WO2007125029A1 - Polyesters hautement ou hyper ramifiés à haute fonctionnalité et à faible indice d'acidité ainsi que leur production et leur utilisation - Google Patents

Polyesters hautement ou hyper ramifiés à haute fonctionnalité et à faible indice d'acidité ainsi que leur production et leur utilisation Download PDF

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WO2007125029A1
WO2007125029A1 PCT/EP2007/053676 EP2007053676W WO2007125029A1 WO 2007125029 A1 WO2007125029 A1 WO 2007125029A1 EP 2007053676 W EP2007053676 W EP 2007053676W WO 2007125029 A1 WO2007125029 A1 WO 2007125029A1
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acid
groups
polyester
polyesters
cycloaliphatic
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PCT/EP2007/053676
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German (de)
English (en)
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Jean-Francois Stumbe
Bernd Bruchmann
Harald Schäfer
Marta Martin-Portugues
Joachim Clauss
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Basf Aktiengesellschaft
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    • 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
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • C08G63/21—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups in the presence of unsaturated monocarboxylic acids or unsaturated monohydric alcohols or reactive derivatives thereof
    • 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
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • 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
    • C08G63/91—Polymers modified by chemical after-treatment

Definitions

  • the present invention relates to specifically constructed high-functionality, highly branched or hyperbranched polyesters having a low acid number based on di-, tri- or polycarboxylic acids and di-, tri- or polyols, processes for their preparation and their use.
  • the high-functionality, highly branched or hyperbranched polyesters according to the invention may i.a. used as adhesion promoters, for example in printing inks, as rheology modifiers or as building blocks for the preparation of polyaddition or polycondensation polymers, for example of paints, coatings, adhesives, sealants, cast elastomers or foams, and as a constituent of binders, optionally with other components such as Isocyanates, epoxy group-containing binders or alkyd resins, in adhesives, inks, inks, pigment pastes, tinting pastes, masterbatches, ballpoint pen pastes, polishes, coatings, foams, coatings and lacquers.
  • adhesion promoters for example in printing inks, as rheology modifiers or as building blocks for the preparation of polyaddition or polycondensation polymers, for example of paints, coatings, adhesives, sealants, cast elastomers or foams, and as a
  • Polyesters are usually obtained from the reaction of carboxylic acids with alcohols.
  • aromatic polyesters i. Polyesters having an acid component in which at least one carboxy group is bonded to an aromatic ring, for example, made from phthalic acid, isophthalic acid or terephthalic acid and ethanediol, propanediol or butanediol, and aliphatic polyesters, i.
  • Polyester having an acid component in which all carboxy groups are bonded to aliphatic or cycloaliphatic carbon atoms prepared from succinic acid, glutaric acid or adipic acid with ethanediol, propanediol, butanediol, pentanediol or hexanediol. See also Becker / Braun, Kunststoff-Handbuch Bd. 3/1, polycarbonates, polyacetals, polyesters, cellulose esters, Carl-Hanser-Verlag, Kunststoff 1992, pages 9-1 16 and Becker / Braun, Kunststoff-Handbuch Bd. 7, Polyurethanes, Carl-Hanser-Verlag, Kunststoff 1993, pages 67-75.
  • the aromatic or aliphatic polyesters described herein are generally linear, strictly difunctional, or constructed with a low degree of branching.
  • Polyesters having an OH 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.
  • 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.
  • EP-A 0 680 981 discloses a process for the synthesis of polyester polyols, which comprises heating a polyol, for example glycerol, and adipic acid to 150-160 ° C. in the absence of catalysts and solvents. This gives products which are suitable as polyester polyol components for rigid polyurethane foams.
  • Such gelation is due to cross-linking, which is expressed in a high viscosity.
  • 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 contain, 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.
  • monocarboxylic acids is carried out according to EP 1 334 989 either by simultaneous reaction of di- or polyfunctional acid, tri- or polyfunctional alcohol and monocarboxylic acid or by two-stage reaction of initially tri- or polyfunctional alcohol with monocarboxylic acid and subsequent reaction of the resulting reaction product with di - or polyfunctional acid.
  • a disadvantage of such a reaction procedure is that the monocarboxylic acids in the first variant are randomly distributed throughout the polyester and act as chain terminators, which leads to a low molecular weight and a wide dispersion of the molecular weight distribution of the product.
  • the functionality of the alcohol component is lowered by the reaction with the monocarboxylic acids, the linear proportion of the polymer increases significantly and the properties of the polyester, for example solubility or crystallinity, are influenced.
  • WO 93/17060 EP 630 389
  • the synthesis is very inflexible, since one relies 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 AB 2 building block, and 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 described in US Pat
  • Coatings systems are used. For example, dimethylolpropionic acid and caprolactone 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 the AB2 building block, are added, if appropriate after chain extension, to the coating system in amounts of from 0.2 to 5% by weight as 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 of production increased by polyesters.
  • WO 02/36697 discloses hyperbranched polyesters which have an acid number of at least 18 mg KOH / g. Such polyesters show good properties in paints and coatings, but unsatisfactory long-term weathering properties.
  • the object of the invention was to provide, by means of a technically simple and inexpensive process, aliphatic or aromatic, highly functional and highly branched polyesters whose structures, degree of branching, functionalities and properties, such as solubilities or melting or glass transition temperatures, easily meet the requirements can be adapted to the application and can combine the advantageous properties, such as high functionality, high reactivity, low viscosity and / or good solubility, in itself.
  • the object could be achieved according to the invention by reacting dicarboxylic acids or their derivatives with a mixture of difunctional and higher-functional alcohols or difunctional alcohols with a mixture of di- and higher-functional carboxylic acids.
  • the invention thus relates to highly functional, highly branched or hyperbranched polyesters having a molecular weight M n of at least 500 g / mol and a polydispersity M w / M n of 1, 2-50 obtainable by
  • C x x-valent aliphatic, cycloaliphatic, araliphatic or aromatic alcohol having more than two OH groups and x is a number greater than 2, preferably between 3 and 8, particularly preferably between 3 and 6, completely more preferably from 3 to 4 and especially 3,
  • one selects the ratio of the reactive groups of the component (s) F to the corresponding reactive groups in the polyester so that one has a molar ratio of 5: 1 to 1: 1, preferably from 4: 1 to 1: 1, particularly preferably from 3 : 1 to 1: 1 and most preferably from 2: 1 to 1: 1,
  • the invention furthermore relates to a process for preparing such highly functional, highly branched or hyperbranched polyesters.
  • Hyperbranched polyesters in the context of this invention are understood as meaning uncrosslinked polyesters having hydroxyl and carboxyl groups which are structurally as well as molecularly nonuniform.
  • Uncrosslinked in the context of this document means that a degree of crosslinking of less than 15% by weight, preferably less than
  • the insoluble portion of the polymer was determined by extraction for 4 hours with the same solvent as used for gel permeation chromatography, ie, tetrahydrofuran or hexafluoroisopropanol, depending on the solvent in which the polymer is more soluble, in a Soxhlet apparatus, and after drying the residue to constant weight Weighing of the remaining residue.
  • Hyperbranched polyesters can be constructed on the one hand, starting from a central molecule analogous to dendrimers, but with nonuniform chain length of the branches. On the other hand, they can also be linear, with functional side be grouped, constructed or, as a combination of the two extremes, linear and branched parts of the molecule have.
  • PJ Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chemistry - A European Journal, 2000, 6, no. 14, 2499.
  • DB degree of branching
  • dendrimer is understood to mean that the degree of branching is 99.9-100%.
  • degree of branching see H. Frey et al., Acta Polym. 1997, 48, 30-35.
  • 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 or fumaric acid.
  • 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-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1, 2-dimethyl-propyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, 2-ethyl-hexyl, 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 for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,
  • substituted dicarboxylic acids examples include 2-methyl-malonic acid, 2-ethylmalonic acid, 2-phenylmalonic acid, 2-methylsuccinic acid,
  • 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, particularly preferably mono- or dimethyl esters or the corresponding mono- or
  • Diethyl ester further mono- and Divinylester and mixed esters, preferably mixed esters with different C1-C4-alkyl components, particularly preferably mixed methyl ethyl esters.
  • 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 or polycarboxylic acids are, for example, aconitic acid, 1,3,5-cyclohexanetricarboxylic acid, 1, 2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid ( Pyromellitic acid) as well as mellitic acid and low molecular weight polyacrylic acids.
  • Tricarboxylic acids or polycarboxylic acids (D y ) can be used in the reaction according to the invention either as such or in the form of derivatives. Derivatives are preferably understood
  • mono-di- or trialkyl preferably mono-, di- or tri-C 1 -C 4 -alkyl, particularly preferably mono-, di- or trimethyl ester or the 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, more preferably mixed methyl ethyl esters.
  • a mixture of a triester of 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.
  • diols (B2) examples are ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,2-diol, butane-1,3-diol, butane.
  • diols used 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.
  • the dihydric alcohols B2 may optionally contain further functionalities such as carbonyl, carboxy, alkoxycarbonyl or sulfonyl, such as dimethylolpropionic acid or dimethylol butyric acid, and their Ci-C 4 alkyl esters, but preferably the alcohols B2 have no other functionalities.
  • further functionalities such as carbonyl, carboxy, alkoxycarbonyl or sulfonyl, such as dimethylolpropionic acid or dimethylol butyric acid, and their Ci-C 4 alkyl esters, but preferably the alcohols B2 have no other functionalities.
  • At least trifunctional alcohols (C x ) include glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, 1, 2,4-butanetriol, tris (hydroxymethyl) amine, tris (hydroxyethyl) amine, tris (hydroxypropyl) amine, pentaerythritol, diglycerol, triglycerol or higher condensation products of glycerol, di (trimethylolpropane), di (pentaerythritol), trishydroxymethylisocyanurate, tris (hydroxyethyl) isocyanurate
  • TSEIC tris (hydroxypropyl) isocyanurate, inositols or sugars, such as glucoses, fructose or sucrose, sugar alcohols, e.g. Sorbitol, mannitol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xyNt, dulcitol (galactitol), maltitol, isomalt, tri- or higher-functional polyetherols based on trifunctional or higher alcohols and ethylene oxide, propylene oxide and / or butylene oxide.
  • sugar alcohols e.g. Sorbitol, mannitol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xyNt, dulcitol (galactitol), maltitol, isomalt, tri- or higher
  • glycerol, diglycerol, triglycerol, trimethylolethane, trimethylolpropane, 1, 2,4-butanetriol, pentaerythritol, tris (hydroxyethyl) isocyanurate and their polyetherols based on ethylene oxide and / or propylene oxide are particularly preferred.
  • the process according to the invention can be carried out in bulk or in the presence of a solvent.
  • 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. It is also possible to distill off water or alcohol formed during the reaction and, for example, to use a water separator in which the water is removed by means of an entraining agent.
  • the separation can be effected by stripping, for example by passing a gas which is inert under the reaction conditions through the reaction mixture, if appropriate in addition to a distillation.
  • Suitable inert gases are preferably nitrogen, noble gases, carbon dioxide or combustion gases.
  • the process according to the invention can be carried out in the absence of catalysts. Preferably, however, one works in the presence of at least one cat lyst. 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.
  • 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 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 (pH ⁇ 6, especially ⁇ 5) and acidic alumina.
  • alumium 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.
  • C3-Ci 2 cycloalkyl for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl xyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl.
  • the 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 according to the invention 0.1 to 10% by weight, preferably 0.2 to 2% by weight, of catalyst is used.
  • Enzymes or decomposition products of enzymes do not belong to the acidic organic catalysts in the sense of the present invention.
  • the dicarboxylic acids reacted according to the invention do not belong to the acidic organic catalysts in the context of the present invention.
  • enzymatic processes are often only applicable to certain substrates. Enzymatic methods also often have long reaction times. To carry out the process according to the invention, it is advantageous to dispense with the use of enzymes.
  • 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 ° C. Preference is given to working at temperatures of 80 to 250, more preferably 100 to 200 ° C.
  • 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 10 to 500 mbar, more preferably below 50 mbar and most preferably below 5 mbar.
  • Temperature and pressure can also be varied during the course of the reaction.
  • 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 substance or solution to 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 made at the beginning of the reaction or at any suitable time in the course of the reaction.
  • the starting substances 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 so that the surface of the reaction mixture is continuously renewed and allows the efficient discharge of low molecular weight condensation products, for example water or methanol.
  • the reaction mixture is stirred at elevated temperatures so that the stirrer forms a gap as small as possible to the edge of the reaction volume in the melt-filled part of the reaction volume and a very large part of the reaction mixture is mixed as ideally as possible.
  • the pressure and temperature course 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 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 surface of the reaction mixture is swept with a slight stream of an inert gas so that a convective discharge of the low molecular weight condensation products promotes the course of the reaction.
  • the pressure in the reaction volume is lowered so that a diffusive discharge of the low molecular weight condensation products promotes the course of the reaction in a vacuum.
  • the composition of the reaction mixture remains constant throughout the reaction time with respect to the molecular units based on di- or higher-functional carboxylic acids and on di- or higher-functional alcohol-based molecular units.
  • the composition of the reaction mixture does not remain constant with respect to the carboxylic acids based on dioder with higher functionality and di- or higher-functional alcohol-based molecular units during the entire reaction time.
  • the composition can be changed by distillative separation of a diol or a cyclic ether based thereon.
  • 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 force absorption of a stirrer motor.
  • the process according to the invention can be carried out batchwise, partly continuously or fully continuously. Mutatis mutandis, information relating to the time course of a discordant embodiment in this document can be transferred to the location space in a continuous embodiment.
  • starting substances a) and b) are introduced into the reaction volume with a catalyst and heated so that a more or less homogeneous melt is formed. Subsequently, the temperature of the reaction mixture is further heated and the pressure optionally adjusted so that react anhydride groups controlled or low molecular weight condensation products are withdrawn from the reaction mixture according to the course of the reaction. With increasing conversion and associated increase in average molecular weight or viscosity, the temperature can be increased gradually and / or the pressure in the reaction volume can be lowered. Upon achievement of the desired reaction progress with respect to the molecular weight of the polyester according to the invention, if appropriate, succession reactions according to c) to f) can be carried out in any suitable order.
  • the highly functional highly branched and hyperbranched polyesters according to the invention can be fed directly from the melt to granulation. the.
  • the polyester according to the invention can be mixed with solvents and converted into a solution or dispersion.
  • the polymer melt is cooled in the reaction volume as soon as the desired mass composition has been reached, so that the progress of the reaction largely ceases and a solvent is added to the reaction volume, a clear solution or a polyester with the polyester according to the invention clear, translucent to turbid dispersion is generated, which is then discharged from the reaction volume.
  • further customary additives may already be added to the mixture in the last process step (for example acid-light UV stabilizers, pH regulation, etc.).
  • polyesters of the invention When the polyesters of the invention are prepared in solution, they may be directly further used, or the polymer may be isolated by stripping the solvent, usually by removing the solvent at reduced pressure, or precipitating the polymer, for example using water as the precipitant. Possibly. The polymer can then be washed and dried.
  • the reaction mixture may be discolored, for example by treatment with activated charcoal or metal oxides, e.g. Alumina, SiIi- cium oxide, magnesium oxide, zirconium oxide, boron oxide or mixtures thereof, in amounts of, for example, 0.1 to 50% by weight, preferably 0.5 to 25% by weight, particularly preferably 1 to 10% by weight at temperatures of, for example, 10 to 200 ° C, preferably 20 to 180 ° C and more preferably 30 to 160 ° C are subjected.
  • activated charcoal or metal oxides e.g. Alumina, SiIi- cium oxide, magnesium oxide, zirconium oxide, boron oxide or mixtures thereof, in amounts of, for example, 0.1 to 50% by weight, preferably 0.5 to 25% by weight, particularly preferably 1 to 10% by weight at temperatures of, for example, 10 to 200 ° C, preferably 20 to 180 ° C and more preferably 30 to 160 ° C are subjected.
  • the decolorization of the reaction mixture can be carried out at any point in the work-up procedure, for example at the stage of the crude reaction mixture or after any pre-wash, neutralization, washing or solvent removal.
  • the reaction mixture can furthermore be subjected to a pre-wash e) and / or a neutralization f) and / or a post-wash g), preferably only a neutralization f).
  • neutralization f) and prewash e) can also be reversed in the order. From the aqueous phase of the washes and / or neutralization contained by-products can be at least partially recovered by acidification and extraction with a solvent and used again.
  • a washing liquid for example water or a 5 to 30 wt%, preferably 5 to 20, particularly preferably 5 to 15 wt% saline, potassium chloride, ammonium chloride, Sodium sulfate or ammonium sulfate solution, preferably water or saline.
  • the quantitative ratio of reaction mixture: washing liquid is generally 1: 0.1-1, preferably 1: 0.2-0.8, particularly preferably 1: 0.3-0.7.
  • the laundry or neutralization may be carried out, for example, in a stirred tank or in other conventional equipment, e.g. in a column or mixer-settler apparatus.
  • Sieve bottom or packed or packed columns, stirred tanks or mixer-settler apparatuses, as well as pulsed columns or those with rotating internals are preferably used.
  • Prewash is preferably used when metal salts, preferably organotin compounds, are used as catalyst (with).
  • a post-wash may be advantageous for removing base or salt traces from the neutralized reaction mixture.
  • the optionally prewashed reaction mixture which may still contain small amounts of catalyst and / or carboxylic acid, with a 5-25, preferably 5 to 20, particularly preferably 5 to 15 wt% aqueous solution of a base such as alkali or alkaline earth metal oxides, hydroxides, carbonates or bicarbonates, preferably sodium hydroxide solution, potassium hydroxide solution, sodium bicarbonate, sodium carbonate, potassium hydrogencarbonate, calcium hydroxide, lime milk, ammonium hydroxide.
  • a base such as alkali or alkaline earth metal oxides, hydroxides, carbonates or bicarbonates, preferably sodium hydroxide solution, potassium hydroxide solution, sodium bicarbonate, sodium carbonate, potassium hydrogencarbonate, calcium hydroxide, lime milk, ammonium hydroxide.
  • ammonia water or potassium carbonate which may optionally be added 5-15% by weight of sodium chloride, potassium chloride, ammonium chloride or ammonium sulfate, particularly preferably with sodium hydroxide or sodium hydroxide solution of sodium chloride, are neutralized.
  • the degree of neutralization is preferably 5 to 60 mol%, preferably 10 to 40 mol%, particularly preferably 20 to 30 mol%, based on the monomers containing acid groups.
  • the base is added in such a way that the temperature in the apparatus does not rise above 60 ° C., preferably between 20 and 35 ° C. and the pH is 4-13.
  • the removal of the heat of neutralization is preferably carried out by cooling the container by means of internal cooling coils or via a double wall cooling.
  • the quantitative ratio of reaction mixture: neutralization liquid is generally 1: 0, 1 to 1, preferably 1: 0.2 to 0.8, particularly preferably 1: 0.3 to 0.7.
  • a solvent is contained in the reaction mixture, this can be substantially removed by distillation. Preference is given to optionally removed solvent after washing and / or neutralization from the reaction mixture, if desired, this can also be done before washing or neutralization.
  • the reaction mixture can be mixed with an amount of storage stabilizer such that, after removal of the solvent, 100-500, preferably 200-500, and more preferably 200-400 ppm thereof are contained in the target ester (residue).
  • distillative removal of the main amount of optionally used solvent or low-boiling by-products takes place for example in a stirred tank with double wall heating and / or internal heating coils under reduced pressure, for example at 20-700 mbar, preferably 30-500 and more preferably 50-150 mbar and a temperature of 40-120 ° C.
  • the distillation can also take place in a falling film or thin film evaporator.
  • the reaction mixture preferably several times in the circulation, under reduced pressure, for example at 20-700 mbar, preferably 30 to 500 and more preferably 50 to 150 mbar and a temperature of 40 to 80 ° C passed through the apparatus.
  • it may be introduced into the distillation apparatus is inert under the reaction conditions, for example, 0.1 to 1, preferably 0,2 - 0,8 and more preferably 0.3 to 0.7 m 3 oxygen containing gas per m 3 reaction mixture and per hour.
  • the residual solvent content in the residue after distillation is generally below 5% by weight, preferably 0.5-5% and particularly preferably 1 to 3% by weight.
  • the separated solvent is condensed and preferably reused.
  • a solvent strip i) can be carried out.
  • the product which may still contain small amounts of solvent or low-boiling impurities, heated to 50 - 150 ° C, preferably 80 - 150 ° C and removed the remaining amounts of solvent with a suitable gas in a suitable apparatus. If necessary, a vacuum can also be applied to assist.
  • Suitable apparatuses are, for example, columns of a type known per se which contain the usual internals, e.g. Soils, beds or directed packings, preferably have beds.
  • all standard installations are suitable as column internals, for example trays, packings and / or random packings.
  • trays bubble-cap trays, sieve trays, valve trays, Thormann trays and / or dual-flow trays are preferred; of the trays are those with rings, coils, calipers, Raschig, Intos or Pall rings, Barrel or Intalox saddles, Top-Pak etc. or braids, preferred.
  • a falling film, thin film or wiped film evaporator such as e.g. a Luwa, Rotafilm or Sambay evaporator, which can be equipped as a splash guard, for example, with a demister.
  • Suitable gases are inert gases under the stripping conditions, in particular those which are heated to 50 to 100 ° C.
  • the amount of stripping gas is for example 5 to 20, more preferably 10 to 20 and most preferably 10 to 15 m 3 of stripping gas per m 3 of reaction mixture and hour.
  • the esterification mixture may at any stage of the work-up procedure, preferably after washing / neutralization and, if appropriate, solvent removal, be subjected to filtration to remove precipitated traces of salts and any decolorizing agent present.
  • a filtration step j) On a pre- or post-washing e) or g) is preferably omitted, only a filtration step j) may be useful.
  • neutralization f) is preferably dispensed with.
  • Another object of the present invention are obtainable by the process according to the invention highly functional, highly branched or hyperbranched polyester. These are characterized by particularly low levels of discoloration and hardening.
  • the polyesters according to the invention have a molecular weight M n of at least 500, preferably at least 600 and more preferably 750 g / mol.
  • the upper limit of the molecular weight M n is preferably 100,000 g / mol, more preferably not more than 80,000 and most preferably not more than 30,000 g / mol.
  • the polydispersity and the number-average and weight-average molecular weight M n and M w relate here to gel permeation chromatographic measurements using polymethyl methacrylate as standard and tetrahydrofuran or hexafluoroisopropanol 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 1, 4 to 40, more preferably 1, 5 to 30 and most preferably to 10.
  • the polyesters of the invention are usually very soluble, i. At 25 ° C., clear solutions containing up to 50% by weight, in some cases even up to 80% by weight, of the polyesters according to the invention in tetrahydrofuran (THF), ethyl acetate, n-butyl acetate, ethanol and represent numerous other solvents, without the naked eye gel particles are detectable. This shows the low degree of crosslinking of the polyesters according to the invention.
  • THF tetrahydrofuran
  • the high-functionality hyperbranched and high-branched polyesters according to the invention are carboxy-terminated, carboxy- and hydroxyl-terminated and are preferably hydroxyl-terminated and can be used for the preparation of e.g. of adhesives, inks, coatings, foams, coatings and paints can be used advantageously.
  • a further aspect of the present invention is the use of the highly functional, 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 inventive highly functional hyperbranched and hyperbranched polyesters 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 ,
  • a further aspect of the present invention are printing inks, adhesives, coatings, foams, coatings and paints containing at least one highly functional hyperbranched polyester according to the invention or polyaddition or polycondensation products prepared from the high-functionality, highly branched and hyperbranched polyesters of the invention characterized by excellent performance characteristics.
  • Another preferred aspect of the present invention are printing inks, in particular packaging inks for flexographic and / or gravure printing, comprising at least one solvent or a mixture of different solvents, at least one colorant, at least one polymeric binder and optionally further additives, wherein at least one of the polymeric binders is a highly branched and hyperbranched high-functionality polyester according to the invention.
  • 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 the printing inks according to the invention include polyvinyl butyral, nitrocellulose, polyamides, polyurethanes, polyacrylates or polyacrylate copolymers.
  • the combination of highly branched and hyperbranched polyesters with nitrocellulose has proved particularly advantageous.
  • the total amount of all binders in the printing ink of the invention 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% by weight, preferably 4% by weight and particularly preferably 5% by weight, should not fall short of the sum of all constituents of the printing 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.
  • the usual dyes in particular conventional pigments can be used.
  • inorganic pigments such as titanium dioxide pigments or iron oxide pigments, interference pigments, carbon blacks, metal powders such as in particular aluminum, brass or copper powder, and organic pigments such as azo, phthalocyanine or isoindoline pigments.
  • organic pigments such as azo, phthalocyanine or isoindoline pigments.
  • the packaging printing ink according to the invention may optionally comprise further 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, di-octyl phthalate, citric acid esters or esters of adipic acid.
  • Dispersing agents can 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.
  • the production of the packaging printing ink according to the invention can be carried out in a manner known in principle 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 later processed further with other constituents 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, and the use of the printing varnishes according to the invention for priming, as a protective varnish 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.
  • the polyesters of the invention may 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, hydroxystyryl (meth) acrylates, linear or branched polyesters, polyethers, polycarboxylic ferrites, melamine resins or urea-formaldehyde resins, together with carboxy- and / or hydroxyl-functional compounds, for example with isocyanates, capped isocyanates, epoxides, carbonates and / or aminoplasts, preferably isocyanates, epoxides or aminoplasts, more preferably with isocyanates or epoxides, and most 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 5 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, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene lendiisocyanat, derivatives of Lysindiisocyanates, trimethylhexane diisocyanate or tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1, 4, 1, 3 or 1 ⁇ -Diisocyanatocyclohexan, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, 1-iso-cyanato 3,3,5-trimethyl-5- (isocyanatomethyl) cycl
  • Suitable polyisocyanates are polyisocyanates having isocyanurate groups, uretdione diisocyanates, biisocyanate-containing polyisocyanates, polyisocyanates containing urethane or allophanate groups, oxadiazinetrione groups or iminooxadiazinedione-containing polyisocyanates, 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 Particularly preferred in this case, the corresponding aliphatic and / or cycloaliphatic isocyanato-isocyanurates and in particular those based on hexamethylene diisocyanate and isophorone diisocyanate.
  • the isocyanurates present in this case are, in particular, trisisocyanatoalkyl or trisisocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or
  • 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 bound 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).
  • biuret polyisocyanates having aromatic, cycloaliphatic or aliphatic bound, preferably cycloaliphatic or aliphatic bound isocyanate groups, in particular tris (6-isocyanatohexyl) biuret or mixtures thereof with its higher homologues.
  • These polyisocyanates containing biuret groups generally have an NCO content of 18 to 23% by weight and an average NCO functionality of 2.8 to 4.5.
  • urethane and / or allophanate polyisocyanates having aromatically, aliphatically or cycloaliphatically bonded, preferably aliphatically or cycloaliphatically bound isocyanate groups, as for example by
  • oxadiazinetrione-containing polyisocyanates preferably derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • Such oxadiazinetrione-containing polyisocyanates can be prepared from diisocyanate and carbon dioxide.
  • polyisocyanates containing iminooxadiazinedione groups preferably derived from hexamethylene diisocyanate or isophorone diisocyanate.
  • Such 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 e.g. Oximes, phenols, imidazoles, pyrazoles, pyrazolinones, triazoles, diketopiperazines, caprolactam, malonic acid esters or compounds as mentioned in the publications of Z.W. Wicks, Prog. Org. Coat. 3 (1975) 73-99 and Prog. Org. Coat 9 (1981), 3-28, by DA Wicks and Z.W. Wicks, Prog. Org. Coat. 36 (1999), 148-172 and Prog. Org. Coat. 41 (2001), 1-83 and in Houben-Weyl, Methods of Organic Chemistry, Vol. XIV / 2, 61 ff. Georg Thieme Verlag, Stuttgart 1963.
  • blocking or blocking agents 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.
  • 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. Such products are commercially available in large numbers. Polyglycidyl compounds of the bisphenol A, F or B type and glycidyl ethers of polyhydric alcohols, for example of butanediol, of 1,6-hexanediol, of glycerol and of pentaerythritol, are particularly preferred.
  • polyepoxide compounds examples include gen Epikote ® 812 (epoxide value: about 0.67 mol / 100g) and Epikote ® 828 (epoxide value: about 0.53 mol / 100g), Epikote ® 1001, Epikote ® 1007 and Epikote ® 162 (epoxide value: ca.
  • Carbonate compounds are those with at least one, preferably with 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 -Butylcarbonat.
  • methylalkoxy groups such as, for example, etherified reaction products of formaldehyde with amines, such as melamine, urea, etc., phenol / formaldehyde adducts, siloxane or silane groups and anhydrides, as described, for example, in US Pat. in US 5,770,650 are described.
  • preferred aminoplasts are particularly preferred urea resins and melamine resins, such.
  • Suitable urea resins are those which are obtainable by reacting ureas with aldehydes and can be modified if appropriate.
  • 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 completely modified, for example by reaction with mono- or polyfunctional alcohols, ammonia or amines (cationically modified urea resins) or with (hydrogen) sulfites (anionically 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 above-mentioned monohydric or polyhydric alcohols.
  • the melamine-formaldehyde resins can also be modified as described above by reaction with amines, aminocarboxylic acids or sulfites.
  • aminoplasts The production of said aminoplasts is carried out according to known methods.
  • melamine-formaldehyde resins including monomeric or polymeric melamine resins, and partially or fully alkylated melamine resins, urea resins, e.g. Methylol ureas such as formaldehyde-urea resins, alkoxy ureas such as butylated formaldehyde-urea resins, but also N-methylol acrylamide emulsions, isobutoxy methyl acrylamide emulsions, polyanhydrides, such. Polysuccinic anhydride, and siloxanes or silanes, e.g. Dimethyldimethoxysilanes.
  • urea resins e.g. Methylol ureas such as formaldehyde-urea resins, alkoxy ureas such as butylated formaldehyde-urea resins, but also N-methylol acrylamide emulsions, isobutoxy methyl acrylamide
  • 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), substantially solvent-free and water-free solid basecoats (powder paints and pigmented paints) Powder coatings) or substantially solvent-free, optionally pigmented powder coating dispersions (powder basecoat paints). They can be thermally, radiation or DuaICure-curable, and self-or externally cross-linking.
  • zinc compounds Compounds of the metals of the IV, V or Vl subgroup (in particular of zirconium, vanadium, molybdenum or tungsten), aluminum, or bismuth compounds are used as catalysts.
  • the highly functional highly branched 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 readily 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, dimethylform
  • a highly functional polyester is to be understood as meaning a product which, in addition to the ester groups which link the polymer backbone, also has at least three, preferably at least six, particularly preferably at least ten functional groups end- and / or pendent.
  • the functional groups are primarily OH groups, but also acid groups.
  • the number of terminal or pendant functional groups is in principle not limited to the top, but products with a very high number of functional groups may have undesirable properties, such as high viscosity.
  • the high-functionality polyesters of the present invention generally have not more than 500 terminal and / or pendant functional groups, preferably not more than 100 terminal and / or pendant functional groups.
  • the polyester according to the invention can be prepared by adding all the carboxylic acid and alcohol monomers together or successively into the reaction vessel and then heating to the reaction temperature.
  • functional groups can also be ether groups, carbonate groups, urethane groups, urea groups, thiol groups, thioether groups, thioester groups, keto or aldehyde groups, mono-, di- or trisubstituted amino groups, nitrile or isonitrile groups, carboxamide groups, sulfonamide groups. groups, silane groups or siloxane groups, sulfonic acid, sulfenic acid or sulfinic acid groups, phosphonic acid groups, vinyl or allyl groups or lactone groups.
  • Such effects can be achieved, for example, by addition of functionalized building blocks E as compounds during the polycondensation which, in addition to hydroxyl groups or carboxyl groups, contain further functional groups or functional elements, such as mercapto groups, primary, secondary or tertiary amino groups, ether groups, carbonyl groups, sulfonic acids or derivatives of sulfonic acids, sulfinic acids or derivatives of sulfinic acids, phosphonic acids or derivatives of phosphonic acids, phosphinic acids or derivatives of phosphinic acids, silane groups, siloxane groups.
  • functionalized building blocks E which, in addition to hydroxyl groups or carboxyl groups, contain further functional groups or functional elements, such as mercapto groups, primary, secondary or tertiary amino groups, ether groups, carbonyl groups, sulfonic acids or derivatives of sulfonic acids, sulfinic acids or derivatives of sulfinic acids, phosphonic acids or derivatives of
  • amide groups can be in the esterification, for example, ethanolamine, propanolamine, isopropanolamine, 2- (butylamino) ethanol, 2- (cyclohexylamino) ethanol, 2-amino-1-butanol, 2- (2 ' aminoethoxy) ethanol or use higher alkoxylation products of ammonia, 4-hydroxypiperidine, 1-hydroxyethylpiperazine, diethanolamine, dipropanolamine, diisopropanolamine, tris (hydroxymethyl) aminomethane, tris (hydroxyethyl) aminomethane, ethylenediamine, propylenediamine, hexamethylenediamine or isophoronediamine.
  • Mercaptoethanol can be used for the modification with mercapto groups, for example.
  • Tertiary amino groups can be produced, for example, by incorporation of N-methyldiethanolamine, N-methyldipropanolamine or N, N-dimethylethanolamine.
  • Ether groups can be generated, for example, by condensation of di- or higher-functional polyetherols.
  • Long-chain alkyl radicals can be introduced by reaction with long-chain alkanediols, and the reaction with alkyl or aryl diisocyanates generates polyesters having aryl and urethane groups.
  • Subsequent functionalization can be obtained by reacting the resulting highly functional, highly branched or hyperbranched polyester in an additional process step with a suitable functionalizing reagent which can react with the OH and / or carboxyl groups of the polyester.
  • a functionalization of hydroxyl-containing polyesters according to the invention with saturated or unsaturated, aliphatic, cycloaliphatic, araliphatic or aromatic monocarboxylic acids F can according to the invention be carried out exclusively retrospectively, ie. after completion of the actual implementation in steps a) and b) in a separate step c) take place.
  • Suitable saturated monocarboxylic acids F may comprise 1 to 30 carbon atoms, preferably 2 to 30, particularly preferably 4 to 25, very particularly preferably 6 to 20 and in particular 8 to 20 carbon atoms.
  • saturated monocarboxylic acids F are formic acid, acetic acid, propionic acid, butyric acid, pivalic acid, caproic acid, 2-ethylhexanoic acid, octanoic acid, isononanoic acid, capric acid, undecanoic acid, lauric acid, myristic acid, penic acid.
  • Suitable ⁇ , ⁇ -unsaturated monocarboxylic acids F may comprise 3 to 20 carbon atoms, preferably 3 to 10, particularly preferably 3 to 6, very particularly preferably 3 to 5 and in particular 3 to 4 carbon atoms.
  • Suitable ⁇ , ⁇ -unsaturated monocarboxylic acids F are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, mesaconic acid or glutaconic acid; preference is given to acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and crotonic acid Particular preference is given to acrylic acid, methacrylic acid, maleic acid, fumaric acid and crotonic acid, very particular preference to acrylic acid and methacrylic acid and, in particular, acrylic acid.
  • the reaction with saturated or unsaturated monocarboxylic acids F can be carried out with their derivatives instead of the carboxylic acids, for example with their anhydrides, chlorides or esters, preferably with their anhydrides or esters, particularly preferably with their esters with C 1 -C 4 -alkyl alcohols, completely especially preferred with their methyl esters.
  • a reaction in the sense of esterification can be carried out, for example, in the presence of at least one esterification catalyst, for example sulfuric acid, aryl or alkylsulfonic acids or mixtures thereof.
  • esterification catalyst for example sulfuric acid, aryl or alkylsulfonic acids or mixtures thereof.
  • arylsulfonic acids are benzenesulfonic acid, para-toluenesulfonic acid or dodecylbenzenesulfonic acid
  • alkylsulfonic acids are methanesulfonic acid, ethanesulfonic acid or trifluoromethanesulfonic acid.
  • Strongly acidic ion exchangers or zeolites can also be used as esterification catalysts. Preference is given to sulfuric acid and ion exchanger.
  • the reaction temperature is generally from 40 to 160 0 C, it may be useful during the reaction water formed with the aid of an azeotroping solvent to remove such as n-pentane, n-hexane, n-heptane, cyclohexane, Methylcyclohexane, benzene, toluene or xylene.
  • the water contained in the reaction mixture is not removed via an azeotroping solvent, it is possible to remove it by stripping with an inert gas, preferably an oxygen-containing gas, more preferably air or lean air.
  • an inert gas preferably an oxygen-containing gas, more preferably air or lean air.
  • An implementation in the sense of a transesterification can be carried out, for example, in the presence of at least one transesterification catalyst, for example metal chelate compound.
  • at least one transesterification catalyst for example metal chelate compound.
  • fertilize of z As hafnium, titanium, zirconium or calcium, alkali metal and Magnesiumalkohola- te, organic tin compounds or calcium and lithium compounds, for example, oxides, hydroxides, carbonates or halides, but preferably titanium, magnesium or aluminum.
  • the alcohol released in the transesterification can be removed, for example, by distillation, stripping or applying a vacuum.
  • the reaction temperature is usually 80-140 ° C.
  • esters of ⁇ , ⁇ -unsaturated carboxylic acids with the polyesters according to the invention can be used, for example, in radiation-curable coating compositions.
  • Hydroxyl-containing high-functionality, high or hyperbranched polyesters can be modified, for example, by adding molecules containing isocyanate groups.
  • polyesters containing urethane groups can be obtained by reaction with alkyl or aryl isocyanates.
  • polyesters containing hydroxyl groups can also be modified by reaction with lactones (e.g., ⁇ -caprolactone). This reaction finds e.g. under Lewis acid catalysis at e.g. 170-180 ° C instead.
  • lactones e.g., ⁇ -caprolactone
  • hyperbranched polyesters according to the invention can also be reacted with alkylene oxides and / or carbodiimides.
  • Monofunctional alkylene oxides and / or carbodiimides are preferred so as to prevent additional crosslinking and possibly gelation.
  • alkylene oxides which are known to the person skilled in the art can be used for the process according to the invention.
  • substituted or unsubstituted alkylene oxides having 2 to 24 carbon atoms in particular alkylene oxides with
  • Halogen, hydroxy, noncyclic ether or ammonium substituents in particular, mention may be made of: aliphatic 1, 2-alkylene oxides having 2 to 4 carbon atoms, for example Ethylene oxide, propylene oxide, vinyl oxirane, 1,2-butylene oxide, 2,3-butylene oxide or isobutylene oxide, aliphatic 1,2-alkylene oxides having 5 to 24 carbon atoms, cycloaliphatic alkylene oxides, for example cyclopentene oxide, cyclohexene oxide or cyclododecatriene (1 , 5,9) -monoxide, araliphatic alkylene oxides, for example styrene oxide.
  • aliphatic 1, 2-alkylene oxides having 2 to 4 carbon atoms for example Ethylene oxide, propylene oxide, vinyl oxirane, 1,2-butylene oxide, 2,3-butylene oxide or isobutylene oxide
  • Preferred substituted alkylene oxides are, for example, 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.
  • Particular preference is given to using 1,2-alkylene oxides having 2 to 4 C atoms, in particular ethylene oxide and / or propylene oxide and especially ethylene oxide, for the process according to the invention.
  • reaction is carried out as follows:
  • the hyperbranched polyester having acid functionalities is dissolved, optionally in a suitable solvent, at temperatures between 0 ° C and 120 ° C, preferably between 10 and 100 ° C and more preferably between 20 and 80 ° C, preferably under protective gas, e.g. Nitrogen, submitted.
  • the alkylene oxide is dissolved continuously or in portions, optionally at a temperature of -30 ° C to 50 ° C, with good mixing so that the temperature of the reaction mixture between 120 and 180 ° C, preferably between 120 and 150 ° 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.
  • the amount of alkylene oxide is adjusted so that per mole of acid functions up to 1, 1 mol of alkylene oxide, preferably up to 1, 05 mol of alkylene oxide and more preferably 1 mol of alkylene oxide are added.
  • up to 50 mol% based on the acid functions more preferably up to 25 mol% and most preferably up to 10 mol% of a catalyst for acceleration may be added, for example water, monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanolamine, ethylene glycol or Diethylene glycol, and alkali metal hydroxides, alcoholates or hydrotalcite, preferably alkali metal hydroxides in water.
  • a catalyst for acceleration may be added, for example water, monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanolamine, ethylene glycol or Diethylene glycol, and alkali metal hydroxides, alcoholates or hydrotalcite, preferably alkali metal hydroxides in water.
  • alkylene oxide After complete metered addition of the alkylene oxide, 10 to 500 minutes, preferably 20 to 300 minutes, more preferably 30 to 180 minutes at temperatures between 30 and 220 ° C, preferably 80 to 200 ° C and particularly preferably 100 to 180 ° C is usually afterreacted 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.
  • the reaction can be carried out, for example, batchwise, semicontinuously or continuously in a stirred reactor or else continuously in a tubular reactor with static mixers.
  • the reaction is carried out completely in the liquid phase.
  • the resulting reaction product can be further processed in crude or processed form.
  • the product can be purified, for example, by crystallization and solid / liquid separation.
  • 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).
  • polyesters obtainable according to the invention generally have a viscosity of not more than 100 Pa.s (measured at 80.degree. C. in accordance with DIN EN 3219).
  • the polyesters obtainable according to the invention generally have a glass transition temperature of -40 to 100.degree.
  • the polyesters obtainable according to the invention have an acid number according to DIN 53240, part 2 of not more than 15 mg KOH / g, preferably not more than 10 mg KOH / g, more preferably not more than 8, very preferably not more than 7, especially not more than 5 and especially not more than 3 mg KOH / g.
  • the OH number according to DIN 53240, Part 2 can be up to 500 mg KOH / g, preferably up to 400, more preferably up to 300 and particularly preferably 40 to 300 mg KOH / g.
  • the glass transition temperature T 9 is determined by DSC (Differential Scanning Calorimetry) according to ASTM 3418/82.
  • such polyesters according to the invention which have a T 9 of -40 to 60 ° C. are used in printing inks, since in this case a 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.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne des polyesters à haute ramification ou hyper ramification de structure ciblée à haute fonctionnalité, présentant un faible indice d'acidité à base de d'acides di-, tri- ou polycarboxyliques et de dipolyols, tripolyols ou polyols, leur procédé de production et leur application.
PCT/EP2007/053676 2006-04-28 2007-04-16 Polyesters hautement ou hyper ramifiés à haute fonctionnalité et à faible indice d'acidité ainsi que leur production et leur utilisation WO2007125029A1 (fr)

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EP06113254.4 2006-04-28

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012140202A1 (fr) * 2011-04-15 2012-10-18 Basf Se Polyesters hyperbranchés dans des encres d'imprimerie
WO2013113587A1 (fr) 2012-02-03 2013-08-08 Basf Se Polymères hyperramifiés pour la modification de systèmes de résine époxyde durcis
US8889780B2 (en) 2008-12-17 2014-11-18 Basf Se Quick-drying coating compounds
EP2808354A1 (fr) 2014-08-08 2014-12-03 Basf Se Masses de revêtement à séchage rapide, élastiques dures, résistances aux rayures et robustes
US8969452B2 (en) 2008-12-17 2015-03-03 Basf Se Quick-drying coating compounds
US9834691B2 (en) 2011-04-15 2017-12-05 Basf Se Hyperbranched polyesters in printing inks
US10604675B2 (en) 2014-03-12 2020-03-31 Basf Se Quick-drying, energy-elastic, scratch-resistant and stable coating compounds

Citations (3)

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Publication number Priority date Publication date Assignee Title
WO2004020503A1 (fr) * 2002-08-30 2004-03-11 Basf Aktiengesellschaft Procede pe preparation de polyesters hyper-ramifies solubles dans l'eau
WO2005037893A1 (fr) * 2003-10-14 2005-04-28 Basf Aktiengesellschaft Polyesters hyper ramifies contenant des groupes ethyleniquement insatures
WO2005118677A1 (fr) * 2004-06-01 2005-12-15 Basf Aktiengesellschaft Polyesters hautement fonctionnels, hautement ramifies ou hyper ramifies, leur production et leur utilisation

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
WO2004020503A1 (fr) * 2002-08-30 2004-03-11 Basf Aktiengesellschaft Procede pe preparation de polyesters hyper-ramifies solubles dans l'eau
WO2005037893A1 (fr) * 2003-10-14 2005-04-28 Basf Aktiengesellschaft Polyesters hyper ramifies contenant des groupes ethyleniquement insatures
WO2005118677A1 (fr) * 2004-06-01 2005-12-15 Basf Aktiengesellschaft Polyesters hautement fonctionnels, hautement ramifies ou hyper ramifies, leur production et leur utilisation

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QIU T ET AL: "MODIFICATION OF END-GROUPS OF ALIPHATIC HYPERBRANCHED POLYESTER", January 2004, POLYMERS FOR ADVANCED TECHNOLOGIES, WILEY & SONS, BOGNOR REGIS, GB, PAGE(S) 65-69, ISSN: 1042-7147, XP001224338 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8889780B2 (en) 2008-12-17 2014-11-18 Basf Se Quick-drying coating compounds
US8969452B2 (en) 2008-12-17 2015-03-03 Basf Se Quick-drying coating compounds
WO2012140202A1 (fr) * 2011-04-15 2012-10-18 Basf Se Polyesters hyperbranchés dans des encres d'imprimerie
US9834691B2 (en) 2011-04-15 2017-12-05 Basf Se Hyperbranched polyesters in printing inks
WO2013113587A1 (fr) 2012-02-03 2013-08-08 Basf Se Polymères hyperramifiés pour la modification de systèmes de résine époxyde durcis
US10604675B2 (en) 2014-03-12 2020-03-31 Basf Se Quick-drying, energy-elastic, scratch-resistant and stable coating compounds
EP2808354A1 (fr) 2014-08-08 2014-12-03 Basf Se Masses de revêtement à séchage rapide, élastiques dures, résistances aux rayures et robustes

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