EP1869094A1 - Procede pour preparer une dispersion polymere aqueuse - Google Patents

Procede pour preparer une dispersion polymere aqueuse

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Publication number
EP1869094A1
EP1869094A1 EP06725631A EP06725631A EP1869094A1 EP 1869094 A1 EP1869094 A1 EP 1869094A1 EP 06725631 A EP06725631 A EP 06725631A EP 06725631 A EP06725631 A EP 06725631A EP 1869094 A1 EP1869094 A1 EP 1869094A1
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EP
European Patent Office
Prior art keywords
acid
compound
ethylenically unsaturated
dicarboxylic acid
reaction stage
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EP06725631A
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German (de)
English (en)
Inventor
Xiang-Ming Kong
Motonori Yamamoto
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
    • 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
    • C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C12P13/00—Preparation of nitrogen-containing organic compounds
    • C12P13/02—Amides, e.g. chloramphenicol or polyamides; Imides or polyimides; Urethanes, i.e. compounds comprising N-C=O structural element or polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

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
  • 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 polyamide dispersions are well known.
  • the preparation is generally carried out in such a way that an organic diamine and an organic dicarboxylic acid are converted to a polyamide.
  • this polyamide is then generally first converted into a polyamide melt and then dispersed with the aid of organic solvents and / or dispersants by various methods in an aqueous medium with formation of a so-called secondary dispersion. If a solvent is used, it must be distilled off again after the dispersing step (see, for example, DE-AS 1028328, US Pat. No. 2,951,054, US Pat. No. 3,130,181, US Pat. No. 4,886,844, US Pat. No.
  • aqueous polyamide dispersions obtainable according to the known processes, or their polyamides themselves, have advantageous properties in many applications, although often further optimization is required.
  • Suitable diamine compound A are all organic diamine compounds which have two primary or secondary amino groups, primary amino groups being preferred.
  • the organic backbone having the two amino groups can have a C 2 -C 20 aliphatic, C 3 -C 2 0-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 ( Neopentyldiamine), 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-diamino-pentane, 1, 4-diaminopentane, 2-methyl-1, 5 diaminopentane, 3-methyl-1,5-di
  • 1,6-diaminohexane 1,1,2-diaminododecane, 2,2-dimethyl-1,3-diaminopropane, 1,4-diaminocyclohexane, isophoronediamine, 3,3'- Diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylmethane, 3,3 '-dimethyl-4,4' - diaminodicyclohexylmethane, m-xylylenediamine and / or p-xylylenediamine 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), C32 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 (ter
  • dicarboxylic acids in particular butanedioic acid, hexanedioic acid, decanedioic acid, dodecanedioic acid, terephthalic acid and / or isophthalic acid or their corresponding dimethyl esters.
  • the proportions of diamine compound A and of dicarboxylic acid compound B are chosen such that the molar ratio of dicarboxylic acid compound B to diamine compound 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 amino groups as carboxyl groups or derivatives thereof. groups (for example, ester groups [-CO 2 -alkyl] or carboxylic acid halides [-CO-Hal]) are present.
  • enzyme C all enzymes which are able to catalyze a polycondensation reaction of diamine 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], for example 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 , Porcine 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.
  • lipase from Pseudomonas cepacia, Burkholderia platarii or Candida antarctica in free and / or immobilized form (for example Novozym® 435 from Novozymes A / S, Denmark).
  • the total amount of enzymes C used is usually 0.001 to 40% by weight, often 0.1 to 15 wt .-% and often 0.5 to 8 wt .-%, each based on the sum of the total amounts of diamine 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 in that the emulsifiers and / or protective colloids are selected such 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 by this in simple preliminary.
  • 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-vinylpyrrolidone, Vinylcaprolactam, N-vinylcarbazole, 1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, acrylamide, methacrylamide, acrylates containing amine groups, methacrylates, acrylamides and / or methacrylamides containing homopolymers and copolymers.
  • a detailed description of further suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry
  • 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.
  • the individual components must be compatible with each other, which can be checked in case of doubt by hand on fewer preliminary tests.
  • anionic emulsifiers are compatible with each other and with nonionic emulsifiers. The same applies to cationic emulsifiers, while anionic and cationic emulsifiers are usually incompatible with each other.
  • emulsifiers are used as dispersant D in particular.
  • Common nonionic emulsifiers are z.
  • B ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 to C 12) and ethoxylated fatty alcohols (EO degree: 3 to 80, alkyl radical: Ce to C36).
  • Lutensol ® A grades C 2 C 4 fatty alcohol EO units: 3 to 8
  • Lutensol ® AO-marks C13C15- oxo alcohol ethoxylates, EO units: 3 to 30
  • Lutensol ® AT brands Ci 6 Ci 8 fatty alcohol ethoxylates, EO degree: 11 to 80
  • Lutensol ® ON brands Cio-oxoalcohol ethoxylates, EO degree: 3 to 11
  • Lutensol ® TO brands C 3 -oxoalcohol ethoxylates, EO grade: 3 to 20
  • Usual anionic emulsifiers are z. B.
  • Alkali metal and ammonium salts of alkyl sulfates (alkyl radical: Ce to Ci 2 ), of sulfuric monoesters of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: C12 to Ci ⁇ ) and ethoxylated alkylphenols (EO degree: 3 to 50, Alkyl radical: C 4 to C 12), of alkylsulfonic acids (alkyl radical: C 12 to C 18) and of alkylarylsulfonic acids (alkyl radical: Cg to C 18).
  • R 1 and R 2 are H atoms or C 4 - to C ⁇ WMkyl and are not simultaneously H atoms, and M 1 and M 2 may be alkali metal ions and / or ammonium ions proved.
  • 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 which contain from 50 to 90 wt .-% of the monoalkylated product, for example Dowfax ® 2A1 (trademark of Dow Chemical Company).
  • the compounds (I) are well known, for. Example, from US-A 4,269,749, and commercially available.
  • Suitable cation-active emulsifiers are generally a primary, secondary, tertiary or quaternary ammonium salt containing C 1 to C 18 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, N, N-trimethyl ammonium) ethylparaffinklar, N-cetylpyridinium sulfate, N-laurylpyridinium and N-cetyl-N, N, N-trimethylammonium sulfate, N-dodecyl-N, N, N-trimethylammonium sulfate, N-octyl-N, N, N-trimethylammonium sulfate, N, N-distearyl-N, N-dimethylammonium sulfate and the gemini-surfactant N, N '- ( lauryl) ethylendiamindisulfat, ethoxylated tallow alkyl-N-methyl ammonium sulfate and ethoxylated oleylamine
  • the anionic counterparts are as low as possible nucleophilic, such as perchlorate, sulfate, phosphate, nitrate and carboxylates, such as acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, and conjugated anions of organosulfonic acids, such as methylsulfonate, trifluoromethylsulfonate and para-toluenesulfonate, furthermore tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-trifluoromethyl) phenyl] borate, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate.
  • nucleophilic such as perchlorate, sulfate, phosphate, nitrate
  • 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 used on diamine compound A and dicarboxylic acid compound B 1 .
  • the total amount of the protective colloids used as dispersing agent D in addition to or instead of the emulsifiers is often from 0.1 to 10% by weight and frequently from 0.2 to 7% by weight, based in each case on the sum of the total amounts of diamine 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 Hydroxyl compounds, such as saturated and unsaturated fatty alcohols having 10 to 28 carbon atoms, for example n-dodecanol, n-tetrade
  • 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 with 1 to 10 carbon atoms in the carboxylic acid moiety and 10 to 28 C Atoms in the alcohol part.
  • 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.
  • Low-water-soluble solvent E should be understood in the context of this document if the solvent E or the mixture of solvent E in deionized water at 2O 0 C and 1 atm (absolute) has a solubility ⁇ 50 g / 1, 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
  • mixtures of the aforementioned monomers F can also be used.
  • 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 have only a moderate to low solubility in water under standard conditions [2O 0 C, 1 atm (absolute)].
  • 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.
  • Examples of such two non-conjugated ethylenically unsaturated double bonds monomers are alkylene glycol diacrylates and dimethacrylates, such as ⁇
  • the C 1 -C 8 -hydroxyalkyl methacrylates and acrylates 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.
  • monomers F are ethylenically unsaturated monomers containing siloxane groups, such as vinyltrialkoxysilanes, for example vinyltrimethoxysilane, alkylvinyldialkoxysilanes, acryloyloxyalkyltrialkoxysilanes, or methacryloxyalkyltrialkoxysilanes, for example acryloxyethyltrimethoxysilane, methacryloxyethyltrimethoxysilane, acryloyloxypropyltrimethoxysilane or methacryloxypropyltrimethoxysilane.
  • These monomers are used in total amounts of up to 5% by weight, frequently from 0.01 to 3% by weight and often from 0.05 to 1% by weight, based in each case on the total amount of monomers F ,
  • such monomers F may additionally include 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 their nitrogen-protonated or alkylated ammonium derivatives are used. Based on the total amount of the monomers F to be polymerized, 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.
  • 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, as well as 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.
  • 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 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- (Nn-propylamino) ethyl acrylate, 2- (Nn-propylamino) ethyl methacrylate, 2 - (N-iso-propylamino) ethyl methacrylate, 2- (N-iso-propylamino) ethyl
  • Examples of monomers FA containing at least one amido group are acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, Nn-propylacrylamide, Nn-propylmethacrylamide, N-iso-propylacrylamide, N isopropyl methacrylamide, N-tert-butylacrylamide, N-tert-butylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide, N, N-di-n -propylacrylamide, N, N-di-n-propylmethacrylamide, N, N-diisopropylacrylamide, N, N-diisopropylmethacrylamide, N, N-di-n-butylacrylamide, N, N-di-
  • 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, N-diethylamino) ethyl methacrylate, 2- (N-tert-butylamino) ethyl methacrylate, N- (3-N ' , N'-dimethylaminopropyl) methacrylamide and 2- (1 -lmidazolin-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.
  • Suitable monomers FA having a quaternary Alkylammonium gleich on the nitrogen may be mentioned by way of example, 2- (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 (e.g., commercially available as NORSOCRYL MADQUAT ® MC 75 from.
  • 2- (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 e.g., commercially available as NORSOCRYL MADQUAT ® MC 75 from.
  • 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 diamine 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 of the invention is advantageously carried out if at least a portion of the diamine compound A, the dicarboxylic acid compound B and optionally the solvent E and / or the monomer F in the aqueous medium as a disperse phase with a mean droplet diameter ⁇ 1000 nm (a so-called oil-in-water Miniemulsion or short miniemulsion).
  • the process according to the invention is carried out in the first reaction stage such that at least a partial amount of diamine compound A, dicarboxylic acid compound B, dispersant D and optionally solvent E and / or monomers F are introduced into a partial or total amount of water, thereafter by means of suitable measures, the diamine compound A, the dicarboxylic acid compound B and optionally the solvent E and / or the monomers F comprehensive disperse phase with a mean droplet diameter ⁇ 1000 nm generated (miniemulsion) and then the aqueous medium at reaction temperature, the total amount of the enzyme C and any residual amounts of water, diamine compound A, dicarboxylic acid compound B, dispersant D and optionally solvent E are added.
  • the enzyme C and any remaining amounts of water, diamine compound A, dicarboxylic acid compound B, dispersant D and optionally solvent E may be added to the aqueous reaction medium batchwise in one portion, discontinuously in several portions and continuously with constant or varying flow rates.
  • the total amounts of diamine compound A, dicarboxylic acid compound B and optionally solvent E and at least a portion 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 dispersing agent D, in the aqueous reaction medium.
  • the mean 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 from Coulter Scientific Instruments.
  • the measurements are carried out on dilute aqueous miniemulsions whose content of non-aqueous constituents is about 0.01% by weight.
  • the dilution is carried out by means of water, which had previously been saturated with the diamine compounds A, dicarboxylic acid compounds B contained in the aqueous mini-emulsion, and optionally 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 in these machines by a achieved 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 released into two mixing nozzles through two oppositely directed nozzles.
  • the fine distribution effect here depends primarily on the hydrodynamic conditions in the mixing chamber.
  • An example of this homogenizer type is the microfluidizer type M 120 E Microfluidics Corp.
  • 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 z. B. also by application of 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 generated in the sound field does not only depend on the sound power applied, but also on other factors, such as noise levels.
  • the intensity distribution of the ultrasound in the mixing chamber, the residence time, the temperature and the physical properties of the substances to be emulsified for example, from the toughness, the interfacial tension and the vapor pressure.
  • the resulting droplet size depends i.a. from the concentration of the dispersant and from the registered during the homogenization of energy and is therefore z.
  • the device described in the earlier German patent application DE 197 56 874 has been described in particular. proven.
  • 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 radiating 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 portion of a flow-through reaction channel, extending over substantially the entire width of the channel, and the depth of the reaction space, which is substantially perpendicular to the emission 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 regard to the lowest possible risk of clogging and easy cleanability and a high product throughput, preferred reaction chamber depths are substantially greater than, for example, the usual gap heights in high-pressure homogenizers and usually above 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 essentially 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 passage extending substantially perpendicular to the direction of flow.
  • the radiating 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 discharge Beam surface in the flow direction, 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 corresponding 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 single ultrasound transmission means a plurality of separate transmission means can be arranged, which are connected in series 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 by a piezoelectric transducer and transmitted to the sonotrode as the transmission element into the sound Medium coupled.
  • 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 set oscillation amplitude is checked online and optionally readjusted automatically. 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. If necessary, the mixing can also be further intensified by an additional agitator.
  • the reaction space is temperature controlled.
  • an organic diol compound G in addition to the diamine compound A and dicarboxylic acid compound B, an organic diol compound G, a hydroxycarboxylic acid compound H, an aminoalcohol compound I, an aminocarboxylic acid compound K and / or an organic compound L, which is at least 3 Hydroxyl, primary or secondary amino and / or carboxyl groups per molecule can be used.
  • 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% by weight or> 1% by weight and often> 5% by weight, based in each case on the sum of the total amounts of diamine compound A and dicarboxylic acid compound B 1 .
  • the diol compound G 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-propanediol or 2,2,4-trimethyl-1,6-hexanediol.
  • 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, 3 Cyclohexanedimethanol (1,3-dimethylolcyclohexane), 1,4-cyclohexanedimethanol (1,4-dimethylolcyclohexane) or 2,2,4,4-tetramethyl-1,3-cyclobutanediol.
  • aromatic diols examples include 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.
  • diol compounds G it is also possible to use 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 whose number average molecular weight (M n ) is usually in the range of 200 to 10,000, preferably from 600 to 5000 g / mol.
  • 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, their cyclic derivatives such as glycolide (1, 4-dioxane-2,5-dione), D-, L-, D, L-dilactide (3,6-dimethyl, 4-dioxane-2,5-dione), ⁇ -caprolactone, ⁇ Butyrolactone, ⁇ -butyrolactone, dodecanolide (oxacyclotridecan-2-one), undecanolide (oxacyclododecan-2-one) or pentadecanolide (oxacyclohexadecan-2-one).
  • amino alcohol 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-aminocyclopentanol, 3-aminocyclopentanol, 2-aminocyclohexanol, 3-aminocyclohexanol, 4-aminocyclohexanol and 4-aminomethylcyclohexanemethanol (1 -Methylol-4-aminomethyl cyclohexane).
  • mixtures of the aforementioned aminoalcohol compounds I can be used.
  • Aminocarboxylic acid compounds K by which in the context of this document amino-carboxylic acids and / or their corresponding lactam compounds are to be understood, can be used in addition to the diamine compound A and the dicarboxylic acid compound B.
  • Examples include the naturally occurring amino carboxylic acids, such as valine, leucine, isoleucine, threonine, methionine, phenylalanine, tryptophan, 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-aminounecanoic acid, 12-aminolauric acid and the lactams ⁇ -propiolactam, Y-butyrolactam, ⁇ -valerolactam, ⁇ -caprolactam, 7-enantholactam, 8-caprylolactam
  • Another component which can optionally be used in the process according to the invention is an organic compound L which is 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 esters or anhydrides), pyromellitic acid (1, 2,4,5-Benzoltetracarbonklare and their esters or anhydrides), 4-hydroxy isophthalic acid, diethylenetriamine, dipropylenetriamine, bis
  • bis (3-aminopropy) ethylenediamine, diethanolamine or triethanolamine foregoing compounds L are characterized by their at least 3 hydroxyl, primary or secondary amino - And / or carboxyl groups per molecule capable of being incorporated simultaneously in at least 2 polyamide chains, which is why compounds L a branching or have crosslinking effect in the polyamide formation.
  • compounds L a branching or have crosslinking effect in the polyamide formation.
  • mixtures of compounds L can also be used here.
  • organic diol compound G hydroxycarboxylic acid compound H, aminoalcohol compound I 1 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 amounts of the compounds A and B and G to L are chosen such that the equivalent Ratio of the carboxyl groups and / or their derivatives (from the individual compounds B, H, K and L) to the sum of amino and / or hydroxyl groups and / or their derivatives (from the individual compounds A, G, H, I 1 K and L ) 0.5 to 1.5, usually 0.8 to 1.3, often 0.9 to 1, and often 0.95 to 1, 05 is.
  • 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 have as many equivalents of carboxyl groups as they contain carboxyl groups per molecule.
  • the diamine compounds A have 2 equivalents of amino groups, the diol compounds G 2 equivalents of hydroxyl groups, the hydroxycarboxylic acid compounds H a hydroxyl xyl phenomenon equivalent, the aminocarboxylic acid compounds K 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 react in particular with the diamine compounds A, dicarboxylic acid compounds B, organic diol 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 react in particular with the diamine compounds A, dicarboxylic acid compounds B, organic diol 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
  • the first reaction stage of the process according to the invention is advantageously such that at least a partial amount of diamine compound A 1 is first dicarboxylic acid compound B, Compound G, H, I, K and / or L, dispersant D and, if appropriate, solvent E and / or ethylenically unsaturated monomer F are introduced into at least a subset of the water, then by means of suitable measures a diamine compound A, the dicarboxylic acid compound B 1 the compound G, H, I, K and / or L and optionally the solvent E and / or the ethylenically unsaturated monomer F comprehensive disperse phase with an average droplet diameter
  • the enzyme C, the residual amounts of diamine compound A, dicarboxylic acid compound B 1 compound G, H, I, K and / or L and solvent E can be added to the aqueous reaction medium separately or together, discontinuously in one portion, batchwise in several portions and be added continuously 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 value (range) is set at 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 hydro
  • 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 stage is selected so that the aqueous polyamide dispersion formed according to the invention has a water content> 30% by weight, frequently> 50 and ⁇ 99% by weight or> 65 and ⁇ 95% by weight and often> 70 and ⁇ 90 wt .-%, each based on the aqueous polyamide dispersion is, corresponding to a Polyamidfeststoffgehalt ⁇ 70 wt .-%, often> 1 and ⁇ 50 wt .-% or> 5 and ⁇ 35 wt .-% and often> 10 and ⁇ 30% by weight.
  • the inventive method both in the first and Also in the second reaction stage advantageously under oxygen-free inert gas atmosphere, for example under a nitrogen or argon atmosphere is performed.
  • 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 polyamide 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.
  • deactivators are, in particular, complex compounds, for example nitrilotriacetic acid or ethylenediaminetetraacetic acid or its alkali metal salts or anionic emulsifiers, for example sodium dodecylsulfate.
  • polyamides may have to +200 0 C glass transition temperatures of -70.
  • polyamides are often required whose glass transition temperatures are within certain ranges.
  • 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).
  • the polyamide particles of the aqueous polyamide 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 about quasi-elastic light scattering (ISO standard 13 321)].
  • the polyamides 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> 3,000 to ⁇ 500,000 g / mol or> 5,000 to ⁇ 100,000 g / mol and frequently> 5,000 to ⁇ 50,000 g / mol or> 6,000 to ⁇ 30,000 g / mol.
  • the determination of the weight-average molecular weights is carried out by means of 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, usually dispersed with the concomitant use of dispersants in an aqueous medium and polymerized by means of at least one water-soluble radical polymerization initiator at polymerization.
  • the dispersant D and its amount must be such that it contains both the polyamide 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.
  • partial amounts 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 in the 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. WEI
  • 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 diamine compound A, dicarboxylic acid compound B and ethylenically unsaturated monomers F 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, based in each case on the sum of the total amounts of diamine compound A, 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 partial amounts 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> 30% by weight, frequently> 40 and ⁇ 99% by weight or> 45 and ⁇ 95% by weight and often> 50 and ⁇ 90% by weight, in each case based on the aqueous polymer dispersion, corresponding to a polymer solids content ⁇ 70% by weight, frequently> 1 and ⁇ 60% by weight or>
  • 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 wt .-% or> 20 and ⁇ 40 wt .-%, each based on the total amount of water used in the process according to the invention.
  • 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 accordingly> 0 and ⁇ 100 wt .-%,> 10 and ⁇ 80 wt .-% or> 30 and ⁇ 60 wt .-%, each based on the total amount of monomers F.
  • the quantitative ratio of the sum of the total amounts of diamine compound A and dicarboxylic acid compound B to the total amount of ethylenically unsaturated monomers F is generally 1:99 to 99: 1, preferably 1: 9 to 9: 1 and advantageously 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 polyamide particles formed in the first reaction stage contain monomers F dissolved or swelled with them, or the polyamide 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 polyamide 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 polymers may comprise up to + 15O 0 C glass transition temperatures of -70.
  • polymers are often 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 " d 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 radical initiators have a water solubility> 2% by weight,> 5% by weight, or> 10% by weight under aforementioned conditions
  • oil-soluble free-radical initiators frequently have a water solubility ⁇ 0.9% by weight, ⁇ 0.8 % By weight, ⁇ 0.7% by weight, ⁇ 0.6% by weight, ⁇ 0.5% by weight, ⁇ 0.4% by weight, ⁇ 0.3% by weight, ⁇ 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
  • alkyl hydroperoxides such as alkyl hydroperoxides
  • Suitable oxidizing agents for redox initiator systems are essentially the abovementioned peroxides.
  • 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 bisulfite, alkali metal bisulfite.
  • sulfites for example potassium and / or sodium metabisulfite, formaldehyde sulfoxylates, for example potassium and / or sodium formaldehyde sulfoxylate, alkali salts, especially potassium and / or sodium salts, aliphatic sulfinic acids and alkali metal hydrogen sulfides, for example potassium and / or sodium hydrosulfide, 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 saccharides, such as sorbose, glucose, fructose and / or dihydroxyacetone be used.
  • polyvalent metals such as Iron (II) sulfate, iron (II) ammonium sulfate, iron (II) phosphate
  • endiols
  • 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 free-radical initiators are dialkyl or diaryl peroxides, 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 (tert-butyl peroxy) -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 peroxynode
  • Is preferred as the 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 .- Butyl peroxyacetate, tert-butyl peroxy-3,5,5-trimethylhexanoate (Trigonox ® 42 S), tert-Butylperoxiisobutanoat, tert-Butylperoxidiethylacetat, tert-butyl peroxypivalate, tert-Butylperoxiisopropylcarbonat, (Trigonox ® BPIC) and tert.
  • Trigonox ® 21 tert-butyl peroxy-2-ethylhexanoate
  • 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 11O 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.
  • emulsion polymerizations are carried out under reduced pressure, pressures of 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 inventive method is such that in the first reaction stage, at least a portion of diamine compound A, d-carboxylic acid compound B, 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 diamine 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 optionally remaining amounts of diamine compound A, dicarboxylic acid compound B and solvent E are added and after completion of the polyamide formation, in the second reaction stage, the remaining amounts of water remaining he 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 inventive method opens up a simple and inexpensive access to new aqueous polymer dispersions, which combine both the product properties of the polyamides and those of the polymers in itself.
  • BASF AG 1, 55 g (5.8 mmol) of diethyl sebacate (98% strength by weight, Sigma-Aldrich Inc.), 1.85 g (17.8 mmol) of styrene and 0.24 g of hexadecane are homogeneously mixed by stirring using a magnetic stirrer , A homogeneous solution (BASF AG nonionic emulsifier, commercial product from.) Were dissolved in this mixture under stirring of 0.24 g of Lutensol ® AT 50 and 23.8 g of a buffer solution (with a pH of 6.87, containing 0.025 mol / l potassium dihydrogen phosphate (KH 2 PO 4 ) and 0.025 mol / l disodium hydrogenphosphate (Na 2 HPO 4 ) in deionized water).
  • a buffer solution with a pH of 6.87, containing 0.025 mol / l potassium dihydrogen phosphate (KH 2 PO 4 ) and 0.025 mol
  • 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 breast vessel and purified by means of an Ultra-Turrax T25 apparatus (from Janke & Kunkel GmbH & Co. KG) for 30 seconds at 20500 rpm. Thereafter, the resulting liquid-heterogeneous mixture for transfer into droplets with an average droplet diameter ⁇ 1000 nm for 3 minutes of ultrasonic treatment by means of an ultrasonic probe (70 W; UW 2070 device from. Bandelin electronic GmbH & Co. KG) subjected.
  • an ultrasonic probe 70 W; UW 2070 device from. Bandelin electronic GmbH & Co. KG
  • a homogeneous enzyme mixture prepared from 0.24 g of lipase from Candida antarctica type B (commercial product from. Fluka AG), 0.14 g Lutensol ® AT 50 and 14, 4 g of the aforementioned buffer solution, then the resulting mixture was heated with stirring to 50 0 C and the mixture was stirred at this temperature for 20 hours under a nitrogen atmosphere.
  • aqueous polymer dispersion having a solids content of 11.5% by weight were obtained.
  • the mean particle size was determined to be 270 nm.
  • the glass transition temperature was determined to 55 ° C (polyamide) and about 100 0 C (polystyrene).
  • the polymer had melting points at 155 0 C and 220 0 C.
  • the solids content was determined by drying a defined amount of the aqueous polymer dispersion (about 5 g) at 18O 0 C in a drying oven to constant weight. 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. 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 of the melting point was made according to DIN 53765 by means of a DSC820 instrument, series TA8000 from Mettler-Toledo Intl. Inc ..

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Microbiology (AREA)
  • General Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Cosmetics (AREA)
  • Sealing Material Composition (AREA)
  • Polyamides (AREA)

Abstract

La présente invention concerne un procédé pour préparer une dispersion polymère aqueuse, comprenant les étapes suivantes: un composé de diamine et un composé d'acide dicarboxylique, sont convertis en un polyamide, dans un milieu aqueux, en la présence d'une enzyme et d'un agent de dispersion, et éventuellement d'un solvant organique peu soluble dans l'eau et/ou d'un monomère éthyléniquement insaturé; puis un monomère éthyléniquement insaturé est polymérisé par voie radicalaire en la présence du polyamide.
EP06725631A 2005-04-07 2006-04-07 Procede pour preparer une dispersion polymere aqueuse Withdrawn EP1869094A1 (fr)

Applications Claiming Priority (2)

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DE102005016226A DE102005016226A1 (de) 2005-04-07 2005-04-07 Verfahren zur Herstellung einer wässrigen Polymerdispersion
PCT/EP2006/061418 WO2006106138A1 (fr) 2005-04-07 2006-04-07 Procede pour preparer une dispersion polymere aqueuse

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EP (1) EP1869094A1 (fr)
JP (1) JP2008538786A (fr)
CN (1) CN101155843A (fr)
BR (1) BRPI0607905A2 (fr)
DE (1) DE102005016226A1 (fr)
WO (1) WO2006106138A1 (fr)

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DE102005005493A1 (de) * 2005-02-04 2006-08-10 Basf Ag Verfahren zur Herstellung einer wässrigen Polymerdispersion
DE102005023386A1 (de) * 2005-05-17 2006-11-23 Basf Ag Verfahren zur Herstellung einer wässrigen Polymerdispersion
FR2949232B1 (fr) * 2009-08-18 2011-10-28 Ceca Sa Composition bitumineuse contenant un polymer supramoleculaire
EP2738198A1 (fr) * 2012-11-29 2014-06-04 Henkel AG & Co. KGaA Synthèse enzymatique de polyamide en mini-émulsion aqueuse
US20150344620A1 (en) 2014-05-28 2015-12-03 Elevance Renewable Sciences, Inc. Aqueous Monomer Compositions and Methods of Making and Using the Same
US20170260554A1 (en) * 2014-07-31 2017-09-14 Karlsruher Institut für Technologie Method For The Enzyme-Catalyzed Production Of Prepolymers For Producing Plastics
WO2016112013A1 (fr) 2015-01-06 2016-07-14 Lawter, Inc. Résines polyamide pour l'enrobage d'agents de soutènement à base de sable ou de céramique utilisés dans la fracturation hydraulique
KR102190917B1 (ko) * 2018-08-31 2020-12-15 씨제이제일제당 주식회사 점착 조성물, 및 이의 제조방법
CN111635521B (zh) * 2020-06-20 2022-08-02 万华化学集团股份有限公司 一种端羟基不饱和聚酰胺及其制备方法和应用

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BRPI0607905A2 (pt) 2016-11-08
US20080194772A1 (en) 2008-08-14
WO2006106138A1 (fr) 2006-10-12
JP2008538786A (ja) 2008-11-06
CN101155843A (zh) 2008-04-02
DE102005016226A1 (de) 2006-10-12

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