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
  • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
  • C08G83/002—Dendritic macromolecules
  • C08G83/005—Hyperbranched macromolecules
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • 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
  • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
• • 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
  • 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
  • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
  • C12P7/00—Preparation of oxygen-containing organic compounds
  • C12P7/62—Carboxylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
  • C12P7/00—Preparation of oxygen-containing organic compounds
  • C12P7/62—Carboxylic acid esters
  • C12P7/625—Polyesters of hydroxy carboxylic acids
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
  • Y10T428/2848—Three or more layers

Definitions

• the present invention relates to a process for the production of highly functional, hyperbranched polyesters, characterized in that a reaction solution containing solvents and
• the present invention highly functional, hyperbranched polyesters relates obtainable by the method described above, and the use of high funktionel thus obtained - len, hyperbranched polyesters in coatings, varnishes, adhesives and Matterzü ⁇ gen.
• Modified, highly functional hyperbranched polyesters and polyester based denimers are known as such, see for example WO 96/19537, and are already used in some applications, for example as an impact modifier.
• dendrimers are too expensive for general use because the syntheses place high demands on the yields of the building reactions and purity of the intermediate and end products and for large-scale use requires expensive reagents.
• the production of hyperbranched, highly functional polyesters produced by conventional esterification reactions usually requires very drastic conditions, cf. WO 96/19537, for example high temperatures and / or strong acids. This can lead to side reactions such as dehydration reactions, decarboxylate ions and, as a result of the side reactions, to undesirable resinification and discoloration.
• GB 2 272 904 discloses a process for the lipase-catalyzed preparation of a polyester in which at least one aliphatic dicarboxylic acid is reacted with itself to form polyesters with at least one aliphatic diol or polyol or at least one aliphatic hydroxycarboxylic acid. The process is carried out at from 10 to 60.degree.
• WO 94/12652 discloses a process for the enzyme-catalyzed synthesis of polyesters which is carried out in the absence of solvents (page 3, line 26). A distinction can be made between two process steps. In the first step, enzymatic oligomers are made from diols and dicarboxylic acids or related products. The enzyme is then either recovered and the reaction continued at an elevated temperature, or the enzyme is left in the reaction mixture and the temperature is increased, accepting a possible irreversible destruction of the enzyme.
• WO 98/55642 describes a special process for the enzyme-catalyzed synthesis of polyesters by reacting either hydroxycarboxylic acids or aliphatic dicarboxylic acids with aliphatic diols or polyols and optionally an aliphatic hydroxycarboxylic acid in a two-stage process, the first stage being optionally in the presence of water - the starting pro reacted products in a molar ratio of 1: 1 to 1.1: 1 and wherein the supported enzyme is removed and recycled before the second stage, the second stage being carried out at elevated temperature.
• the method disclosed does not convert sterically hindered secondary hydroxyl groups (page 7, lines 27/28), the secondary hydroxyl group of, for example, glycerol being classified as sterically hindered (page 8, line 4), so that linear products are involved in the reaction of glycerol be preserved.
• WO 99/46397 discloses the synthesis of polyesters by reacting, for example, a polyol having two primary and at least one secondary alcohol function with one or more di- or tricarboxylic acids in the presence of an effective amount of a lipase, preferably under reduced pressure, so that linear polyester.
• the object was therefore to provide a process for the production of highly functional, hyperbranched polyesters which avoids the disadvantages known from the prior art and which, in particular, prevents uncontrolled changes in the reaction conditions. There was still the task of providing new, highly functional, hyperbranched polyesters. Finally, the task was to provide new uses for highly functional, hyperbranched polyesters. It has now surprisingly been found that the object can be achieved by the method defined at the outset.
• reaction solution containing is implemented by the process according to the invention
• Highly functional hyperbranched polyesters in the sense of the present invention are molecularly and structurally inconsistent. They differ from dendrimers in their molecular inconsistency and can therefore be produced with considerably less effort.
• the dicarboxylic acids which can be converted into reaction solutions according to variant (a) include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane- ⁇ , ⁇ -dicarboxylic acid, dodecan- ⁇ , ⁇ -dicarboxylic acid , ice and trans-cyclohexane-l, 2-dicarboxylic acid, ice and trans-cyclohexane-1, 3-dicarboxylic acid, ice and trans-cyclohexane-l, 4-dicarboxylic acid, ice and trans-cyclopentane -l, 2-dicarboxylic acid and ice and trans-cyclopentane-1,3-dicarboxylic acid,
• dicarboxylic acids can be substituted with one or more radicals selected from Ci-Cio-alkyl groups, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethyl propyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl or n-decyl,
• Ci-Cio-alkyl groups for example methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert
• C 3 -C -cycloalkyl groups for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
• Alkylene groups such as methylene or ethylidene or
• C 6 -Ci 4 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, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl.
• Exemplary representatives for substituted dicarboxylic acids are: 2-methylmalonic acid, 2-ethylmalonic acid, 2-phenylmalonic acid, 2-methylsuccinic acid, 2-ethylsuccinic acid, 2-phenylsuccinic acid, itaconic acid, 3, 3-dimethylglutaric acid.
• dicarboxylic acids which can be reacted according to variant (a) include ethylenically unsaturated acids such as, for example, maleic acid and fumaric acid, and aromatic dicarboxylic acids such as, for example, phthalic acid, isophthalic acid or terephthalic acid.
• the dicarboxylic acids can be used either as such or in the form of derivatives.
• Mono- or dialkyl esters preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters, but also those of higher alcohols such as n-propanol, iso- Propanol, n-butanol, isobutanol, tert. -Butanol, n-pentanol, n-hexanol derived mono- and dialkyl esters,
• mixed esters preferably methyl ethyl ester.
• Succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid or their mono- or dimethyl esters are particularly preferably used.
• Adipic acid is very particularly preferably used.
• Commercially available mixtures of succinic acid, glutaric acid and adipic acid are also used with very particular preference.
• the following can be used as at least trifunctional alcohols, for example: glycerol, 1,2-butane, 4-triol, 1,2-pentane, 5-triol, 1,3-n-pentane, 3,5-triol, n-hexane -1,2, 6-triol, n-hexane-l, 2,5-triol, n-hexane-1,3, 6-triol, trimethylolbutane, trimethylolpropane or di-trimethylolpropane, trimethylolethane, pentaerythritol or dipentaerythritol; Sugar alcohols such as brasserythritol, threitol, sorbitol, mannitol or mixtures of the above at least trifunctional alcohols. Glycerol, trimethylolpropane, trimethylolethane and pentaerythritol are preferably used.
• tricarboxylic acids or polycarboxylic acids which can be used in reaction solutions are, for example, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarbonic acid and mellitic acid.
• the tricarboxylic acids or polycarboxylic acids can be used either as such or in the form of derivatives.
• Mono-, di- or trialkyl esters preferably mono-, di- or tri-methyl esters or the corresponding mono-, di- or triethyl esters, but also those of higher alcohols such as n-propanol, iso-propanol, n-butanol , Isobutanol, tert-butanol, n-pentanol, n-hexanol derived mono-, di- and triesters, furthermore mono-, di- or trivinyl esters
• diols for reaction solutions according to variant (b) of the present invention use is made, for example, of ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,2-diol, butane-1,3-diol , Butane-l, 4-diol, butane-2,3-diol, pentane-1,2-diol, pentane-1,3-diol, pentane-1,4-diol, pentane-1,5-diol, pentane -2, 3-diol, pentane-2,4-diol, hexane-1,2-diol, hexane-1,3-diol, hexane-1,4-diol, hexane-1,5-diol, hexane -1,6-diol, hexane-2,5-d
• One or both hydroxyl groups in the above-mentioned diols can also be substituted by SH groups.
• Ethylene glycol, propane-1,2-diol and diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol are preferred.
• Reaction solutions which can be reacted according to variant (c) contain, for example, one or more triols and one or more tetracarboxylic acids or one or more derivatives thereof.
• one or more tricarboxylic acids or one or more derivatives thereof can also be reacted with one or more tetra-functional alcohol.
• the reaction of a trifunctional alcohol, with a tricarboxylic acid or derivatives is preferably possible in the process according to the invention if if the hydroxyl groups or the carboxyl groups have very different reactivities.
• the molar ratio of hydroxyl groups to carboxyl groups in the variants (a) to (c) is 3: 1 to 0.3: 1, preferably 2: 1 to 0.5: 1, in particular 1.5: 1 to 0.66: 1.
• Reaction solutions which can be reacted according to variant (d) contain one or more di- or polyhydroxycarboxylic acids which have at least 2 hydroxyl groups per molecule, for example dimethylolpropionic acid, dimethylolbutyric acid, tartaric acid, 3,4-dihydroxyhydrocinnamic acid, 2,3-dihydroxybenzoic acid, 2,4 -Dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid and 2,6-dihydroxybenzoic acid or mixtures thereof.
• di- or polyhydroxycarboxylic acids which have at least 2 hydroxyl groups per molecule, for example dimethylolpropionic acid, dimethylolbutyric acid, tartaric acid, 3,4-dihydroxyhydrocinnamic acid, 2,3-dihydroxybenzoic acid, 2,4 -Dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid and 2,6
• Reaction solutions which can be reacted according to variant (e) contain one or more hydroxydi- or hydroxypolycarboxylic acids, for example tartaric acid, citric acid, malic acid, 4-hydroxyphthalic acid, 2-hydroxyterephthalic acid or mixtures thereof.
• hydroxydi- or hydroxypolycarboxylic acids for example tartaric acid, citric acid, malic acid, 4-hydroxyphthalic acid, 2-hydroxyterephthalic acid or mixtures thereof.
• di- or polyhydroxycarboxylic acids or hydroxydi- or hydroxypolycarboxylic acids from variants (d) and (e) can be used either as such or in the form of derivatives.
• Esters with other carboxylic acids for example with acetic acid
• Mono- or dialkyl esters preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters, but also those of higher alcohols such as n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, n -Hexanol-derived esters,
• di- or polyhydroxycarboxylic acids or hydroxydi- or hydroxypolycarboxylic acids and one or more of their derivatives it is also possible within the scope of the present invention to use a mixture of several different derivatives of one or more di- or polyhydroxycarboxylic acids or hydroxydi- or hydroxypolycarboxylic acids.
• variants (a) to (c) are used to react the reaction solution
• reaction solutions ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ , ⁇ , ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
• the water formed during the reaction is removed, preferably in the presence of a water-removing agent as an additive which is added at the start of the reaction.
• a water-removing agent as an additive which is added at the start of the reaction.
• weakly acidic silica gels weakly acidic aluminum oxides, molecular sieves, in particular molecular sieve 4 ⁇ , MgS0 4 and NaS0 4 are suitable.
• the use of strongly acidic silica gels is also conceivable.
• Additional dehydrating agents can also be added during the reaction, or dehydrating agents can be replaced by fresh dehydrating agents.
• the process according to the invention is carried out in the presence of an enzyme. The use of lipases or esterases is preferred.
• Well-suited lipases and esterases are, for example, from Burkholderia Alantarii, Candida cylindracea, Candida lipolytica, 5 Candida rugosa, Candida antarctica, Candida utilis, Chromobacter- iu viscosum, Geotrichum viscosum, Geotrichum candidum, Mucor javanicus, Mucor mihei, pig pancaspp, p. , pseudomonas fluorescens, Pseudomonas cepacia, Rhizopus arrhizus, Rhizopus delemar, Rhizopus niveus, Rhizopus oryzae, Aspergillus niger,
• Penicillium roquefortii Penicillium camembertii or esterase from Bacillus spp. and Bacillus thermoglucosidasius.
• Candida antarctica lipase B is particularly preferred.
• the enzymes listed are commercially available, for example from Novozymes Biotech Ine. , Denmark.
• the enzyme is preferably used in immobilized form, for example on silica gel or Lewatit®.
• Methods for immobilizing enzymes are known per se, for example from Kurt Faber, "Biotransformations in organic chemistry", 3rd edition
• Immobilized enzymes are commercially available, for example from Novozymes Biotech Inc., Denmark.
• the amount of immobilized enzyme used is 0.1 to 25 20% by weight, in particular 10-15% by weight, based on the mass of the starting materials used to be converted.
• the inventive method is carried out at temperatures above 60 ° C. Is preferably carried out at temperatures of 100 ° C 30 or below. Temperatures up to 80 ° C are preferred, very particularly preferably from 62 to 75 ° C and even more preferably from 65 to 75 ° C.
• hydrocarbons such as paraffins or aromatics are suitable.
• paraffins are n-heptane and cyclohexane.
• aromatics are toluene, ortho-xylene, meta-xylene, para-xylene, xylene as a mixture of isomers, ethylbenzene, chlorobenzene and ortho- and meta-dichlorobenzene.
• ethers such as dioxane or tetrahydrofuran and ketones such as methyl ethyl ketone and methyl isobutyl ketone.
• the amount of solvent added is at least 5 parts by weight, based on the mass of the starting materials used, preferably at least 50 parts by weight and particularly preferably at least 100 parts by weight. Quantities over 10,000 Parts by weight of solvent are not desired because the reaction rate drops significantly at significantly lower concentrations, which leads to uneconomical long reaction times.
• the process according to the invention is carried out at pressures above 500 mbar.
• the reaction at atmospheric pressure is preferred.
• the reaction time of the process according to the invention is usually 4 hours to 6 days, preferably 5 hours to 5 days and particularly preferably 8 hours to 4 days.
• the highly functional hyperbranched polyesters can be isolated, for example by filtering off the enzyme and concentrating, the concentration usually being carried out under reduced pressure.
• Other well-suited processing methods are precipitation after adding water and subsequent washing and drying.
• Another object of the present invention are the highly functional, hyperbranched polyesters obtainable by the process according to the invention. They are characterized by low levels of discoloration and resinification.
• hyperbranched polymers see also: P.J. Flory, J. Am. Che. Soc. 1952, 74, 2718 and A. Sunder et al., Chem. Eur. J. 2000, 6, No.l, 1-8.
• “highly functional hyperbranched” is understood to mean that in variants (a) to (c) in at least 20 mol% of every second monomer unit, in variants (d) and (e) in each There is a branching with a functional group.
• the polyesters according to the invention have a molecular weight M n of 1000 to 30,000 g / mol, preferably 2000 to 20,000, particularly preferably 3000 to 7000 and very particularly preferably 4000 g / mol.
• the polydispersity is 1.2 to 50, preferably 1.4 to 40, particularly preferably 1.5 to 30 and very particularly preferably up to 10.
• the highly functional hyperbranched polyesters according to the invention are carboxy-terminated, carboxy- and hydroxyl-terminated and preferably hydroxyl-terminated and can be used for Production of adhesives, coatings, foams, coatings and lacquers can be used advantageously.
• Another aspect of the present invention is the use of the highly functional, hyperbranched polyesters according to the invention for the production of polyaddition or polycondensation products, for example polycarbonates, polyurethanes, polyethers and linear polyesters.
• Preferred is the use of the hydroxyl group-terminated, highly functional, hyperbranched polyesters for the production of polyaddition or polycondensation products, such as Polycarbonates or polyurethanes.
• Another aspect of the present invention is the use of the highly functional hyperbranched polyesters according to the invention and the polyaddition or polycondensation products produced from highly functional, hyperbranched polyesters as a component of adhesives, coatings, foams, coatings and lacquers.
• Another aspect of the present invention is adhesives, coatings, foams, coatings and lacquers containing the highly functional hyperbranched polyesters according to the invention or polyaddition or polycondensation products made from the highly functional, hyperbranched polyesters according to the invention. They are characterized by excellent technical properties.

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• Organic Chemistry (AREA)
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• Chemical Kinetics & Catalysis (AREA)
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• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
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• 2001
  • 2001-12-20 DE DE10163163A patent/DE10163163A1/de not_active Withdrawn
• 2002
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