invention which have a glass transition temperature T 9 of at least 0 ° C. are used in coating compositions and paints in combination with polyesters according to the invention which have a glass transition temperature T 9 of below 0 ° C.
• polyesters according to the invention can also be used in combination with other binders such as non-inventive polyesters, acrylates, polyurethanes, polyethers, polycarbonates or their hybrids.
• the glass transition temperature T 9 is determined by the DSC method (Differential Scanning Calorimetry) according to ASTM 3418/82, the heating rate is preferably 10 ° C./min.
• the reaction product was obtained as a transparent solid, which could be clearly dissolved in n-butyl acetate without residue.
• the final sample had an acid number of 15.2 mg KOH / g polymer and a hydroxyl number of 345.8 mg KOH / g polymer.
• the condensate values and the acid and hydroxyl numbers show that the conversion is about 90% of the carboxylic acid groups (deficiency functionality). From GPC measurements in dimethylacetamide (DMAc), molecular masses Mn of 800 g / mol and Mw of 2,450 g / mol were determined using linear PMMA standards.
• the polyester had a glass transition at 19.8 ° C in the DSC and no crystalline enthalpies of fusion.
• the polyester of this example according to the invention was uncrosslinked and unpegged.
• the mixture was initially using a heating mantle to 160 0 C, then at 180 0 C, and finally heated to 200 0 C. At atmospheric pressure, about 36 g of water were distilled off. After cooling, the reaction product was obtained as a transparent solid, which could be clearly dissolved in n-butyl acetate without residue.
• the final sample had an acid number of 78.3 mg KOH / g polymer and a hydroxyl number of 199.1 mg KOH / g polymer.
• the mixture was first heated by means of a heated mushroom to 160 0 C, then to 180 0 C, finally to 200 ° C. At atmospheric pressure, about 57 g of water were distilled off. Even during the reaction, the viscosity of the melt increased so that the product could only be mechanically discharged from the flask. After cooling, the reaction product was present as a transparent solid which could not be dissolved in any common solvent but could only be swollen in hexafluoroisopropanol (HFIP).
• HFIP hexafluoroisopropanol
• the polyester of this example was gelled, possibly crosslinked, and does not match the selection of the invention.
• Example 4 In a 1 l four-necked flask equipped with stirrer, internal thermometer and water-cooled condensate separator, 301 g (1.75 mol) of cyclohexane-1,4-dicarboxylic acid (CHDA), 58.0 g (analogously to Example 1), 0.40 mol) of 1,4-bis (hydroxymethyl) cyclohexane (cyclohexane-1,4-dimethanol, CHDM), 17.3 g (0.87 mol) of 2-ethyl-2-hydroxymethyl-1,3-propanediol (Trimethylolpropane, TMP) and 23.8 g (0.17 mol) of 2,2-bis (hydroxymethyl) -1, 3-propanediol (pentaerythritol) and 150 mg of dibutyltin dilaurate submitted.
• CHDA cyclohexane-1,4-dicarboxylic acid
• CHDM 1,4-bis (hydroxymethyl)
• the mixture was initially using a heating mantle to 160 0 C, then at 180 0 C, and finally heated to 200 0 C. At atmospheric pressure, about 46 g of condensate were distilled off. Analysis of the condensate gave a water content> 95%.
• the reaction product was obtained as a transparent solid, which could be clearly dissolved in n-butyl acetate without residue.
• the final sample had an acid number of 88.8 mg KOH / g polymer and a hydroxyl number of 154.2 mg KOH / g polymer.
• the polyester of this example according to the invention was uncrosslinked and unpegged.
• the mixture was first heated by means of a heated mushroom to 160 0 C, then to 180 0 C, finally to 200 ° C. At atmospheric pressure about 54.1 g of condensate were distilled off. Analysis of the condensate showed a water content of 85% by weight with 15% by weight of ethylene glycol.
• the last melt sample before gel showed a viscosity of 4000 mPas at 125 ° C.
• the final melt sample before gelation had an acid number of 90.9 mg KOH / g polymer and a hydroxyl number of 158.2 mg KOH / g polymer.
• Example 4 From the acid and hydroxyl numbers, a conversion of about 75% based on the monomer mixture used was estimated. On the basis of the condensate values and the acid and hydroxyl numbers, a degree of conversion in the polymer as described above was estimated at about 75% of the carboxylic acid groups (minority functionality).
• the different course compared to Example 4 is not trivial and does not open to the expert from the prior art. The example shows that outside the limits of the invention, disadvantageous products arise.
• the polyester of this example not according to the invention is gelled and possibly crosslinked.

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• 2007
  • 2007-11-08 US US12/514,801 patent/US20100048813A1/en not_active Abandoned
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• 2012
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