EP1819754A2 - Procede pour produire une dispersion de polyamide aqueuse - Google Patents

Procede pour produire une dispersion de polyamide aqueuse

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Publication number
EP1819754A2
EP1819754A2 EP05814289A EP05814289A EP1819754A2 EP 1819754 A2 EP1819754 A2 EP 1819754A2 EP 05814289 A EP05814289 A EP 05814289A EP 05814289 A EP05814289 A EP 05814289A EP 1819754 A2 EP1819754 A2 EP 1819754A2
Authority
EP
European Patent Office
Prior art keywords
acid
aqueous
solvent
polyamide
compounds
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.)
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Application number
EP05814289A
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German (de)
English (en)
Inventor
Xiang-Ming Kong
Motonori Yamamoto
Dietmar HÄRING
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BASF SE
Original Assignee
BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1819754A2 publication Critical patent/EP1819754A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/16—Preparatory processes

Definitions

  • the present invention is a process for the preparation of an aqueous polyamide dispersion, which is characterized in that in an aqueous medium
  • Aqueous polyamide dispersions are widely used, for example, for the production of hotmelt adhesives, coating formulations, printing inks, paper coating slips, etc.
  • aqueous polyamide dispersions are well known.
  • the preparation is generally carried out in such a way that an organic aminocarboxylic acid compound is converted to a polyamide compound.
  • This polyamide compound is then in a subsequent stage usually first in a polyamide 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.
  • a solvent 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. 5,236,996, US Pat -B 6,777,488, WO 97/47686 or WO 98/44062).
  • Bonklareinstitut - without additional dispersion / distillation stage - provides in good yields.
  • Suitable aminocarboxylic acid compounds A are all organic compounds which have an amino and a carboxy group in free or dehvated form, but in particular the C 2 -C 3 o-aminocarboxylic acids, the C 1 -C 5 -alkyl esters of the abovementioned aminocarboxylic acids, the corresponding C 3 -Ci 5 - lactam compounds, the C 2 -C 3 o-aminocarboxamides or the C 2 -C 30 - Aminocarbon Acid.
  • Examples of the free CrCso-aminocarboxylic acids are the naturally occurring aminocarboxylic acids, such as valine, leucine, isoleucine, threonine, methionine, phenylalanine, tryptophan, lysine, alanine, arginine, aspartic acid, cysteine, glutamic acid, glycine, histidine, proline, serine, thyosine , 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, 13-aminotridecanoic acid, 14 Aminotetradecanoic acid or 15-aminopentadecanoic acid.
  • Examples of the C 1 -C 5 -alkyl esters of the abovementioned aminocarboxylic acids are 3-aminopropionic acid, 4-aminobutyric acid, 5-aminovaleric acid, 6-aminocaproic acid, 7-aminoanthic acid, 8-aminocaprylic acid, 9-aminoparactone, Called 10-aminocapric acid, 11-aminoundecanoic acid, 12-aminolauric acid, 13-aminotridecanoic acid, 14-aminotetradecanoic acid or 15-aminopentadecanoic acid methyl and ethyl ester.
  • C 3 -C 5 -lactam compounds are ⁇ -propiolactam, ⁇ -butyrolactam, ⁇ -valerolactam, ⁇ -caprolactam, 7-enantholactam, 8-caprylolactam, 9-pelargolactam, 10-caprinlactam, 11-undecanoic acid lactam, ⁇ - Laurinlactam, 13-Tridecan Textrelactam, 14-Tetradecanklaklandellactam or 15-Pentadecanklandrelactam called.
  • aminocarboxamides are 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, 13-aminotridecanoic acid, 14-aminotetradecanoic acid or 15-aminopentadecanoic acid amide and, as examples of the aminocarboxylic acid nitriles, 3-aminopropionic, 4-aminobutyric, 5-aminovaleric, 6-aminocapronate, 7-aminoanthantric , 8-aminocapryl, 9-aminopelargon, 10-aminocaprin, 11-aminoundecane, 12-aminolaurin, 13-aminotridecane, 14-aminotetradecane or 15-
  • the hydrolase B is selected so that it undergoes a polycondensation reaction of the amino groups and the carboxy groups in free or derivatized form, for example with elimination of water (free aminocarboxylic acids), alcohol (esters of aminocarboxylic acids) or hydrogen halide (halides of aminocarboxylic acids) and / or a ring opening with subsequent polyaddition, for example, in the aforementioned C 3 -Ci 5- lactam compounds to catalysis can.
  • hydrolases B are, 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.
  • Carboxyl esterases [EC 3.1.1.1] and / or lipases [EC 3.1.1.3] are particularly advantageous in accordance with the invention.
  • lipomas from Achromobacter sp., Aspergillus sp., Candida sp., Candida antarctica, Mucor sp., Penicilium sp., Geotricum sp., Rhizopus sp, Burkholde- ria 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 hydrolases B used is generally 0.001 to 40 wt .-%, often 0.1 to 15 wt .-% and often 0.5 to 8 wt .-%, each based on the total amount of aminocarboxylic acid compound A.
  • the dispersants C 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 hydrolases B used and do not deactivate them. Which emulsifiers and / or protective colloids can be used in a particular hydrolase B, 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 homopolymers and copolymers.
  • suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV /
  • 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.
  • cationic emulsifiers while anionic and cationic emulsifiers are usually incompatible with each other.
  • An overview of suitable emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg-Thieme-Verlag, Stuttgart, 1961, p 192 to 208.
  • dispersants C are used as dispersants.
  • Common nonionic emulsifiers are, for example, ethoxylated mono-, di- and Tn-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) 36 ).
  • Lutensol ® A grades C 12 C 14 fatty alcohol ethoxylates, EO units: 3 to 8
  • Lutensol ® AO-marks C 13 C 15 - oxo alcohol ethoxylates, EO units: 3 to 30
  • Lutensol ® AT grades C 16 C 18 - fatty alcohol ethoxylates, EO grade: 11 to 80
  • Lutensol ® ON grades C 10 - oxo alcohol ethoxylates, EO grade: 3 to 11
  • Lutensol ® TO grades C 13 - Oxoalkoholethoxylate, EO degree: 3 to 20
  • Typical anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C 8 to C 12 ), of sulfuric monoesters of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: C 12 to C 18 ) and ethoxylated alkylphenols (EO radicals). degree: 3 to 50, alkyl radical: C 4 to C 12), of alkylsulfonic acids (alkyl radical: C 12 to C 8) and of Al kylarylsulfonkla (alkyl radical: C 9 to C 18).
  • Further anionic emulsifiers further compounds of the general formula (I)
  • R 1 and R 2 are H atoms or C 4 - to C 24 alkyl and are not simultaneously HI 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 are compounds (I) 1 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 having C 6 -C 18 -alkyl, -alkylaryl or heterocyclic radicals, 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-trimethylammonium) ethylparaffinklaer, N-Cetylpyridiniumsulfat, N-
  • Laurylpyridiniumsulfat and N-Cetyl-N N, N-trimethylammoniumsulfat, N-dodecyl-trimethylammoniumsulfat NNN, 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 sulfate and ethoxylated oleylamine (for example Uniperol.RTM ® AC from.
  • BASF AG about 12 ethylene oxide.
  • Numerous other examples can be found in H. Stumblee, Tensid-Taschenbuch, Carl-Hanser-Verlag, Kunststoff, Vienna, 1981 and in McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989.
  • the anionic counterparts 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- ormethylsulf
  • the emulsifiers preferably used as dispersant C 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 total amount of aminocar - Bonklarethetic A, used.
  • the total amount of protective colloids used as dispersing agent C 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, in each case based on the total amount of aminocarboxylic acid compound A.
  • Suitable solvents D are liquid aliphatic and aromatic hydrocarbons having 5 to 30 carbon atoms, such as 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 from 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 having 1 to 10 carbon atoms in the carboxylic acid moiety and 10 to 28 carbon atoms in the alcohol part.
  • 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 having 1 to 10 carbon atoms in the carboxylic acid moiety and 10 to 28 carbon atoms in the alcohol part.
  • esters such as fatty acid esters having 10 to 28 carbon atoms in the acid moiety and 1 to 10 carbon atom
  • the total amount of optionally used solvent D 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 used.
  • the solvent D and its amount are chosen so that the solubility of the solvent D in the aqueous medium under reaction conditions ⁇ 50 wt .-%, ⁇ 40 wt .-%, ⁇ 30 wt .-%, ⁇ 20 wt % or ⁇ 10 wt .-%, each based on the total amount of solvent, and thus is present as a separate phase in the aqueous medium.
  • Solvents D are used in particular when the aminocarboxylic acid compound A has a good solubility in an aqueous medium under reaction conditions, ie its solubility> 10 g / l,> 30 g / l or frequently> 50 g / l or> 100 g / l.
  • the process according to the invention is advantageous if at least a portion of the aminocarboxylic acid compound A and / or, if appropriate, of the solvent D is present in the aqueous medium as a disperse phase with an average droplet diameter ⁇ 1000 nm (a so-called oil-in-water miniemulsion or short miniemulsion) ,
  • the inventive method is such that at least a partial amount of aminocarboxylic acid compound A, dispersant C and optionally solvent D are introduced into a partial or the total amount of water, then by means of suitable measures an amino carboxylic acid compound A and / or optionally Solvent D 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 hydrolase B and any residual amounts of water, amino carboxylic acid compound A, dispersant C and optionally solvent D is added.
  • hydrolase B and any residual amounts of water, aminocarboxylic acid compound A, dispersant C and optionally solvent D may be added to the aqueous reaction medium discontinuously in one portion, discontinuously in several portions and continuously with constant or varying flow rates.
  • the total amounts of aminocarboxylic acid compound A and optionally solvent D and at least a subset of the dispersant C are introduced into the main or total amount of water and after formation of the miniemulsion at reaction temperature, the total amount of the hydrolase B, optionally together with the residual amounts of water and the dispersant C, 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).
  • the values for d z thus determined for the so-called miniemulsions are normally ⁇ 700 nm, frequently ⁇ 500 nm.
  • the d z range is from 100 nm to 400 nm or from 100 nm to 300 nm d z of the aqueous miniemulsion to be used according to the invention is> 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 NS1001 L 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 jet is filtered in a microchannel tem divided into two beams, which are guided at an angle of 180 ° to each other.
  • Another example of a homogenizer operating according to this type of homogenization is the Nanojet Type Expo from Nanojet Engineering GmbH. However, instead of a fixed duct system, the Nanojet has two homogenizing valves that can be adjusted mechanically.
  • homogenization may be e.g. also by using ultrasound (e.g., Branson Sonifier Il 450).
  • ultrasound e.g., 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 noise.
  • the resulting droplet size depends i.a. from the concentration of the dispersing agent as well as the energy introduced during the homogenization and is therefore selectively adjustable by corresponding change in the homogenization pressure or the corresponding ultrasound energy.
  • the apparatus 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 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 to mean 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 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 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 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 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 can be use of the reverse piezoelectric effect are generated.
  • high-frequency electrical oscillations (usually in the range of 10 to 100 kHz, preferably between 20 and 40 kHz) are generated by means of generators, converted by a piezoelectric transducer into mechanical vibrations of the same frequency and with the sonotrode as a transmission element in the to be sonicated Medium coupled.
  • the sonotrode is designed as a rod-shaped, axially radiating ⁇ / 2 (or multiple of ⁇ / 2) longitudinal oscillator.
  • a sonotrode can be fastened in an opening of the housing, for example, by means of a flange provided on one of its vibration nodes.
  • 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 can be regulated, that is to say the oscillation amplitude set in each case is checked online and, if appropriate, 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.
  • the mixing can also be further intensified by an additional agitator.
  • the reaction space is temperature controlled.
  • Suitable diamine compounds E 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 may have a C 2 -C 2 o-aliphatic, C 3 -C 2 o-cycloaliphatic, aromatic or heteroaromatic structure.
  • Examples of two primary amino-containing compounds E are 1,2-diaminoethane, 1, 3-diaminopropane, 1, 2
  • 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 or p-xylylenediamine as optional Dia- mintheticen E used.
  • dicarboxylic acid compounds F it is possible in principle to use all C 2 -C 4 0-aliphatic, C 3 -C 20 -cycloaliphatic, aromatic or heteroaromatic compounds which have two carboxylic acid groups (carboxy groups; -COOH) or derivatives thereof.
  • Particularly suitable derivatives are dC 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 anhydrides use.
  • 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), C 32 -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 (
  • the free dicarboxylic acids in particular butanedioic acid, hexanedioic acid, decanedioic acid, dodecanedioic acid, terephthalic acid or isophthalic acid or their corresponding dimethyl ester.
  • 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 are used as optional diol compounds G.
  • 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-propy
  • 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 examples include 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, polyethylene 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).
  • poly-THF polyethylene glycol or polypropylene glycol find compounds use woveng whose number average molecular weight (M n ) is usually in the range of 200 to 10,000, preferably from 600 to 5000 g / mol.
  • mixtures of the aforementioned diol G can be used.
  • hydroxycarboxylic acid compounds H it is possible to use the free hydroxycarboxylic acids, their C 1 -C 5 -alkyl esters 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 (oxacyclotridecan-2-one), undecanolide (oxacyclododecan-2-one) or pentadecanolide (ox
  • all but preferably C 2 -C 12 -aliphatic, C 5 -C 10 -cycloaliphatic or aromatic organic compounds which have only one hydroxyl group and one secondary or primary, but preferably one primary amino group, can be used as optional aminoalcohol compounds I .
  • 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).
  • organic compounds K which have at least 3 hydroxyl, primary or secondary amino and / or carboxy groups per molecule.
  • organic compounds K which have at least 3 hydroxyl, primary or secondary amino and / or carboxy groups per molecule.
  • examples which may be mentioned are tartaric acid, citric acid, malic acid, methylolpropane, trimethylolethane, pentaerythritol, polyether triols, glycerol, sugars (for example glucose, mannose, fructose, galactose, glucosamine, sucrose, lactose, trehalose, maltose, cellobiose, gentianose, kestose, Maltotriose, raffinose, thme- mesic acid (1, 3,5-benzenetricarboxylic acid and its esters or anhydrides), trimellitic acid (1, 2,4-benzenetricarboxylic acid and its esters or anhydrides), py
  • Hydroxyisophthalic acid diethylenetriamine, dipropylenetriamine, bishexamethylenetriamine, N, N'-bis (3-aminopropyl) ethylenediamine, diethanolamine or triethanolamine.
  • the aforementioned compounds K are, by virtue of their at least 3 hydroxyl, primary or secondary amino and / or carboxy groups per molecule, able to be incorporated simultaneously in at least two polyamide chains, for which reason compound K has a branching or crosslinking action in the polyamide formation , The higher the content of compounds K, or the more amino, hydroxy and / or carboxy groups present per molecule, the higher the degree of branching / crosslinking in polyamide formation.
  • mixtures of compounds K can also be used here.
  • the amounts of the compounds A and E, F, G, H, I and / or K are chosen such that the equivalent Ratio of the carboxy groups and / or their derivatives (from the individual compounds A, F 1 H and K) to the sum of amino and / or hydroxy groups and / or their derivatives (from the individual compounds A, E, G, H, I and K) 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.
  • the equivalent ratio is 1, ie the same number of amino and / or hydroxyl groups as carboxy groups or groups derived therefrom are present.
  • the aminocarboxylic acid compound A has one equivalent of carboxy groups
  • the dicarboxylic acid compound F free acid, ester, halide or anhydride 2 equivalents of carboxy groups
  • the hydroxycarboxylic acid compound H one equivalent of carboxy groups
  • the organic compound K as many equivalents of carboxy groups has as it contains carboxy groups per molecule.
  • the aminocarboxylic acid Compound A is one equivalent of amino groups
  • the diamine compound E is 2 equivalents of amino groups
  • the diol compound G is 2 equivalents of hydroxy groups
  • the hydroxycarboxylic acid compounds H is a hydroxy group equivalent
  • the aminoalcohol compound I is an amino group and one hydroxy group equivalent
  • the organic compound K is as many equivalents to hydroxy or amino groups, as containing hydroxyl or amino groups in the molecule.
  • the hydrolases B are selected in particular with the amino carboxylic acid compound A used, diamine compound E 1 dicarboxylic acid compound F, diol compound G, hydroxycarboxylic acid compound H, aminoalcohol compound I and / or organic compound K which contains at least 3 hydroxy, primary or secondary amino and / or carboxy groups per molecule or are compatible with the dispersant C and the solvent D and are not deactivated by them.
  • the expert knows or can be determined from this in simple preliminary experiments.
  • the process according to the invention advantageously takes place in such a way that first at least one subset of aminocarboxylic acid compound A, compound E, F, G , H, I and / or K, dispersing agent C and, if appropriate, solvent D are introduced into a partial or total amount of water, then by means of suitable measures an amino carboxylic acid compound A and the compound E, F 1 G 1 H, I and / or K and / or optionally the solvent D 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 hydrolase B and any remaining amounts of water, aminocarboxylic acid compound A, compound E 1st F, G, H, I and / or K 1 dispersant C and optionally solvent D is added.
  • hydrolase B and any remaining amounts of water, aminocarboxylic acid compound A, compound E, F, G, H, I and / or K, dispersant C and optionally solvent D discontinuous to the aqueous reaction medium in one portion, discontinuously in several portions and continuously added with constant or varying flow rates.
  • the process of the invention is generally carried out at a reaction temperature of 20 to 90 0 C 1, often from 35 to 60 0 C and often from 45 to 55 0 C at a pressure (absolute values) of usually from 0.8 to 10 bar, preferably from 0.9 to 2 bar and in particular at 1 bar (atmospheric pressure).
  • the aqueous reaction medium 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 hydrolase B 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, or buffer substances, for example potassium dihydrogenphosphate / disodium hydrogenphosphate, acetic acid / sodium acetate, ammonium hydroxide / Ammonium chloride, potassium dihydrogen phosphate / sodium hydroxide, borax / hydro
  • water is used, which is clear and often has drinking water quality.
  • deionized water is advantageously used for the process according to the invention.
  • the amount of water is chosen so that the present invention accessible aqueous polyamide dispersion has a water content> 30 wt .-%, often> 50 and ⁇ 99 wt .-% or> 65 and ⁇ 95 wt .-% and often> 70 and ⁇ 90 wt .-%, each based on the aqueous polyamide dispersion is, corresponding to a polyamide 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 a nitrogen or argon atmosphere.
  • an adjuvant is added to the aqueous polyamide dispersion following or at the end of the enzymatically catalyzed polymerization reaction which is capable of deactivating the hydrolase B used according to the invention (ie destroying the catalytic activity of hydrolase B) or to inhibit).
  • deactivator it is possible to use all compounds which are capable of deactivating the respective hydrolase B.
  • Complex compounds for example nitrilotriacetic acid or ethylenediaminetetraacetic acid or their alkali metal salts or anionic compounds, may frequently be used as deactivators
  • Emulsifiers for example sodium dodecyl sulfate can be used.
  • polyamides for example, as binders in coating formulations using the composition of the compounds used is selected so that the produced polyamides glass transition temperatures from -40 to +150 0 C 1 often from 0 to +100 0 C, and often from +20 to + 80 0 C have.
  • 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 , determined by quasi-elastic light scattering (ISO standard 13 321)].
  • the polyamides obtainable by the process according to the invention generally have a weight-average molecular weight in the range> 2000 to ⁇ 1 000 000 g / mol, often> 3000 to ⁇ 500 000 g / mol and frequently> 5000 to ⁇ 300 000 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 aqueous polyamide 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 primers, for finishing leather and textiles, for fiber bonding and for modifying mineral binders or asphalt.
  • aqueous polyamide dispersions obtainable according to the invention can be converted by drying into the corresponding polyamide powders.
  • Corresponding drying methods for example freeze-drying or spray-drying, are known to the person skilled in the art.
  • the polyamide powders obtainable according to the invention can be advantageously used as pigment, filler in plastic formulations, as a component in adhesives, sealing compounds, plastic plasters, paper coating slips, printing inks, cosmetic formulations, powder coatings and paints, for finishing leather and textiles, for fiber bonding and for modifying use mineral binders or asphalt.
  • the average particle diameter of the polyamide particle was generally on by dynamic light scattering on a 0.005 to 0.01 weight percent aqueous disper- at 23 0 C using an Autosizer IIC from. Malvern Instruments, England determined.
  • the mean diameter of the cumulant evaluation (cumulant z-average) of the measured autocorrelation function (ISO standard 13321) is given.
  • 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 having an average droplet diameter ⁇ 1000 nm (miniemulsion) for 3 minutes of an ultrasonic treatment by means of an ultrasonic probe (70 W; UW 2070 device from. Bandelin electronic GmbH & Co.
  • the average particle size was determined to be about 220 nm.
  • the glass transition temperature and the melting point of the polyamide obtained 10 g of the obtained aqueous polyamide dispersion were subjected to centrifugation (3000 rpm) for 10 minutes, the polyamide particles precipitating as a sediment.
  • the supernatant clear aqueous solution was decanted and the polyamide particles slurried with 10 g of deionized water and stirred for 10 minutes. Subsequently, the deposition by centrifuge, decanting the supernatant clear solution, etc. took place again.
  • the resulting polyamide particles were treated by the aforementioned procedure three times with 10 g of deionized water and then three times with 10 g of tetrahydrofuran.
  • the remaining polymeric residue was then dried for 5 hours at 50 ° C / 1 mbar (absolute).
  • the resulting polyamide (about 0.25 g) had a weight-average molecular weight Mw of 212,000 g / mol and a number-average molecular weight Mn of 47,000 g / mol.
  • the melting point was determined to be about 200 0 C.
  • the remaining polymeric residue was then dried for 5 hours at 50 ° C / 1 mbar (absolute).
  • the polyamide (about 1 g) thus obtained had a weight average molecular weight Mw of 16600 g / mol and melting points at 94 0 C and about 210 0 C.

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Abstract

L'invention concerne un procédé pour produire une dispersion de polyamide aqueuse par transformation catalysée par hydrolase d'une liaison aminoacide dans un milieu aqueux.
EP05814289A 2004-12-01 2005-11-29 Procede pour produire une dispersion de polyamide aqueuse Withdrawn EP1819754A2 (fr)

Applications Claiming Priority (2)

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DE102004058073A DE102004058073A1 (de) 2004-12-01 2004-12-01 Verfahren zur Herstellung einer wässrigen Polyamid-Dispersion
PCT/EP2005/012731 WO2006058696A2 (fr) 2004-12-01 2005-11-29 Procede pour produire une dispersion de polyamide aqueuse

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DE102005023386A1 (de) * 2005-05-17 2006-11-23 Basf Ag Verfahren zur Herstellung einer wässrigen Polymerdispersion
FR2914856B1 (fr) * 2007-04-12 2012-08-03 Arkema France Composition cosmetique comprenant une poudre fine
AU2012202501B2 (en) * 2007-04-12 2012-09-13 Arkema France Cosmetic composition comprising a fine powder
JP2010524675A (ja) 2007-04-26 2010-07-22 ビーエーエスエフ ソシエタス・ヨーロピア マイクロカプセルの酵素的製造法
BRPI0919589A2 (pt) * 2008-10-24 2015-12-08 Basf Se processos para preprarar micropartículas, para combater o crescimento de plantas indesejáveis, e para combater infestação de ácaros ou de insetos indesejáveis nas plantas e/ou para combater fungos fitopatogênicos, micropartícula, formulação agroquímica, e, semente
WO2014067746A1 (fr) * 2012-11-01 2014-05-08 Evonik Industries Ag Procédé pour la formation enzymatique de liaisons amide
CA2972613C (fr) 2015-01-06 2023-08-01 Lawter, Inc. Resines polyamide pour l'enrobage d'agents de soutenement a base de sable ou de ceramique utilises dans la fracturation hydraulique
CN111534458B (zh) * 2020-04-13 2022-01-14 浙江工业大学 无色杆菌tbc-1及其在降解1,3,6,8-四溴咔唑中的应用
WO2024024855A1 (fr) * 2022-07-29 2024-02-01 住友精化株式会社 Papier couché et son procédé de production

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US4886844A (en) * 1988-02-03 1989-12-12 Union Camp Corporation Polyamide resin dispersions and method for the manufacture thereof
US5236996A (en) * 1991-07-24 1993-08-17 Union Camp Corporation Stable polyamide resin dispersions containing piperasine and methods for the manufacture thereof
JP4404988B2 (ja) * 1999-04-21 2010-01-27 住友精化株式会社 ポリアミド樹脂水性分散液の製造方法
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CN101068856A (zh) 2007-11-07
WO2006058696A2 (fr) 2006-06-08

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