EP1883656A1 - Procede pour produire une dispersion polymere aqueuse - Google Patents

Procede pour produire une dispersion polymere aqueuse

Info

Publication number
EP1883656A1
EP1883656A1 EP06755194A EP06755194A EP1883656A1 EP 1883656 A1 EP1883656 A1 EP 1883656A1 EP 06755194 A EP06755194 A EP 06755194A EP 06755194 A EP06755194 A EP 06755194A EP 1883656 A1 EP1883656 A1 EP 1883656A1
Authority
EP
European Patent Office
Prior art keywords
compound
acid
ethylenically unsaturated
dicarboxylic acid
reaction stage
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06755194A
Other languages
German (de)
English (en)
Inventor
Xiang-Ming Kong
Motonori Yamamoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1883656A1 publication Critical patent/EP1883656A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • 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

Definitions

  • the present invention is a process for the preparation of an aqueous polymer dispersion, which is characterized in that in an aqueous medium in a first reaction stage
  • an ethylenically unsaturated monomer F is radically polymerized.
  • the present invention also provides the aqueous polymer dispersions obtainable by the process according to the invention, the polymer powders obtainable therefrom, and the use thereof.
  • aqueous polyester dispersions are well known.
  • the preparation is generally carried out in such a way that an organic diol and an organic dicarboxylic acid are converted to a polyester.
  • This polyester is then converted in a subsequent stage usually first in a polyester melt and then dispersed with the aid of organic solvents and / or dispersants by various methods in an aqueous medium to form a so-called secondary dispersion (see, for example, EP-A 927219 and cited literature). If a solvent is used, it must be distilled off again after the dispersing step.
  • the enzyme-catalyzed preparation of aqueous dispersions based on polyesters is disclosed in WO 04/035801.
  • the aqueous polyester dispersions obtainable according to the known processes, or their polyesters themselves, have advantageous properties in many applications, although often further optimization is required.
  • the diol compound A used according to the invention are branched or linear alkanediols having 2 to 18 carbon atoms, preferably 4 to 14 carbon atoms, cycloalkanediols having 5 to 20 carbon atoms or aromatic diols.
  • alkanediols examples include ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 1,6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1, 12-dodecanediol, 1, 13-tridecanediol, 2,4-dimethyl-2-ethyl-1,3-hexanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propan
  • Particularly suitable are ethylene glycol, 1,3-propanediol, 1, 4-butanediol and 2,2-dimethyl-1,3-propanediol, 1, 6-hexanediol or 1,12-dodecanediol.
  • cycloalkanediols are 1, 2-cyclopentanediol, 1, 3-cyclopentanediol, 1,2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol (1, 2-dimethylolcyclohexane), 1, 3rd Cyclohexanedimethanol (1,3-dimethylolcyclohexane), 1,4-cyclohexanedimethanol (1,4-dimethylolcyclohexane) or 2,2,4,4-tetramethyl-1,3-cyclobutanediol.
  • aromatic diols 1, 4-dihydroxybenzene, 1, 3
  • Dihydroxybenzene 1, 2-dihydroxybenzene, bisphenol A [2,2-bis (4-hydroxyphenyl) propane], 1, 3-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene or 1, 7-dihydroxynaphthalene.
  • suitable diol compounds A are also polyether diols, for example diethylene glycol, triethylene glycol, polyethylene glycol (with> 4 ethylene oxide units), propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol (with> 4 propylene oxide units) and polytetrahydrofuran (polyTHF), in particular diethylene glycol , Triethylene glycol and polyethylene glycol (with> 4 ethylene oxide units) are used.
  • poly-THF polyethylene glycol or polypropylene glycol find compounds use strigg whose number average molecular weight (M n ) is usually in the range of 200 to 10,000, preferably from 600 to 5000 g / mol. It is also possible to use mixtures of the abovementioned diol compounds.
  • especially preferred diol compounds A are ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,2-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol I 1, 5-pentanediol, 1, 6-hexanediol, 1, 10-decanediol and / or 1, 12-dodecanediol used.
  • dicarboxylic acid compound B in principle all C2-C4o-aliphatic, C3-C20-cycloaliphatic, aromatic or heteroaromatic compounds can be used which have two carboxylic acid groups (carboxyl groups) or derivatives thereof.
  • Particularly suitable derivatives are C 1 -C 10 -alkyl, preferably methyl, ethyl, n-propyl or isopropyl mono- or diesters of the abovementioned dicarboxylic acids, the corresponding dicarboxylic acid halides, in particular the dicarboxylic acid dichlorides and the corresponding dicarboxylic acid anhydrides.
  • Examples of such compounds are ethanedioic acid (oxalic acid), propanedioic acid (malonic acid), butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid), octanedioic acid (suberic acid), nonanedioic acid (azelaic acid), decanedioic acid (Sebacic acid), undecanedioic acid, dodecanedioic acid, tridecanedioic acid (brassylic acid), C3 2 dimer fatty acid (commercial product from Cognis Corp., USA) benzene-1, 2-dicarboxylic acid (phthalic acid), benzene-1,3-dicarboxylic acid (isophthalic acid ) or benzene-1, 4-dicarboxylic acid (tere
  • dicarboxylic acids in particular butanedioic acid, hexanedioic acid, decanedioic acid, dodecanedioic acid, terephthalic acid or isophthalic acid or their corresponding dimethyl esters.
  • the proportions of diol compound A and dicarboxylic acid compound B are chosen such that the molar ratio of dicarboxylic acid compounds Bond B to diol A is 0.5 to 1.5, usually 0.8 to 1.3, often 0.9 to 1.1 and often 0.95 to 1.05. It is particularly favorable if the molar ratio is 1, ie the same number of hydroxyl groups as carboxyl groups or groups derived therefrom (for example ester groups [-CCV alkyl] or carboxylic acid halides [-CO-Hal)] are present.
  • polycondensation reaction is understood as meaning a reaction of the hydroxyl groups from the diol compound A with the carboxyl groups or the groups derived therefrom from the dicarboxylic acid compound B with elimination of water (dicarboxylic acids or dicarboxylic acid anhydrides), alcohol (esters) or hydrogen halides (carboxylic acid halides) to form a polyester ,
  • enzyme C all enzymes which are capable of catalyzing a polycondensation reaction of diol compound A and dicarboxylic acid compound B in an aqueous medium can be used as enzyme C in principle.
  • Particularly suitable as enzyme C are hydrolases [EC 3.x.x.x] and / or transferases [EC 2.x.x.x].
  • hydrolases used are esterases [EC 3.1.x.x], proteases [EC 3.4.x.x] and / or hydrolases which react with other C-N bonds as peptide bonds.
  • carboxylesterases [EC 3.1.1.1] and / or lipases [EC 3.1.1.3] are used.
  • lipomas from Achromobacter sp., Aspergillus sp., Candida sp., Candida antarctica, Mucor sp., Penicilium sp., Geotricum sp., Rhizopus sp, Burkholderia sp., Pseudomonas sp., Pseudomonas cepacia, Thermomyces sp , Pig pancreas or wheat germ and carboxylesterases from Bacillus sp., Pseudomonas sp., Burkholderia sp., Mucor sp., Saccharomyces sp., Rhizopus sp., Thermoanaerobium sp., Pork liver or horse liver.
  • acyltransferases [EC 2.3.x.x] are used as transferases.
  • these are poly (3-hydroxyalkanoate) polymerase [EC 2.3.1.-] from Pseudomonas oleovorans, Chromobacterium violaceum, Methylobacterium extorquens and / or Acetyl-CoA-C-acetyltransferase [EC 2.3.1.9] from Chromobacterium violcume.
  • poly (3-hydroxyalkanoate) polymerase [EC 2.3.1.-] from Pseudomonas oleovorans, Chromobacterium violaceum, Methylobacterium extorquens and / or Acetyl-CoA-C-acetyltransferase [EC 2.3.1.9] from Chromobacterium violcume.
  • Lipase from Pseudomonas cepacia, Burkholderia platarii or Candida antarctica is preferably in free and / or immobilized form (for example Novozym ® 435 from. Novozymes A / S, Denmark) are used.
  • the total amount of enzymes C used is generally 0.001 to 40% by weight, often 0.1 to 15% by weight and often 0.5 to 8% by weight, based in each case on the sum of the total amounts of diol compound A. and dicarboxylic acid compound B.
  • the dispersants D used by the process according to the invention can in principle be emulsifiers and / or protective colloids. It goes without saying that the emulsifiers and / or protective colloids are selected so that they are compatible in particular with the enzymes C used and do not deactivate them. Which emulsifiers and / or protective colloids can be used in a particular enzyme C, the expert knows or can be determined from this in simple preliminary experiments.
  • Suitable protective colloids are, for example, polyvinyl alcohols, polyalkylene glycols, alkali metal salts of polyacrylic acids and polymethacrylic acids, gelatin derivatives or acrylic acid, methacrylic acid, maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and / or 4-styrenesulfonic acid-containing copolymers and their alkali metal salts but also N-vinylpyrrolidone, N-vinylcaprolactam, N- vinylcarbazole, 1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, acrylamide, methacrylamide, amines group-bearing acrylates, methacrylates, acrylamides and / or methacrylamides containing homo- and copolymers.
  • suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromo
  • mixtures of protective colloids and / or emulsifiers can be used.
  • dispersants used are exclusively emulsifiers whose relative molecular weights, in contrast to the protective colloids, are usually below 1000. They may be anionic, cationic or nonionic in nature.
  • anionic emulsifiers are compatible with each other and with nonionic emulsifiers.
  • anionic and cationic emulsifiers are usually incompatible with each other.
  • emulsifiers are used as dispersant D in particular.
  • Common nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 to C 12) and also ethoxylated fatty alcohols (EO degree: 3 to 80, alkyl radical: C 8 to C 3 e).
  • Lutensol ® A grades C 2 C 4 fatty alcohol EO units: 3 to 8
  • Lutensol ® AO-marks C 13 C 15 - oxo alcohol ethoxylates, EO units: 3 to 30
  • Lutensol ® AT grades Ci 6 Ci 8 - fatty alcohol ethoxylates, EO grade: 11 to 80
  • Lutensol ® ON grades C 1 0 oxo alcohol ethoxylates, EO grade: 3 to 11
  • Lutensol ® TO grades C13- Oxoalkoholethoxylate, EO degree: 3 to 20
  • Typical anionic emulsifiers include alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C 8 to C12), ethoxylated sulfuric acid monoesters of alkanols (EO units: 4 to 30, alkyl radical: C12 to C 8) and ethoxylated alkylphenols (EO units: 3 to 50, alkyl radical: C4 to C12), of alkylsulfonic acids (alkyl radical: C1 2 to C 8) and of Al kylarylsulfonkla (alkyl radical: Cg to Ci ⁇ ).
  • R 1 and R 2 are H atoms or C 4 - to C 24 -alkyl and are not simultaneously H atoms
  • M 1 and M 2 may be alkali metal ions and / or ammonium ions.
  • R 1 and R 2 are preferably linear or branched alkyl radicals having 6 to 18 C atoms, in particular having 6, 12 and 16 C atoms or hydrogen, where R 1 and R 2 are not both simultaneously H and Atoms are.
  • M 1 and M 2 are preferably sodium, potassium or ammonium, with sodium being particularly preferred.
  • Particularly advantageous compounds (I) are those in which M 1 and M 2 are sodium, R 1 is a branched alkyl radical having 12 C atoms and R 2 is an H atom or R 1 .
  • Industrial mixtures are used having the monoalkylated product containing from 50 to 90 wt .-%, such as, for example, Dowfax ® 2A1 (trademark of Dow Chemischen mical Company).
  • the compounds (I) are well known, for example, from US-A 4,269,749, and commercially available.
  • Suitable cationic emulsifiers are generally a primary, secondary, tertiary or quaternary ammonium salt containing C 6 -C 16 -alkyl, -alkylaryl or heterocyclic, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolinium salts and salts of amine - oxides, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts.
  • Examples include dodecylammonium acetate or the corresponding sulfate, the sulfates or acetates of the various 2- (N 1 N 1 N-trimethyl ammonium) ethyl paraffins, N-cetylpyridinium sulfate, N-laurylpyridinium sulfate and N-cetyl-N, N, N-trimethylammonium sulfate, N-dodecyl-N, N, N-trimethylammoniumsulfat, N-octyl-N, N, N-trimethlyammoniumsulfat, N 1 N- distearyl-N, N-dimethylammonium sulfate, and also the gemini surfactant N 1 N'-(lauryl) ethylendiamindisulfat, ethoxylated tallow alkyl-N-methyl ammonium sulphate, and ethoxylated oleylamine
  • BASF AG about 12 ethylene oxide.
  • Numerous other examples can be found in H. Stumblee, Tensid-Taschenbuch, Carl Hanser Verlag, Kunststoff, Vienna, 1981, and McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989.
  • the anionic counterparts are as possible are low nucleophilic, such as perchlorate, sulfate, phosphate, nitrate and carboxylates such as acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, as well as conjugated anions of organosulfonic acids, such as methyl sulfonate, Triflu- ormethylsulfonat and para-toluenesulfonate , furthermore tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-trifluoromethyl) phenyl] borate, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate.
  • organosulfonic acids such as methyl sulfonate, Triflu- or
  • the emulsifiers preferably used as dispersant D are advantageously in a total amount of 0.005 to 20 wt .-%, preferably 0.01 to 15 wt .-%, in particular 0.1 to 10 wt .-%, each based on the sum of the total amounts of diol compound A and dicarboxylic acid compound B used.
  • the total amount of the protective colloids used as dispersing agent D in addition to or instead of the emulsifiers is often 0.1 to 10% by weight and frequently 0.2 to 7% by weight, in each case based on the sum of the total amounts of diol compound A and dicarboxylic acid compound B.
  • emulsifiers in particular nonionic emulsifiers, as dispersant D.
  • the first reaction stage it is optionally possible to additionally use even slightly water-soluble organic solvents E and / or ethylenically unsaturated monomers F.
  • Suitable solvents E are liquid aliphatic and aromatic hydrocarbons having 5 to 30 carbon atoms, such as, for example, n-pentane and isomers, cyclopentane, n-hexane and isomers, cyclohexane, n-heptane and isomers, n-octane and isomers, n-nonane and isomers, n-decane and isomers, n-dodecane and isomers, n-tetradecane and isomers, n-hexadecane and isomers, n-octadecane and isomers, benzene, toluene, ethylbenzene, cumene, o-, m- or p-xylene , Mesitylene, and generally hydrocarbon mixtures in the boiling range of 30 to 250 0 C.
  • hydroxy Compounds such as saturated and unsaturated fatty alcohols having 10 to 28 carbon atoms, for example n-dodecanol, n-tetradecanol, n-hexadecanol and their isomers or cetyl alcohol, esters, such as fatty acid esters having 10 to 28 carbon atoms in the acid moiety and 1 to 10 carbon atoms in the alcohol moiety or esters of carboxylic acids and fatty alcohols containing 1 to 10 carbon atoms in the carboxylic acid moiety and 10 to 28 carbon atoms in the alcohol moiety.
  • esters such as fatty acid esters having 10 to 28 carbon atoms in the acid moiety and 1 to 10 carbon atoms in the alcohol moiety or esters of carboxylic acids and fatty alcohols containing 1 to 10 carbon atoms in the carboxylic acid moiety and 10 to 28 carbon atoms in the alcohol moiety.
  • esters such as fatty acid esters having 10 to 28 carbon atoms in the acid moiety and
  • the total amount of solvent is up to 60 wt .-%, preferably 0.1 to 40 wt .-% and particularly preferably 0.5 to 10 wt .-%, each based on the total amount of water in the first reaction stage.
  • solubility of ⁇ 50 g / 1 1 should in the context be understood, when the solvent E or mixture of solvents e in entionisier- tem water at 20 0 C and 1 atm (absolute) preferably ⁇ 10 g / 1 and advantageously ⁇ 5 g / 1.
  • Suitable ethylenically unsaturated monomers F are, in principle, all radically polymerizable ethylenically unsaturated compounds.
  • Particularly suitable monomers F are free-radically polymerizable ethylenically unsaturated monomers, for example ethylene, vinylaromatic monomers, such as styrene, ⁇ -methylstyrene, o-chlorostyrene or vinyltoluenes, esters of vinyl alcohol and monocarboxylic acids having from 1 to 18 carbon atoms , such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate, esters of ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids preferably having 3 to 6 carbon atoms, in particular acrylic acid, methacrylic acid, maleic acid, fumaric acid and itacon - Acid, having generally 1 to 12, preferably 1 to 8 and in particular 1 to 4
  • the stated monomers F as a rule form the main monomers which, based on the total amount of the monomers F to be polymerized by the process according to the invention, normally contain> 50% by weight, preferably> 80% by weight or advantageously> 90 Wt .-% to unite.
  • these monomers in water under normal conditions [20 0 C, 1 atm (absolute)] only a moderate to low solubility.
  • Other monomers F which usually increase the internal strength of the polymer obtainable by polymerization of the ethylenically unsaturated monomers F, normally have at least one epoxy, hydroxyl, N-methylol or carbonyl group, or at least two non-conjugated ethylenically unsaturated double bonds.
  • Examples include two vinyl radicals containing monomers, two vinylidene radicals having monomers and two alkenyl radicals having monomers.
  • Particularly advantageous are the diesters of dihydric alcohols with ⁇ . ⁇ -monoethylenically unsaturated monocarboxylic acids, of which acrylic and methacrylic acid are preferred.
  • alkylene glycol diacrylates and dimethacrylates such as ethylene glycol diacrylate, 1,2-propylene glycol diacrylate, 1,3-propylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate and ethylene glycol dimethacrylate, 1,2.
  • the methacrylic and acrylic C 1 -C 8 -hydroxyalkyl esters such as n-hydroxyethyl, n-hydroxypropyl or n-hydroxybutyl acrylate and methacrylate, and also compounds such as diacetone acrylamide and acetylacetoxyethyl acrylate or methacrylate.
  • the abovementioned monomers based on the total amount of ethylenically unsaturated monomers F, are used in amounts of up to 5% by weight, frequently 0.1 to 3% by weight and often 0.5 to 2% by weight.
  • ethylenically unsaturated monomers containing siloxane groups such as the vinyltrialkoxysilanes, for example vinyltrimethoxysilane, alkylvinyldialkoxysilanes, acryloyloxyalkyltrialkoxysilanes, or methacryloxyalkyltrialkoxysilanes, for example acryloxyethyltrimethoxysilane, methacryloxyethyltrimethoxysilane, acryloxypropyltrimethoxysilane or methacryloxypropyltrimethoxysilane.
  • These monomers are used in total amounts of up to 5 wt .-%, often from 0.01 to 3 wt .-% and often from 0.05 to 1 wt .-%, each based on the total amount of the monomers F used.
  • monomers F which may additionally contain those ethylenically unsaturated monomers FS which contain either at least one acid group and / or their corresponding anion or those ethylenically unsaturated monomers FA which contain at least one amino, amido, ureido or N-heterocyclic group and / or or their nitrogen-protonated or alkylated ammonium derivatives are used.
  • the amount of monomers FS or monomers FA is up to 10% by weight, often 0.1 to 7% by weight and frequently 0.2 to 5% by weight.
  • monomers FS ethylenically unsaturated monomers having at least one acid group are used.
  • the acid group may be, for example, a carboxylic acid, sulfonic acid, sulfuric acid, phosphoric acid and / or phosphonic acid group be.
  • Examples of such monomers FS are acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, 4-styrenesulfonic acid, 2-methacryloxyethylsulfonic acid, vinylsulfonic acid and vinylphosphonic acid and phosphoric acid monoesters of n-hydroxyalkyl acrylates and n-hydroxyalkyl methacrylates, such as, for example, phosphoric acid monoesters of hydroxyethyl acrylate, n-hydroxypropyl acrylate, n-hydroxybutyl acrylate and hydroxyethyl methacrylate, n-hydroxypropyl methacrylate or n-hydroxybutyl methacrylate.
  • ammonium and alkali metal salts of the aforementioned at least one acid group-containing ethylenically unsaturated monomers can also be used according to the invention.
  • Particularly preferred alkali metal is sodium and potassium.
  • these are the ammonium, sodium and potassium salts of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, 4-styrenesulfonic acid, 2-methacryloxyethylsulfonic acid, vinylsulfonic acid and vinylphosphonic acid, and the mono- and di-ammonium, sodium and Potassium salts of the phosphoric acid monoesters of hydroxyethyl acrylate, n-hydroxypropyl acrylate, n-hydroxybutyl acrylate and hydroxyethyl methacrylate, n-hydroxypropyl methacrylate or n-hydroxybutyl methacrylate.
  • the monomers FA used are ethylenically unsaturated monomers which contain at least one amino, amido, ureido or N-heterocyclic group and / or their nitrogen-protonated or alkylated ammonium derivatives.
  • Examples of monomers FA 1 containing at least one amino group are 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 4-amino-n-butyl acrylate, 4-amino-n-butyl methacrylate, 2- (N-methylamino) ethyl acrylate, 2- (N-methylamino) ethyl methacrylate, 2- (N-ethylamino) ethyl acrylate, 2- (N-ethylamino) ethyl methacrylate, 2- (N-)
  • Examples of monomers FA which contain at least one amido group are acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, Nn-propylacrylamide, Nn-propylmethacrylamide, N-iso-propylacrylamide, N-iso -Propylmethacrylamid, N-tert-butylacrylamide, N-tert-butyl methacrylamide, N, N-dimethylacrylamide, N, N-dimethyl methacrylamide, N 1 N- diethylacrylamide, N, N-diethyl methacrylamide, N, N-di-n-propylacrylamide, N , N-di-n-propylmethacrylamide, N, N'-di-iso-propylacrylamide, N, N'-di-isopropyl methacrylamide, N, N-di-n-butyl
  • N'-dimethylaminopropyl) methacrylamide diacetone acrylamide, N, N 'methylenebisacrylamide, N- (diphenylmethyl) acrylamide, N-cyclohexyl acrylamide, as well as N-vinylpyrrolidone and N-vinylcaprolactam.
  • Examples of monomers FA contained at least one ureido N 1 N '- divinylethyleneurea and 2- (1-imidazolin-2-onyl) ethyl methacrylate (for example commercially available as NORSOCRYL ® 100 from Elf Atochem.).
  • Examples of monomers FA containing at least one N-heterocyclic group are 2-vinylpyridine, 4-vinylpyridine, 1-vinylimidazole, 2-vinylimidazole and N-vinylcarbazole.
  • the following compounds are preferably used as monomers FA: 2-vinylpyridine, 4-vinylpyridine, 2-vinylimidazole, 2- (N, N-dimethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N) diethylamino) ethyl acrylate, 2- (N 1 N-diethylamino) ethyl methacrylate, 2- (N-tert-butylamino) ethyl methacrylate, N- (3-N ', N' - dimethylaminopropyl) methacrylamide and 2- (1-imidazolin-2 -onyl) ethyl methacrylate,
  • a part or the total amount of the abovementioned nitrogen-containing monomers FA may be present in the nitrogen-quaternary ammonium form.
  • Sen as monomers FA which shows any quaternary Alkylammonium gleich on the nitrogen are, 2- exemplified (N) N, N-trimethyl ammonium) ethylacrylatchlorid (for example commercially available as NORSOCRYL ® ADAMQUAT MC 80 from Elf Atochem), 2- (N. , N, N-trimethylammonium) ethyl methacrylate chloride (for example, conciseally available as NORSOCRYL MADQUAT ® MC 75 from. Elf Atochem), 2- (N-methyl-
  • N, N-diethylammonium) ethyl acrylate chloride 2- (N-methyl-N, N-diethylammonium) ethyl methacrylate chloride, 2- (N-methyl-N, N-dipropylammonium) ethyl acrylate chloride, 2- (N-methyl-N, N-dipropylammonium ), ethyl methacrylate 2- (N-benzyl-N, N-dimethylammonium) ethylacrylatchlorid (for example commercially available as NORSOCRYL ® ADAMQUAT BZ 80 from. Elf Atochem), 2- (N-benzyl-N, N-dimethylammonium) ethyl methacrylate chloride (e.g. commercially available as
  • NORSOCRYL ® MADQUAT BZ 75 from. Elf Atochem 2- (N-benzyl-N, N-diethylammonium) ethylacrylatchlorid, 2- (N-benzyl-N, N-diethylammonium) ethyl methacrylate, 2- (N-benzyl-N , N-dipropylammonium) ethyl acrylate chloride, 2- (N-benzyl-N, N-dipropylammonium) ethyl methacrylate chloride, 3- (N 1 N 1 N-
  • Trimethylammonium) propylacrylatchlorid 3- (N 1 N 1 N- Trimethylammoniumjpropylmethacrylatchlorid, 3- (N-methyl-N, N-diethylammonium) propylacrylatchlorid, 3- (N-methyl-N, N-diethylammonium) propylmethacrylate, 3- (N- Methyl N, N-dipropyl ammonium) propyl acrylate chloride, 3- (N-methyl-N, N-dipropyl ammonium) propyl methacrylate chloride, 3- (N-benzyl-N, N-dimethyl ammonium) propyl acrylate chloride, 3- (N-benzyl-N, N dimethylammonium propylmethacrylate chloride, 3- (N-benzyl-N, N-diethylammonium) propylacrylate chloride, 3- (N-benzyl-N, N-diethylammonium) prop
  • mixtures of the aforementioned ethylenically unsaturated monomers FS and FA can be used.
  • ethylenically unsaturated monomers F or mixtures of monomers F which likewise have a low water solubility (analogously to solvent E).
  • the amount of ethylenically unsaturated monomers F optionally used in the first reaction stage is from 0 to 100% by weight, frequently from 30 to 90% by weight and often from 40 to 70% by weight, based in each case on the total amount of monomers F.
  • the solvent E and / or the ethylenically unsaturated monomer F and their amounts in the first reaction stage are chosen such that the solubility of the solvent E and / or the ethylenically unsaturated monomer F in the aqueous medium under reaction conditions of the first reaction stage 50% by weight, ⁇ 40% by weight, ⁇ 30% by weight, ⁇ 20% by weight or ⁇ 10% by weight, in each case based on the total amount of solvent E and optionally used in the first reaction stage or monomers F, and thus is present as a separate phase in the aqueous medium.
  • the first reaction stage preferably takes place in the presence of solvent E and / or monomers F, but more preferably in the presence of monomer F and in the absence of solvent E.
  • Solvents E and / or monomers F are used in the first reaction stage in particular when the diol compound A and / or the dicarboxylic acid compound B have a good solubility in the aqueous medium under the reaction conditions of the first reaction stage, i. whose solubility is> 50 g / l or> 100 g / l.
  • the process according to the invention is advantageously carried out if at least a subset of the diol compound A, the dicarboxylic acid compound B and, if appropriate, the solvent E and / or the monomer F are dispersed in the aqueous medium as a disperse phase having an average droplet diameter ⁇ 1000 nm (a so-called oil-in-solution). Water miniemulsion or short miniemulsion).
  • the process according to the invention is carried out in the first reaction stage in such a way that at least a partial amount of diol compound A, dicarboxylic acid compound B, dispersant D and optionally solvent E and / or monomers F is introduced into a partial or total amount of water. Then, by means of suitable measures, a disperse phase containing the diol compound A, the dicarboxylic acid compound B and optionally the solvent E and / or the monomers F having a mean droplet diameter ⁇ 1000 nm is produced (miniemulsion) and subsequently added to the aqueous medium at reaction time.
  • the total amount of the enzyme C and any remaining amounts of water, diol compound A, dicarboxylic acid compound B, dispersant D and optionally solvent E is added.
  • the enzyme C and any residual amounts of water, diol compound A, dicarboxylic acid compound B, dispersant D and optionally solvent E may be added to the aqueous reaction medium discontinuously in one portion, discontinuously in several portions and continuously with constant or changing flow rates.
  • the total amounts of diol A compound, dicarboxylic acid compound B and optionally solvent E and at least a subset of the dispersant D are introduced into the main or total amount of water and after formation of the miniemulsion at reaction temperature, the total amount of the enzyme C, optionally together with the residual amounts of water and the dispersant D, in the aqueous reaction medium.
  • the average size of the droplets of the disperse phase of the aqueous miniemulsion advantageously to be used according to the invention can be determined according to the principle of quasi-elastic dynamic light scattering (the so-called z-mean droplet diameter d z of the unimodal analysis of the autocorrelation function), for example by means of a Coulter N4 Plus particle analyzer Coulter Scientific Instruments.
  • the measurements are carried out on dilute aqueous miniemulsions whose content of non-aqueous constituents is about 0.01 to 1% by weight.
  • the dilution is carried out by means of water, which had previously been saturated with the diol compounds A, dicarboxylic acid compounds B present in the aqueous miniemulsion and, if appropriate, slightly water-soluble organic solvents E and / or ethylenically unsaturated monomers F.
  • the latter measure is intended to prevent the dilution from resulting in a change in the droplet diameter.
  • the values thus determined for the miniemulsions are for d z typically ⁇ 700 nm, frequently ⁇ 500 nm. It is favorable according to the invention the DZ-range from 100 nm to 400 nm or from 100 nm to 300 nm. Normally, d is e.g. the aqueous miniemulsion to be used according to the invention> 40 nm.
  • high-pressure homogenizers can be used for this purpose.
  • the fine distribution of the components is achieved in these machines by a high local energy input.
  • Two variants have proven particularly useful in this regard.
  • the aqueous macroemulsion is compressed via a piston pump to over 1000 bar and then expanded through a narrow gap.
  • the effect is based on an interaction of high shear and pressure gradients and cavitation in the gap.
  • An example of a high-pressure homogenizer that works on this principle is the Niro-Soavi high-pressure homogenizer type NS1001L Panda.
  • the compressed aqueous macroemulsion is expanded via two nozzles directed against each other into a mixing chamber.
  • the fine distribution effect depends above all on the hydrodynamic conditions in the mixing chamber.
  • An example of this homogenizer type is the microfluidizer type
  • the aqueous macroemulsion is compressed by means of a pneumatically operated piston pump to pressures of up to 1200 atm and released via a so-called "interaction chamber".
  • the emulsion beam is split into two beams in a microchannel system, which are guided at an angle of 180 °.
  • Another example of a homogenizer operating according to this type of homogenization is the Nanojet Type Expo from Nanojet Engineering GmbH. However, in the Nanojet instead of a fixed channel system, two homogenizing valves are installed, which can be adjusted mechanically.
  • the homogenization can also be carried out, for example, by using ultrasound (eg Branson Sonifier Il 450).
  • ultrasound eg Branson Sonifier Il 450
  • the fine distribution is based here on cavitation mechanisms.
  • the devices described in GB-A 22 50 930 and US Pat. No. 5,108,654 are also suitable in principle.
  • the quality of the aqueous miniemulsion produced in the sound field depends not only on the sound power introduced, but also on other factors, such as the intensity distribution of the ultrasound sound in the mixing chamber, the residence time, the temperature and the physical properties of the substances to be emulsified, for example on the toughness, the interfacial tension and the vapor pressure.
  • the resulting droplet size depends, inter alia, on the concentration of the dispersant and of the energy introduced during the homogenization and can therefore be specifically adjusted, for example, by a corresponding change in the homogenization pressure or the corresponding ultrasound energy.
  • the device described in the earlier German patent application DE 197 56 874 has proved particularly suitable for the preparation of the aqueous miniemulsion from conventional macroemulsions by means of ultrasound which is advantageously used according to the invention.
  • This is a device which has a reaction space or a flow-through reaction channel and at least one means for transmitting ultrasonic waves to the reaction space or the flow-through reaction channel, wherein the means for transmitting ultrasonic waves is designed such that the entire reaction space, or the Flow reaction channel in a section, can be uniformly irradiated with ultrasonic waves.
  • the emission surface of the means for transmitting ultrasonic waves is designed so that it substantially corresponds to the surface of the reaction space or, when the reaction space is a partial section of a flow-through reaction channel, extends substantially over the entire width of the channel and that the depth of the reaction space substantially perpendicular to the radiating surface is less than the maximum effective depth of the ultrasound transmission means.
  • depth of the reaction space is understood here essentially the distance between the emission surface of the ultrasound transmission means and the bottom of the reaction space.
  • Preferred reaction depths are up to 100 mm.
  • the depth of the reaction space should not be more than 70 mm and particularly advantageously not more than 50 mm.
  • the reaction spaces can also have a very small depth, but with a view to minimizing the risk of clogging and easy cleanability and high product throughput, preferred reaction chamber depths are substantially greater than, for example, the usual gap heights in high-pressure homogenizers and usually over 10 mm ,
  • the depth of the reaction space is advantageously variable, for example, by different depth deep into the housing ultrasonic transmitting agent.
  • the emitting surface of the means for transmitting ultrasound substantially corresponds to the surface of the reaction space.
  • This embodiment serves for the batch production of the miniemulsions used according to the invention.
  • ultrasound can act on the entire reaction space. In the reaction space a turbulent flow is created by the axial sound radiation pressure, which causes an intensive cross-mixing.
  • such a device has a flow cell.
  • the housing is designed as a flow-through reaction channel, which has an inflow and an outflow, wherein the reaction space is a subsection of the flow-through reaction channel.
  • the width of the channel is the channel extending substantially perpendicular to the flow direction.
  • the emission surface covers the entire width of the flow channel transversely to the flow direction.
  • the length of the radiating surface perpendicular to this width that is to say the length of the radiating surface in the direction of flow, defines the effective range of the ultrasound.
  • the flow-through reaction channel has a substantially rectangular cross-section.
  • a likewise rectangular ultrasonic transmission medium with appropriate dimensions is installed in one side of the rectangle, a particularly effective and uniform sound is guaranteed.
  • a round transmission medium due to the turbulent flow conditions prevailing in the ultrasonic field, it is also possible, for example, to use a round transmission medium without disadvantages.
  • a plurality of separate transmission means can be arranged, which are connected one behind the other in the flow direction. In this case, both the radiating surfaces and the depth of the reaction space, that is, the distance between the radiating surface and the bottom of the flow channel vary.
  • the means for transmitting ultrasonic waves is designed as a sonotrode whose end remote from the free emitting surface is coupled to an ultrasonic transducer.
  • the ultrasonic waves may be generated, for example, by utilizing the reverse piezoelectric effect.
  • High-frequency electrical oscillations (usually in the range from 10 to 100 kHz, preferably between 20 and 40 kHz) are generated by means of generators, converted into mechanical oscillations of the same frequency via a piezoelectric transducer and coupled to the sonotrode as a transmission element in the medium to be irradiated ,
  • the sonotrode is designed as a rod-shaped, axially radiating ⁇ / 2 (or multiple of ⁇ / 2) longitudinal oscillator.
  • a sonotrode can be fastened, for example, by means of a flange provided on one of its vibration nodes in an opening in the housing.
  • the implementation of the sonotrode can be formed in the housing pressure-tight, so that the sound can be carried out under elevated pressure in the reaction chamber.
  • the oscillation amplitude of the sonotrode is adjustable, that is, the respectively inserted
  • the vibration amplitude is checked online and readjusted automatically if necessary. The checking of the current oscillation amplitude can be done for example by a mounted on the sonotrode piezoelectric transducer or a strain gauge with downstream evaluation.
  • fittings for improving the flow-through and mixing behavior are provided in the reaction space.
  • These internals may be, for example, simple baffles or different, porous body.
  • the mixing can also be further intensified by an additional agitator.
  • the reaction space is temperature controlled.
  • the sum of the total amounts of individual compounds G, H, I, K and L is ⁇ 50% by weight, preferably ⁇ 40% by weight and particularly preferably ⁇ 30% by weight, or frequently> 0, 1 wt .-% or> 1 wt .-% and often> 5 wt .-%, each based on the sum of the total amounts of diol A and dicarboxylic acid compound B.
  • Suitable diamine compounds G are all organic diamine compounds which have two primary or secondary amino groups, primary amino groups being preferred.
  • the two amino groups have the organic basic skeleton having a C2-C 2 o-aliphatic, C3-C 2 o-cycloaliphatic, aromatic or heteroaromatic structure.
  • Examples of compounds having two primary amino groups are 1, 2-diaminoethane, 1, 3-diaminopropane, 1, 2-diaminopropane, 2-methyl-1,3-diaminopropane, 2,2-dimethyl-1,3-diaminopropane (neo- pentyldiamine), 1,4-diaminobutane, 1,2-diaminobutane, 1,3-diaminobutane, 1-methyl-1,4-diaminobutane, 2-methyl-1,4-diaminobutane, 2,2-dimethyl-1,4 diaminobutane, 2,3- Dimethyl-1,4-diaminobutane, 1,5-diaminopentane, 1,2-diaminopentane, 1,3-diaminopentane, 1,4-diaminopentane, 2-methyl-1,5-diaminopentane, 3-methyl-1,5 dia
  • hydroxycarboxylic acid compound H it is possible to use hydroxycarboxylic acids and / or their lactones. Examples include: glycolic acid, D-, L-, D, L-lactic acid, 6-hydroxyhexanoic acid (6-hydroxycaproic acid), 3-hydroxybutyric acid, 3-
  • Hydroxyvaleric acid 3-hydroxycaproic acid, p-hydroxybenzoic acid whose cyclic derivatives such as glycolide (1, 4-dioxane-2,5-dione), D-, L-, D, L-dilactide (3,6-dimethyl-1 , 4-dioxane-2,5-dione), ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, dodecanolide (oxacyclo- ridecan-2-one), undecanolide (oxacyclododecan-2-one) or pentadecanolide (oxacyclohexadecane). 2-one).
  • hydroxycarboxylic H mixtures of different hydroxycarboxylic H can be used.
  • aminoalcohol compound I it is possible in principle to use all, but preferably C 2 -C 12 -aliphatic, C 1 -C 10 -cycloaliphatic or aromatic organic compounds which have only one hydroxyl group and one secondary or primary, but preferably one, primary amino group.
  • Examples which may be mentioned are 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, 2-aminocyciopentanol, 3-aminocyclopentanol, 2-aminocyclohexanol, 3-aminocyclohexanol, 4-aminocyciohexanol and 4-aminomethylcyclohexanemethanol (1-methylol -4-aminomethyl).
  • mixtures of the aforementioned aminoalcohol compounds I can be used.
  • Aminocarboxylic acid compounds K which are understood in the context of this document as meaning aminocarboxylic acids and / or their corresponding lactam compounds, can be used in addition to the diol compound A and the dicarboxylic acid compound B.
  • Examples which may be mentioned are the naturally occurring aminocarboxylic acids, such as valine, leucine, isoleucine, threonine, methionine, phenylalanine, trypanecarboxylic acids.
  • tophan lysine, alanine, arginine, aspartic acid, cysteine, glutamic acid, glycine, histidine, proline, serine, tyrosine, asparagine or glutamine, and 3-aminopropionic acid, 4-aminobutyric acid, 5-aminovaleric acid, 6-aminocaproic acid, 7-aminoanthic acid, 8-aminocaprylic acid, 9-aminopelargonic acid, 10-aminocapric acid, 11-aminoundecanoic acid, 12-aminolauric acid and the lactams ⁇ -propiolactam, v-
  • Another component which can be used optionally in the process according to the invention is an organic compound L which contains at least 3 hydroxyl, primary or secondary amino and / or carboxyl groups per molecule.
  • organic compound L which contains at least 3 hydroxyl, primary or secondary amino and / or carboxyl groups per molecule.
  • examples include: tartaric acid, citric acid, malic acid, trimethylololpropane, trimethylolethane, pentaerythritol, polyether triols, glycerol, sugars (for example glucose, mannose, fructose, galactose, glucosamine, sucrose, lactose, trehalose, maltose, cellobiose, gentianose, kestose, maltotriose , Raffinose, trimellitic acid (1, 3,5-benzenetricarboxylic acid and its esters or anhydrides), trimellitic acid (1, 2,4-benzenetricarboxylic acid and its
  • the aforementioned compounds are characterized by their L at least 3 hydroxyl, primary or second coordination sphere of amino and / or carboxyl groups per molecule are able to be incorporated simultaneously into at least 2 polyester chains, which is why compounds L have a branching or v have a wringing effect in polyester formation.
  • mixtures of compounds L can also be used here.
  • organic diamine compound G hydroxycarboxylic acid compound H, aminoalcohol compound I, aminocarboxylic acid compound K and / or organic compound L which contains at least 3 hydroxyl, primary or secondary amino and / or carboxyl groups per molecule.
  • the equivalent ratio is 1, ie the same number of amino and hydroxyl groups as carboxyl groups or groups derived therefrom are present.
  • the dicarboxylic acid compounds B free acid, ester, halide or anhydride
  • the hydroxycarboxylic acid compounds H and aminocarboxylic acid compounds K each have one equivalent of carboxyl groups
  • the organic compounds L so many equivalents of carboxyl groups how they contain carboxyl groups per molecule.
  • the diol compounds A have 2 equivalents of hydroxyl groups, the diamine compounds G 2 equivalents of amino groups, the hydroxycarboxylic acid compounds H a hydroxyl group equivalent, the aminocarboxylic acid compounds K an amino group equivalent and the organic compounds L as many equivalents of hydroxyl or amino groups, as they contain hydroxyl or amino groups in the molecule.
  • the enzymes C are selected such that they contain, in particular, the diol compounds A, dicarboxylic acid compounds B, organic diamine compounds G, hydroxycarboxylic acid compounds H, aminoalcohol compounds I, aminocarboxylic acid compounds K, organic compounds L, which contain at least 3 hydroxyl, primary or secondary amino and / or carboxyl groups per molecule, or are compatible with the dispersants D, the solvents E and / or the ethylenically unsaturated monomers F and are not deactivated by them.
  • the enzymes C are selected such that they contain, in particular, the diol compounds A, dicarboxylic acid compounds B, organic diamine compounds G, hydroxycarboxylic acid compounds H, aminoalcohol compounds I, aminocarboxylic acid compounds K, organic compounds L, which contain at least 3 hydroxyl, primary or secondary amino and / or carboxyl groups per molecule, or are compatible with the dispersants D, the solvents E and / or the ethylenically unsaturated
  • the first reaction stage of the process according to the invention is advantageously such that at least a partial amount of diol compound A, dicarboxylic acid compound B, Compound G, H, I, K and / or L, dispersant D and optionally solvent E and / or ethylenically unsaturated monomer F are introduced into at least a subset of the water, then by suitable means a diol compound A, the dicarboxylic acid compound B, the compound G, H, I, K and / or L and optionally the solvent E and / or the ethylenically unsaturated monomer F comprehensive disperse phase having a mean droplet diameter ⁇ 1000 nm generated (miniemulsion) and then the aqueous medium at reaction temperature, the total amount of enzyme C and any residual amounts of diol compound A remaining , Dicarbox
  • the enzyme C optionally remaining amounts of diol A, dicarboxylic acid compound B, compound G 1 H, I 1 K and / or L and solvent E the aqueous reaction medium separately or together, discontinuously in one portion, discontinuously in several portions and continuously be added with constant or changing flow rates.
  • the aqueous reaction medium in the first reaction stage at room temperature (20 to 25 0 C) has a pH> 2 and ⁇ 11, often> 3 and ⁇ 9 and often> 6 and ⁇ 8.
  • a pH (range) is set in which the enzyme C has an optimum action. Which pH value (range) this is, the expert knows or can be determined by him in a few preliminary experiments.
  • acid for example sulfuric acid
  • bases for example aqueous solutions of alkali metal hydroxides, in particular sodium or potassium hydroxide
  • buffer substances for example potassium dihydrogen phosphate / disodium hydrogen phosphate, acetic acid / sodium acetate, ammonium hydroxide Ammonium chloride, potassium dihydrogen phosphate / sodium hydroxide, borax
  • the inventive method usually water is used, which is clear and often has drinking water quality.
  • deionized water for the process according to the invention and sterile deionized water in the first reaction stage.
  • the amount of water in the first reaction onscut selected such that the aqueous polyester dispersion according to the invention formed a water content> 30 wt .-%, frequently> 50 and ⁇ 99 wt .-% or> 65 and ⁇ 95 wt ⁇ -% and often> 70 and ⁇ 90% by weight, in each case based on the aqueous polyes- terdispersion, is, corresponding to a polyester solids content ⁇ 70 wt .-%, often> 1 and ⁇ 50 wt .-% or> 5 and ⁇ 35 wt .-% and often> 10 and ⁇ 30 wt .-%.
  • the process according to the invention is advantageously carried out under an oxygen-free inert gas atmosphere, for example under
  • an adjuvant which is capable of deactivating the enzyme C used according to the invention (ie the catalytic action of the enzyme C) is added to the aqueous polyester dispersion of the first reaction stage following or at the end of the enzymatically catalyzed polymerization reaction to destroy or inhibit).
  • deactivator it is possible to use all compounds which are capable of deactivating the respective enzyme C.
  • Complex compounds for example nitrilotriacetic acid or ethylenediaminetetraacetic acid or their alkali metal salts or anionic emulsifiers, for example sodium dodecylsulfate, can frequently be used as deactivators.
  • the zugängli- by the novel process in the first reaction stage chen polyesters may contain up to +200 0 C glass transition temperatures of from -100. Depending on the application, polyesters are often required whose glass transition temperatures are within certain ranges. By suitably selecting components A and B and G to L used in the process according to the invention, it is possible for a person skilled in the art to prepare polyesters whose glass transition temperatures are within the desired range.
  • the glass transition temperature T 9 it is meant the glass transition temperature limit which it strives for with increasing molecular weight, according to G. Kanig (Kolloid-Zeitschrift & Zeitschrift fur Polymere, vol. 190, page 1, equation 1).
  • the glass transition temperature is determined by the DSC method (differential scanning calorimetry, 20 K / min, midpoint measurement, DIN 53 765).
  • polyester particles of the aqueous polyester dispersions obtainable by the process according to the invention have average particle diameters which are generally between 10 and 1000 nm, frequently between 50 and 700 nm and often between 100 and 500 nm [indicated are the cumulant z-average values on quasielastisehe light scattering (ISO standard 13 321)].
  • the polyesters obtainable by the process according to the invention in the first reaction stage generally have a weight-average molecular weight in the range> 2000 to ⁇ 1 000 000 g / mol, often> 3000 to ⁇ 500 000 g / mol or> 5000 to ⁇ 100 000 g / mol and more frequently> 5000 to ⁇ 50,000 g / mol or> 6000 to ⁇ 30,000 g / mol.
  • the determination of the weight-average molecular weights is carried out by gel permeation chromatography on the basis of DIN 55672-1.
  • the free-radically initiated aqueous emulsion polymerization is usually carried out in such a way that the ethylenically unsaturated monomers are dispersed, as a rule, with the concomitant use of dispersants in an aqueous medium and polymerized by means of at least one water-soluble free-radical polymerization initiator at the polymerization temperature.
  • the dispersant D and its amount must be such that it contains both the polyester particles formed in the first reaction stage and the ethylenically unsaturated monomer F in the form of monomer droplets used for the polymerization of the second reaction stage polymer particles formed in the free-radical polymerization reaction can be stabilized in the aqueous medium as disperse phases.
  • the dispersant D of the second reaction stage may be identical to that of the first reaction stage. But it is also possible that in the second reaction stage, a further dispersant D is added. It is also possible that the total amount of dispersant D was added to the aqueous medium already in the first reaction stage.
  • portions of dispersant D can be added to the aqueous medium in the second reaction stage before, during or after, in particular before or during the free-radical polymerization-this is especially the case-if -first-reaction stage other or smaller amounts of dispersant D were used or in the second reaction stage, a partial or total amount of the ethylenically unsaturated monomer F is used in the form of an aqueous monomer emulsion.
  • which dispersant D and in what quantity these are additionally used in the second reaction stage are known to the person skilled in the art or can be determined from this in simple preliminary experiments.
  • the amount of dispersant D added in the first reaction stage is> 1 and ⁇ 100% by weight,> 20 and ⁇ 90% by weight or> 40 and ⁇ 70% by weight and in the second reaction stage therefore> 0 and ⁇ 99 wt .-%,> 10 and ⁇ 80 wt .-% or> 30 and ⁇ 60 wt .-%, each based on the total amount of dispersant used in the process according to the invention.
  • the emulsifiers preferably used as dispersant D are advantageously in a total amount of 0.005 to 20 wt .-%, preferably 0.01 to 10 wt .-%, in particular 0.1 to 5 wt .-%, each based on the sum of the total amounts to diol compound A, dicarboxylic acid compound B and ethylenically unsaturated monomers F used.
  • the total amount of protective colloids used as dispersing agent D in addition to or instead of the emulsifiers is often 0.1 to 10% by weight and frequently 0.2 to 7% by weight, based in each case on the sum of the total amounts of diol compound A 1 of dicarboxylic acid compound B and ethylenically unsaturated monomers F.
  • emulsifiers in particular nonionic emulsifiers, are preferably used as sole dispersants D.
  • the total amount of water used in the process according to the invention can already be used in the first reaction stage. However, it is also possible to add aliquots of water in the first and in the second reaction stage.
  • the addition of portions of water in the second reaction stage takes place in particular when the addition of ethylenically unsaturated monomers F in the second reaction stage takes place in the form of an aqueous monomer emulsion and the addition of the free-radical initiator in the form of a corresponding aqueous solution or aqueous dispersion of the radical initiator.
  • the total amount of water is usually selected so that the aqueous polymer dispersion formed according to the invention has a water content of> 30% by weight, frequently> 40 and ⁇ 99% by weight or> 45 and ⁇ 95% by weight and often > 50 and ⁇ 90 wt .-%, each based on the aqueous polymer dispersion having, corresponding to a polymer solids content ⁇ 70 wt .-%, often> 1 and ⁇ 60 wt .-% or> 5 and ⁇ 55 wt. -% and often> 10 and ⁇ 50 wt .-%.
  • the amount of water added in the first reaction stage > 10 and ⁇ 100 wt .-%,> 40 and ⁇ 90 wt .-% or> 60 and ⁇ 80 wt .-% and in the second reaction stage therefore> 0 and ⁇ 90 wt %,> 10 and ⁇ 60% by weight or> 20 and ⁇ 40% by weight, based in each case on the total amount of water used in the process according to the invention
  • the total amount of monomers F used in the process according to the invention can be used both in the first and in the second reaction stage. However, it is also possible to add portions of monomers F in the first and in the second reaction stage.
  • the total amount of monomers F in the second reaction stage takes place in particular in the form of an aqueous monomer emulsion.
  • the amount of monomers F added in the first reaction stage is> 0 and ⁇ 100% by weight,> 20 and ⁇ 90% by weight or> 40 and ⁇ 70% by weight and in the second reaction stage therefore> 0 and ⁇ 100 wt .-%,> 10 and ⁇ 80 wt .-% or> 30 and ⁇ 60 wt .-%, in each case based on the total amount of monomers F.
  • the quantitative ratio of the sum of the total amounts of diol compound A and dicarboxylic acid compound B to the total amount of ethylenically unsaturated monomers F is generally from 1:99 to 99: 1, preferably from 1: 9 to 9: 1 and advantageously from 1: 5 to 5 : 1.
  • At least one subset, but preferably the total amount of monomers F used in the first reaction stage has the advantage that the polyester particles formed in the first reaction stage contain monomers F dissolved or swelled with them, or the polyester is dissolved or dispersed in the droplets of the monomers F. Both have an advantageous effect on the formation of polymer (hybrid) particles, which are composed of the polyester of the first reaction stage and the polymer of the second reaction stage.
  • the accessible by the novel process in the second reaction stage of the monomers F polymerizates may have to +150 0 C glass transition temperatures of -70.
  • polymers are frequently required whose glass transition temperatures lie within certain ranges.
  • Glass transition temperatures of each of only one of the monomers 1, 2, .... n constructed polymers in degrees Kelvin are known and are listed, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., Vol. A21, page 169, Verlag Chemie, Weinheim, 1992; Other sources of glass transition temperatures of homopolymers include, for example, J. Brandrup, EH Immergut, Polymer Handbook, 1 st Ed., J. Wiley, New York, 1966; 2 nd ed. J. Wiley, New York, 1975 and 3 rd Ed. J. Wiley, New York, 1989.
  • water-soluble free-radical initiators are generally understood to mean all those radical initiators which are conventionally used in the free-radically initiated aqueous emulsion polymerization, while oil-soluble free-radical initiators are understood to be all those free-radical initiators which the person skilled in the art customarily uses in the free-radically initiated solution polymerization.
  • water-soluble free radical initiators all those free-radical initiators are understood to be at 20 0 C and atmospheric pressure in deionized water solubility> 1 wt .-% have while under oil-soluble radical initiators all free-radical initiators are understood to be under the aforementioned conditions a solubility ⁇ 1 wt .-% have.
  • water-soluble free-radical initiators have a water solubility> 2% by weight,> 5% by weight, or> 10% by weight under the abovementioned conditions
  • oil-soluble free-radical initiators frequently have a water solubility ⁇ 0.9% by weight, ⁇ 0 , 8 wt .-%, ⁇ 0.7 wt .-%, ⁇ 0.6 wt .-%, ⁇ 0.5 wt .-%, ⁇ 0.4 wt .-%, ⁇ 0.3 wt. %, ⁇ 0.2 wt .-% or ⁇ 0.1 wt .-% have.
  • the water-soluble radical initiators may be, for example, both peroxides and azo compounds.
  • redox initiator systems come into consideration.
  • inorganic peroxides such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-alkali metal or ammonium salts of peroxodisulfuric acid, such as, for example, their mono- and di-sodium, potassium or ammonium salts
  • organic peroxides such as alkyl hydroperoxides
  • the azo compound is essentially 2,2'-azobis (isobutyronitrile),
  • Suitable reducing agents may be sulfur compounds having a low oxidation state, such as alkali metal sulfites, for example potassium and / or sodium sulfite, alkali hydrogen sulfites, for example potassium and / or sodium hydrogen sulfite, alkali metal metabisulfites, for example potassium and / or sodium metabisulfite, formaldehyde sulfoxylates, for example potassium and potassium / or sodium formaldehyde sulfoxylate, alkali metal salts, especially potassium and / or sodium salts of aliphatic sulfinic acids and alkali metal hydrogensulfides, for example potassium and / or sodium hydrogen sulfide, salts of polyvalent metals, such as iron (II) sulfate, iron (II) ammonium sulfate, Iron (II) phosphate, endiols, such as dihydroxymaleic acid, benzoin and / or ascorbic acid and reducing sacchar
  • water-soluble free-radical initiators a mono- or di-alkali metal or ammonium salt of peroxodisulfuric acid, for example dipotassium peroxidisulfate, disodium peroxydisulfate or diammonium peroxodisulfate.
  • a mono- or di-alkali metal or ammonium salt of peroxodisulfuric acid for example dipotassium peroxidisulfate, disodium peroxydisulfate or diammonium peroxodisulfate.
  • mixtures of the aforementioned water-soluble radical initiators are also possible to use mixtures of the aforementioned water-soluble radical initiators.
  • oil-soluble radical initiators are exemplified dialkyl or diarylperoxides, such as di-tert-amyl peroxide, dicumyl peroxide, bis (tert-butylperoxiisopropyl) benzene, 2,5-bis (tert-butylperoxy) -2,5-dimethylhexane, tert Butyl cumene peroxide, 2,5-bis (t-butylperoxy) -2,5-dimethyl-3-hexene, 1, 1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1, 1-bis (tert-butylperoxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane or di-tert-butyl peroxide, aliphatic and aromatic peroxyesters, such as cumyl peroxineodecanoate, 2,4,4-trimethylpentyl-2-peroxineode
  • butylperoxy) cyclohexane tert-butyl peroxiisobutanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxyacetate, tert-amyl peroxibenzoate or tert-butyl peroxybenzoate, dialkanoyl or dibenzoylper oxides, such as diisobutanoyl peroxide, bis (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, didecanoyl peroxide, 2,5-bis (2-ethylhexanoyl peroxy) -2,5-dimethylhexane or dibenzoyl peroxide, and also peroxycarbonates, such as bis (4- tert-butylcyclohexyl) peroxydicarbonate, bis (2-ethylhexyl) peroxydicarbonate, di-tert
  • oil-soluble radical initiator is a compound selected from the group consisting of tert-butyl peroxy-2-ethylhexanoate (Trigonox ® 21), tert-Amylperoxi- 2-ethylhexanoate, tert-butyl peroxybenzoate (Trigonox ® C), tert-Amylperoxibenzoat, tert. - Butylperoxiacetat, tert-butyl peroxy-3,5,5-trimethylhexanoate (Trigonox ® 42 S), tert Butylperoxiisobutanoat, Jert.
  • Trigonox ® 21 tert-butyl peroxy-2-ethylhexanoate
  • Trigonox ® C tert-Amylperoxibenzoat
  • tert. - Butylperoxiacetat tert-butyl peroxy-3,5,5-trimethylhexanoate
  • the total amount of radical initiator used is 0.01 to 5 wt .-%, often 0.5 to 3 wt .-% and often 1 to 2 wt .-%, each based on the total amount of monomers F.
  • the reaction temperature for the radical polymerization reaction of the second reaction stage is - inter alia, depending on the radical initiator used - the entire range of 0 to 170 0 C into consideration. In this case, temperatures of 50 to 120 0 C, often 60 to 110 0 C and often 70 to 100 0 C are usually applied.
  • the free-radical polymerization reaction of the second reaction stage can be carried out at a pressure of less than or equal to 1 atm (absolute), the polymerization temperature exceeding 100 ° C. and up to 170 ° C.
  • volatile monomers such as ethylene, butadiene or vinyl chloride are polymerized under elevated pressure.
  • the pressure may be 1, 2, 1, 5, 2, 5, 10, 15 bar or even higher values.
  • ⁇ pressures 950 mbar, often 900 mbar and often 850 mbar (absolute) are set.
  • the free-radical polymerization reaction is carried out at atmospheric pressure under an inert gas atmosphere.
  • the radical polymerization of the second reaction stage is generally carried out up to a conversion of the monomers F of> 90 wt .-%, preferably> 95 wt .-% and preferably> 98 wt .-%.
  • the process according to the invention takes place such that in the first reaction stage at least a partial amount of diol compound A, dicarboxylic acid compound B 1 dispersant D and optionally solvent E and / or ethylenically unsaturated monomer F are introduced into at least a subset of the water, thereafter by means of suitable measures, a diol compound A, dicarboxylic acid compound B, and optionally the solvent E and / or optionally the ethylenically unsaturated monomers F comprehensive disperse phase having a mean droplet diameter ⁇ 1000 nm generated and then the aqueous medium at reaction temperature, the total amount of the enzyme C and the residual amounts of diol compound A, dicarboxylic acid compound B and solvent E which may remain are added and, after completion of the ester formation, in the second reaction stage any remaining amounts of water, Dispersant D and / or ethylenically unsaturated monomer F and the total amount of a radical initiator may be added.
  • aqueous polymer dispersions obtainable by the process according to the invention are advantageously suitable as components in adhesives, sealants, plastic plasters, paper coating slips, printing inks, cosmetic formulations and paints, for finishing leather and textiles, for fiber bonding and for modifying mineral binders or asphalt.
  • aqueous polymer dispersions obtainable according to the invention can be converted by drying into the corresponding polymer powders.
  • Corresponding drying methods for example freeze-drying or spray-drying, are known to the person skilled in the art.
  • the polymer powders obtainable according to the invention can be advantageously used as a pigment, filler in plastic formulations, as a component in adhesives, sealants, plastic plasters, paper coating slips, printing inks, cosmetic formulations, powder coatings and paints, for finishing leather and textiles, for fiber bonding and for modifying mineral binders or asphalt deploy.
  • the process according to the invention provides a simple and cost-effective access to novel aqueous polymer dispersions which combine both the product properties of the polyesters and of the polymers.
  • the resulting heterogeneous mixture was then stirred for 10 minutes with a magnetic stirrer at 60 revolutions per minute (rpm), then likewise transferred under nitrogen into an 80 ml steep tube vessel and purified by means of an Ultra-Turrax T25 instrument (from Janke & Kunkel GmbH & Co.). Co. KG) for 30 seconds at 20500 rpm. Thereafter, the obtained liquid-heterogeneous Mixture for transfer into droplets with a mean droplet diameter ⁇ 1000 nm (miniemulsion) for 3 minutes subjected to ultrasound treatment by means of an ultrasonic probe (70 W, UW 2070 device from Bandelin electronic GmbH & Co. KG).
  • Amano Lipase PS Pseudomonas cepacia, commercial product of Sigma-Aldrich Inc., # 53464-1
  • aqueous polymer dispersion having a solids content of about 14.3% by weight were obtained.
  • the average particle size was determined to be about 450 nm.
  • the polymer obtained had a glass transition temperature of about 100 0 C and a melting point at 43 0 C.
  • the solids content was determined by (ca. 5 g) at 180 0 C in a drying oven until a constant weight was dried, a defined amount of the aqueous poly merdispersion. Two separate measurements were carried out in each case. The value given in the example represents the mean value of the two measurement results.
  • the average particle diameter of the polymer particles was determined by dynamic light scattering on a 0.005 to 0.01 weight percent aqueous polymer dispersion at 23 C C using an Autosizer HC from Malvern Instruments, England.
  • the mean diameter of the cumulant evaluation (cumulant z-average) of the measured autocorrelation function (ISO standard 13321) is given.
  • the determination of the glass transition temperature or the melting points was carried out according to DIN 53765 by means of a DSC820 instrument, TA8000 series from Mettler-Toledo Int. Inc ..

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Zoology (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Biochemistry (AREA)
  • Genetics & Genomics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biotechnology (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Microbiology (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne un procédé pour produire une dispersion polymère aqueuse. Ce procédé consiste, dans une première étape réactionnelle, à mettre en réaction dans un milieu aqueux un composé diol et un composé d'acide dicarboxylique, en présence d'une enzyme, d'un agent dispersant et éventuellement d'un solvant organique peu soluble dans l'eau et/ou d'un monomère éthyléniquement insaturé, afin de produire un polyester, puis ensuite, dans une seconde étape réactionnelle, à polymériser par voie radicalaire un monomère éthyléniquement insaturé, en présence dudit polyester.
EP06755194A 2005-05-17 2006-05-15 Procede pour produire une dispersion polymere aqueuse Withdrawn EP1883656A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005023386A DE102005023386A1 (de) 2005-05-17 2005-05-17 Verfahren zur Herstellung einer wässrigen Polymerdispersion
PCT/EP2006/062317 WO2006122922A1 (fr) 2005-05-17 2006-05-15 Procede pour produire une dispersion polymere aqueuse

Publications (1)

Publication Number Publication Date
EP1883656A1 true EP1883656A1 (fr) 2008-02-06

Family

ID=36660788

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06755194A Withdrawn EP1883656A1 (fr) 2005-05-17 2006-05-15 Procede pour produire une dispersion polymere aqueuse

Country Status (7)

Country Link
US (1) US20080194771A1 (fr)
EP (1) EP1883656A1 (fr)
JP (1) JP2008545818A (fr)
CN (1) CN101180322A (fr)
BR (1) BRPI0610420A2 (fr)
DE (1) DE102005023386A1 (fr)
WO (1) WO2006122922A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005005493A1 (de) * 2005-02-04 2006-08-10 Basf Ag Verfahren zur Herstellung einer wässrigen Polymerdispersion
DE102005016226A1 (de) * 2005-04-07 2006-10-12 Basf Ag Verfahren zur Herstellung einer wässrigen Polymerdispersion
JP4872445B2 (ja) * 2006-04-25 2012-02-08 富士ゼロックス株式会社 樹脂粒子分散液及びその製造方法、静電荷像現像トナー及びその製造方法、静電荷像現像剤、並びに、画像形成方法
US20090280429A1 (en) * 2008-05-08 2009-11-12 Xerox Corporation Polyester synthesis
US20100055750A1 (en) * 2008-09-03 2010-03-04 Xerox Corporation Polyester synthesis
FR2949232B1 (fr) * 2009-08-18 2011-10-28 Ceca Sa Composition bitumineuse contenant un polymer supramoleculaire
WO2013147737A1 (fr) * 2012-03-26 2013-10-03 Empire Technology Development Llc Adhésifs et procédés pour leur fabrication et utilisation
JP6059621B2 (ja) * 2012-09-19 2017-01-11 積水化成品工業株式会社 発泡性スチレン改質熱可塑性ポリエステル系樹脂粒子及びその製造方法、スチレン改質熱可塑性ポリエステル系樹脂予備発泡粒子及びスチレン改質熱可塑性ポリエステル系樹脂発泡成形体
CN103172797B (zh) * 2013-03-13 2015-05-20 华南师范大学 聚丙烯酸酯∕聚酯树脂互穿网络结构的预聚物及制备方法及含有该预聚物的粉末涂料
US20170260554A1 (en) * 2014-07-31 2017-09-14 Karlsruher Institut für Technologie Method For The Enzyme-Catalyzed Production Of Prepolymers For Producing Plastics
CN106832143B (zh) * 2017-03-02 2019-05-17 河北科技大学 一种聚合物共混物微球的制备方法
US20210340337A1 (en) * 2018-09-27 2021-11-04 Basf Se Latex styrene butadiene powders and asphalt composition comprising said powder
WO2022158566A1 (fr) * 2021-01-21 2022-07-28 花王株式会社 Émulsion de polyester pour la modification d'asphalte

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4946932A (en) * 1988-12-05 1990-08-07 Eastman Kodak Company Water-dispersible polyester blends
DE3939918A1 (de) * 1989-12-02 1991-06-06 Henkel Kgaa Polymere stabilisatoren fuer die emulsionspolymerisation
DE4405204A1 (de) * 1994-02-18 1995-08-24 Henkel Kgaa Verfahren zur Herstellung von Emulsionspolymerisaten
DE19638686A1 (de) * 1996-09-20 1998-03-26 Basf Ag Wäßrige Dispersion eines biologisch abbaubaren Polyesters sowie deren Verwendung
DE10248455A1 (de) * 2002-10-17 2004-04-29 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Enzymatische Polymerisation von Miniemulsionen
DE102004058072A1 (de) * 2004-12-01 2006-06-08 Basf Ag Verfahren zur Herstellung einer wässrigen Polyamid-Dispersion
DE102004058073A1 (de) * 2004-12-01 2006-06-08 Basf Ag Verfahren zur Herstellung einer wässrigen Polyamid-Dispersion
DE102005005493A1 (de) * 2005-02-04 2006-08-10 Basf Ag Verfahren zur Herstellung einer wässrigen Polymerdispersion
DE102005016226A1 (de) * 2005-04-07 2006-10-12 Basf Ag Verfahren zur Herstellung einer wässrigen Polymerdispersion
DE102005026135A1 (de) * 2005-06-06 2006-12-07 Basf Ag Verfahren zur Herstellung einer wässrigen Polymerdispersion

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006122922A1 *

Also Published As

Publication number Publication date
US20080194771A1 (en) 2008-08-14
DE102005023386A1 (de) 2006-11-23
JP2008545818A (ja) 2008-12-18
BRPI0610420A2 (pt) 2016-11-08
CN101180322A (zh) 2008-05-14
WO2006122922A1 (fr) 2006-11-23

Similar Documents

Publication Publication Date Title
WO2006122922A1 (fr) Procede pour produire une dispersion polymere aqueuse
EP1891140A1 (fr) Procede de production d'une dispersion polymere aqueuse
WO2006106138A1 (fr) Procede pour preparer une dispersion polymere aqueuse
EP1819826A1 (fr) Procede pour produire une dispersion de polyamide aqueuse
WO2006082234A1 (fr) Procede pour produire une dispersion de polymere aqueuse
EP2197965B1 (fr) Liant aqueux pour substrats fibreux ou granuleux
WO2006058696A2 (fr) Procede pour produire une dispersion de polyamide aqueuse
EP2147717A1 (fr) Adjuvant dispersant pour la polymérisation d'émulsion et de suspension
EP2072578B1 (fr) Liant aqueux pour substrats en forme de fibres ou de grains
EP2177563A1 (fr) Liant aqueux pour substrats granuleux et/ou fibreux
EP1856160B1 (fr) Procede de production d'une dispersion polymere
EP1758940A1 (fr) Procede pour produire des dispersions polymeres aqueuses
EP2337803B1 (fr) Procédé de préparation de particules de polymère par polymérisation en émulsion
EP3206996A1 (fr) Utilisation de compositions de poudres polymères redispersibles dans l'eau à fonctionnalité cationique en tant qu'agent favorisant la floculation
EP1636282A1 (fr) Procede de production d'une dispersion polymere aqueuse
EP3126432B1 (fr) Procédé de fabrication d'éléments de moulage
EP3129414B1 (fr) Procédé de fabrication une dispersion aqueuse de polymère
WO2011069891A1 (fr) Procédé de fabrication de revêtements structurés au niveau de la charge

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20071217

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BASF SE

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20081021

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20090303