EP1904536A1 - Procede de production d'une dispersion aqueuse de polymere - Google Patents

Procede de production d'une dispersion aqueuse de polymere

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Publication number
EP1904536A1
EP1904536A1 EP06763799A EP06763799A EP1904536A1 EP 1904536 A1 EP1904536 A1 EP 1904536A1 EP 06763799 A EP06763799 A EP 06763799A EP 06763799 A EP06763799 A EP 06763799A EP 1904536 A1 EP1904536 A1 EP 1904536A1
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EP
European Patent Office
Prior art keywords
polymer
membrane
polymer solution
microporous membrane
weight
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
EP06763799A
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German (de)
English (en)
Inventor
Jacob Wildeson
Thomas Danner
Sonja Viereck
Andreas Bauder
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BASF SE
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BASF SE
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Publication date
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Publication of EP1904536A1 publication Critical patent/EP1904536A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/147—Microfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B01F23/41—Emulsifying
    • B01F23/4105—Methods of emulsifying
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/20—Concentration
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions

Definitions

  • the present invention is a process for the preparation of an aqueous polymer dispersion, which is characterized in that
  • the crude emulsion obtained is passed through a microporous membrane to form an oil-in-water emulsion having an average droplet diameter ⁇ 1000 nm (miniemulsion), and thereafter
  • aqueous polymer dispersions are often carried out by the method of free-radically initiated aqueous emulsion polymerization. This method has been described many times and is therefore sufficiently known to the person skilled in the art [cf. for example, Encyclopedia of Polymer Science and Engineering, Vol. 8, pp. 659-677, John Wiley & Sons, Inc., 1987; DC Blackley, Emulsion Polymerization, pp. 155-465, Applied Sciences Publishers, Ltd., Essex, 1975; . DC Blackley, polymer latices, 2 nd Edition, Vol 1, pages 33 to 415, Chapman & Hall, 1997; H.
  • the free-radically initiated aqueous emulsion polymerization is usually carried out by dispersing the ethylenically unsaturated monomers, generally with the concomitant use of dispersing aids, in aqueous medium and polymerizing them by means of at least one free-radical polymerization initiator.
  • the residual contents of unreacted monomers are also chemical and / or physical methods known to the person skilled in the art [see, for example, EP-A 771328, DE-A 19624299, DE-A 19621027, DE-A 19741184, DE-A 19741187, DE-A 19805122, DE-A 19828183, DE-A 19839199, DE-A 19840586 and 19847115], adjusted the polymer solids content by dilution or concentration to a desired value or added to the aqueous polymer dispersion further conventional additives, such as bactericidal or foam-damping additives ,
  • a disadvantage of the method of aqueous emulsion polymerization is that aqueous polymer dispersions can only be obtained starting from ethylenically unsaturated monomers.
  • aqueous polymer dispersions in the form of so-called secondary aqueous polymer dispersions is known (see, for example, Eckersley et al., Am. Chem. Soc, Div. Polymer Chemistry, 1977, 38 (2), pages 630, 631, US A 3,360,599, US-A 3,238,173, US-A 3,726,824, US-A 3,734,686 or US-A 6,207,756).
  • the preparation of the secondary aqueous polymer dispersions is generally carried out in such a way that the polymer is dissolved in an organic solvent and dispersed to form an aqueous polymer / solvent (mini) emulsions in an aqueous medium.
  • a disadvantage of the abovementioned secondary aqueous polymer dispersions is their broad particle size distribution and the required relatively large amounts of dispersing assistant in order to keep the polymer particles in disperse-distributed form. Further disadvantages are the high energy inputs required for the production, combined with high shear forces and the resulting high coagulum contents of the resulting secondary aqueous polymer dispersions.
  • the object of the present invention was to provide a process for the preparation of secondary aqueous polymer dispersions, which does not have the aforementioned disadvantages.
  • low water solubility should be understood as meaning that the polymer or the organic solvent in deionized water at 20 ° C. and 1 atm (absolute) has a solubility ⁇ 50 g / l, preferably ⁇ 10 g / l and advantageously ⁇ 5 g / 1 and ⁇ 1 g / 1, respectively.
  • polymers which have a low solubility in water and which are capable of forming a homogeneous polymer solution with an organic solvent which is sparingly soluble in water.
  • the following polymers can be used in the process according to the invention: polyolefins based on linear or branched C 2 - to C 20 -aliphatic or aromatic mono- or diethylenically unsaturated compounds, for example the homopolymers or copolymers based on ethene, propene, 1-butene, 2-butene, 2-methylpropene (isobutene), 1,3-butadiene, isoprene, styrene, in particular the homopolymers polyethene, polypropene , Poly-1-butene, polyisobutene, polybutadiene or polystyrene or the corresponding copolymers of ethene / propene, ethene / 1-but
  • esters of acrylic and / or methacrylic acid with alkanols having 1 to 20 C atoms in particular esters of acrylic and / or methacrylic acid with methanol, ethanol, propanol, isopropanol, n-butanol or 2-ethylhexanol, or
  • polyolefins and chemically modified polyolefins especially by oxidation-modified polyolefins (see, for example, US-A 3,786,116) should include.
  • Suitable as low water-soluble organic solvents are, for example, liquid saturated and unsaturated aliphatic and aromatic hydrocarbons having 5 to 9 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-pentene and isomers, cyclopentene, n-hexene and isomers, cyclohexene, n-heptene and isomers, n-octene and isomers, n-nonene and isomers, benzene, Toluene, ethylbenzene, cumene, o-, m- or p-xylene, mesitylene and esters of C 1 - to C 4 -aliphatic carboxylic acids and
  • gaseous compounds for example hydrocarbons and / or C 1 -C 4 fluorochlorohydrocarbons, which, although under gaseous conditions (20 ° C./1 atm, absolute), are liquid under elevated pressure.
  • gaseous compounds for example hydrocarbons and / or C 1 -C 4 fluorochlorohydrocarbons, which, although under gaseous conditions (20 ° C./1 atm, absolute), are liquid under elevated pressure.
  • Propane liquefaction: 8.8 bar [overpressure], 21 ° C.
  • propene liquefaction: 10 bar [overpressure], 21 ° C.
  • n-butane liquefaction: 2.1 bar [overpressure], 21 0 C
  • n-butene liquefaction: 2.7 bar [overpressure], 21 0 C
  • C4 sections of a naphtha cracker in particular the raffinate II section (consisting of 30 to 50 wt .-% Bu-1, 30 to 50 wt .-% butene-2, 10 to 30 wt % n-butane and ⁇ 10% by weight of other compounds).
  • the low water-soluble organic solvents used according to the invention have, at atmospheric pressure (1 atm, absolute) boiling points in the range> -100 and ⁇ +100 0 C, advantageously> -60 and ⁇ +80 0 C or ⁇ +50 0 C and particularly advantageous > -60 and ⁇ +15 0 C on. It goes without saying that for all organic solvents which have a boiling point ⁇ 30 0 C, at least the process steps a) to d) are carried out at a pressure which ensures that at the temperature under which the process steps a) to d), the organic solvent is in liquid form.
  • the pressures may have values> 5 bar,> 10 bar,> 20 bar or> 40 bar (overpressure). At the top, the pressures are not limited in principle, but pressures of 1000 bar are usually not exceeded for reasons of apparatus.
  • a polymer solution of low water-soluble polymer and low-water-soluble organic solvent is prepared.
  • the polymer content in the polymer solution is not limited.
  • the polymer solution often contains> 5 and ⁇ 80% by weight, often> 10 and ⁇ 65% by weight or advantageously> 15 and ⁇ 50% by weight of polymer. It is also important that the polymer is completely and homogeneously dissolved in the organic solvent.
  • the measures for producing a homogeneous polymer solution are familiar to the person skilled in the art.
  • the polymer solution prepared in process step a) is introduced in process step b) according to the invention into an aqueous medium which contains dispersing aids, a heterogeneous mixture being formed.
  • an aqueous medium which contains dispersing aids
  • the introduction of the polymer solution into an aqueous medium for example, in a vessel.
  • the dispersants used by the process according to the invention can in principle be emulsifiers and / or protective colloids.
  • Suitable protective colloids are, for example, polyvinyl alcohols, polyalkylene glycols, alkali metal salts of polyacrylic acids and polymethacrylic acids, gelatin derivatives or acrylic acid, methacrylic acid, maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and / or 4-styrenesulfonic acid-containing copolymers and their alkali metal salts but also N-vinylpyrrolidone, N-vinylcaprolactam, N- vinylcarbazole, 1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, acrylamide, methacrylamide, amines group-bearing acrylates, methacrylates, acrylamides and / or methacrylamides containing homo- and copolymers.
  • suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromo
  • mixtures of protective colloids and / or emulsifiers can be used.
  • dispersing aids 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, pages 192 to 208.
  • Common nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 to C 12) and also ethoxylated fatty alcohols (EO degree: 3 to 80, alkyl radical: C 8 to C 36 ).
  • Lutensol ® A grades C 2 Ci4-fatty alcohol ethoxylates, EO units: 3 to 8
  • Lutensol ® AO-marks C13C15- oxo alcohol ethoxylates, EO units: 3 to 30
  • Lutensol ® AT-marks Ci 6 Ci 8 - fatty alcohol ethoxylates, EO grade: 11 to 80
  • Lutensol ® ON grades C10 oxo alcohol ethoxylates, EO grade: 3 to 11
  • Lutensol ® TO grades C 13 oxo alcohol ethoxylates, EO grade: 3 to 20
  • Typical anionic emulsifiers include alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C 8 to C12), ethoxylated sulfuric acid monoesters of alkanols (EO units: 4 to 30, alkyl radical: C12 to C 8) and ethoxylated alkylphenols (EO units: 3 to 50, alkyl radical: C 4 to C 2), of alkylsulfonic acids (alkyl: C 2 to C 8) and of Al kylarylsulfonkla (alkyl radical: C 9 to C 8).
  • R 1 and R 2 are H atoms or C 4 - to C 24 alkyl and are not H atoms at the same time, and M 1 and M 2 may be alkali metal ions and / or ammonium ions have been found suitable.
  • 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 .
  • HAU fig technical mixtures are used which have a proportion of 50 to 90 wt .-% of the monoalkylated product, such as Dowfax ® 2A1 (trademark of the Dow Chemical Company).
  • the compounds (I) are well known, for example, from US-A 4,269,749, and commercially available.
  • Suitable cationic emulsifiers are generally primary, secondary, tertiary or quaternary ammonium salts having C 1 to C 6 alkyl, alkylaryl or heterocyclic groups, 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) ethylparaffinklareester, N-cetylpyridinium, N-Laurylpyridiniumsulfat and N-cetyl-N, N, N-trimethylammonium sulfate, N- dodecyl N, N, N-trimethylammoniumsulfat, N-octyl-N, N, N-trimethlyammoniumsulfat, N 1 N- distearyl-N, N-dimethylammonium sulfate, and also the gemini surfactant N 1 N'-(lauryl) ethylendiamindisulfat, ethoxylated tallow -N-methyl ammonium sulfate and ethoxylated oleylamine (for example Uniperol.R
  • 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.
  • anionic counterparts are as possible are low nucleophilic, such as perchlorate, sulfate, phosphate, nitrate and carboxylates, such as acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, as well as conjugated anions of organosulfonic acids, such as methyl sulfonate, trifluoromethylsulfonate and para Toluenesulfonate, further tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-trifluoromethyl) phenyl] borate, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate.
  • organosulfonic acids such as methyl sulfonate, trifluoromethylsul
  • the emulsifiers preferably used as dispersing agents are advantageously in a total amount> 0.005 and ⁇ 20 wt .-%, preferably> 0.01 and ⁇ 15% by weight, in particular> 0.1 and ⁇ 10 wt .-%, each based on the total amount of polymer used.
  • the total amount of the protective colloids used as dispersing aids in addition to or instead of the emulsifiers is often> 0.1 and ⁇ 10% by weight and frequently> 0.2 and ⁇ 7% by weight, in each case based on the total amount of polymer.
  • anionic and / or nonionic emulsifiers preference is given to using anionic and / or nonionic emulsifiers and, with particular preference, anionic emulsifiers as dispersion auxiliaries.
  • the aqueous medium in addition to the dispersing agent may optionally contain other auxiliaries, such as rheology aids (eg associate thickeners), foam inhibitors, biocidal agents, finely divided inorganic solids and / or conventional stabilizers in any conventional amounts.
  • auxiliaries such as rheology aids (eg associate thickeners), foam inhibitors, biocidal agents, finely divided inorganic solids and / or conventional stabilizers in any conventional amounts.
  • the weight ratio of organic polymer solution to aqueous medium depending on the polymer content of the polymer solution and the desired polymer content of the aqueous polymer dispersion, usually> 0.1 and ⁇ 5, often> 0.5 and ⁇ 3 and more often> 1 and ⁇ 2.
  • the nature and amount of low water-soluble polymer and organic solvent are chosen so that> 80 wt .-%, preferably> 85 wt .-% and particularly preferably> 90 wt .-% of the resulting polymer solution in the raw and present in the miniemulsion as a separate liquid phase.
  • the heterogeneous mixture obtained in process step b) is converted by means of suitable measures into an oil-in-water emulsion having an average droplet diameter> 2 ⁇ m (crude emulsion).
  • the average droplet diameter of the aqueous crude and miniemulsion can be determined, for example, by means of an ultrasound extinction probe (for example by means of an Opus device from Sympatec GmbH) or by the method of static light scattering.
  • the average droplet diameter is the so-called Sauter diameter (d 3 , 2).
  • the skilled person is familiar with the introduction of energy, for example by mixing using conventional agitators, nozzles, static and / or dynamic mixing devices. If, therefore, the heterogeneous mixture in process step b) was prepared, for example, batchwise in a vessel, in particular a mixing vessel, the crude emulsion is usually prepared by stirring the heterogeneous mixture with a stirrer.
  • the heterogeneous mixture is continuously prepared by the joint introduction of the polymer solution and the aqueous medium into a pipeline
  • the crude emulsion is advantageously produced by passing the heterogeneous mixture through static and / or dynamic mixers which are located in the pipeline downstream of the inlet points the polymer solution and the aqueous medium downstream (to an intermediate container in which the crude emulsion is stored or directly to the microporous membrane) are arranged. It is essential to the process that the raw emulsion thus obtained is passed through at least one microporous membrane to form the oil-in-water emulsion having a mean droplet diameter ⁇ 1000 nm (miniemulsion).
  • the selection of the microporous membrane takes place in such a way that it is capable of forming a miniemulsion taking into account temperature, pressure conditions, exposure to crude emulsion, etc.
  • microporous membranes with an average pore diameter ⁇ 1000 nm are often used for this purpose.
  • microporous membranes especially the microporous membranes having an average pore diameter ⁇ 1000 nm may be conventional ultrafiltration and microfiltration membranes.
  • the mechanical stability of the microporous membrane is based on a coarsely porous first layer (substructure). It is free-bearing and pressure-stable, without the need for a support device would be required. It serves as a carrier for one or more microporous membranes with a mean pore diameter ⁇ 1000 nm. The respective microporous membranes with an average pore diameter ⁇ 1000 nm are generally thinner than the substructure.
  • At least two series-arranged microporous membranes having an average pore diameter ⁇ 1000 nm are applied to the first coarse-pored layer, the mean pore diameter of which decreases with increasing distance from the first layer.
  • the crude emulsion is first passed through the coarse-pored first layer and subsequently through the microporous membrane (s) having an average pore diameter ⁇ 1000 nm arranged thereon. Clogging of the microporous membrane (s) is largely prevented by such asymmetric construction.
  • the pore diameter of the coarsely porous first layer is advantageously in the range between 1.5 and 20 microns and their thickness in the range of 0.1 to 10 mm.
  • a particularly suitable pore diameter of the substructure is of the same order of magnitude as the droplet diameter of the disperse phase of the crude emulsion, that is to say in the range of> 2 ⁇ m.
  • the pore diameter of the microporous membrane which is directly related to the droplet diameter of the miniemulsion and its droplet size distribution, is preferably in a range> 10 and ⁇ 1000 nm, in particular ⁇ 900 nm, ⁇ 700 nm or ⁇ 500 nm and> 50 nm,> 100 nm or> 150 nm.
  • the mean pore diameter is in the range> 50 nm and ⁇ 800 nm or > 70 nm and ⁇ 600 nm.
  • the determination of the mean pore diameter of a microporous membrane is generally carried out by means of a Coulter Porometer according to ASTM E 1294 with isopropanol as wetting agent.
  • suitable microporous membranes have a porosity according to DIN ISO 30911-3 of 1% to 70%.
  • the thickness of a microporous membrane is often in the range between 1 and 5000 .mu.m, in particular in the range 1 and 2000 microns.
  • the average pore diameter of the first microporous membrane in contact with the crude emulsion is greater than or equal to the mean pore diameter of the second and any further microporous membrane. It is particularly advantageous if the average pore diameter of the first microporous membrane in contact with the crude emulsion is greater than the average pore diameter of the second and any further microporous membrane. It is favorable if the mean pore diameter of each further microporous membrane decreases further with increasing distance from the first microporous membrane.
  • the microporous membrane can be used in a wide variety of geometries and sizes. For example, flat geometries, tube geometries and multi-channel geometries with several tube geometries integrated in one unit, as well as capillary or coil geometries are possible.
  • the microporous membrane has a tubular geometry with an inner or outer coarse-pored first layer or a planar geometry. Pressure-stable self-supporting membrane structures are preferred which ensure sufficient pressure stability even at high transmembrane pressure differences and throughputs on an industrial scale without additional support elements.
  • microporous membranes are advantageously sintered metal membranes, ceramic membranes, glass membranes, graphite membranes, and / or polymer membranes. According to the invention, the microporous membranes are selected such that they are stable to the components of the crude emulsion under conditions of passage (pressure, temperature, etc.).
  • microporous membranes which are composed of hydrophilic materials such as, for example, metal, ceramic, regenerated cellulose, polyacrylonitrile, hydrophilized polyacrylonitrile, hydrophilized polysulfone or hydrophilized polyethersulfone or hydrophilized polyetheretherketone (see, for example, Ullmann 's Encyclopedia of Industrial Chemistry
  • hydrophilicity of a substance is the contact angle of a drop of deionized water on a horizontal, smooth-surfaced and clean, in particular fat-free surface of this substance be under hydrophilic substances understood as having a contact angle ⁇ 90 °, ⁇ 80 ° or ⁇ 70 °.
  • microporous membranes can be produced, for example, by sintering the corresponding powder materials, stretching the corresponding polymer films, irradiating the polymer films with high-energy electromagnetic radiation, by etching processes and phase reversal of homogeneous polymer solutions or polymer melts.
  • microporous membrane is constructed symmetrically or integrally asymmetric.
  • Integrally asymmetric microporous membranes are understood as meaning those whose average pore diameter within the microporous membrane layer increases by a factor of 3 to 1000 from one side to the other side.
  • the area of the microporous membrane used to make the miniemulsion is i.a. highly dependent on the type and geometry of the microporous membrane used, the composition and temperature of the crude emulsion used and the time within which the passage through the microporous membrane is to take place; it can be detected by the expert in simple routine tests.
  • the temperatures for the passage through the microporous membrane (s) according to the invention are basically not limited. Often they are in the range> 0 and ⁇ 200 0 C, in particular in the range> 20 and ⁇ 150 0 C and often in the range> 60 and ⁇ 120 0 C.
  • the pressure to be applied in order to pass the aqueous crude emulsion through the porous membranes is produced in particular by means of a pump, gas pressure or by hydrostatic height.
  • the transmembrane pressure difference between aqueous crude emulsion and aqueous miniemulsion, which influences the mean droplet diameter and the droplet size distribution, is frequently between 0.1 and 1000 bar, preferably between 0.5 and 100 bar, more preferably between 1 and 50 bar.
  • Process step d) is usually carried out in such a way that the miniemulsion is prepared by passing the crude emulsion through the at least one microporous membrane, but frequently several serially connected microporous membranes or by passing it through the at least one microporous membrane and by combinations of the abovementioned variants.
  • the aqueous miniemulsion obtained according to process step d) contains droplets of the polymer solution having a mean diameter ⁇ 1000 nm as disperse phase aqueous polymer dispersion is obtained therefrom by separating the organic solvent from the aqueous miniemulsion.
  • the separation of the organic solvent is carried out by customary methods, for example by distillation, by stripping with inert gas, for example nitrogen or argon, and by stripping with steam.
  • step e) If the separation of the organic solvent in step e) by distillation, it is advantageously carried out at a pressure (absolute), which is lower than the pressure prevailing in the process steps a) to d). Therefore, a method is advantageous in which the process steps a) to d) are carried out at a higher pressure than process step e). If the process steps a) to d) are carried out, for example, at atmospheric pressure, then process step e) is advantageously carried out at a pressure which is less than the atmospheric pressure. The pressure is chosen so that, although distilled off the solvent, but the water does not boil.
  • the pressure is ⁇ 1 bar, ⁇ 950 mbar, ⁇ 900 mbar, ⁇ 850 mbar, ⁇ 800 mbar (absolute) or even lower values.
  • process steps a) to d) are carried out in the overpressure range (> 1 atm absolute) because organic solvents are used which are gaseous at atmospheric pressure, it is often sufficient to depressurise to atmospheric pressure to remove the organic solvent in process step e) becomes.
  • the separation of the organic solvent is the simpler, the higher its vapor pressure at a given temperature or the greater the difference between the vapor pressure of the organic solvent and the vapor pressure of the water (at identical temperature).
  • water-soluble organic solvents having a boiling point ⁇ 30 0 C, ⁇ 20 0 C, ⁇ 10 0 C or ⁇ 0 0 C at atmospheric pressure.
  • the organic solvent is separated in process step e) usually to> 80 wt .-%, often to> 85 wt .-% and often to> 90 wt .-% of the miniemulsion. Residual amounts of solvent remaining in the polymer particles generally do not interfere with the further use of the aqueous polymer dispersion. If, for example, the aqueous polymer dispersions are used as binders in paint and coating formulations, the remaining organic solvent often aids in the filming of the polymer and is then released from it over an extended period of time into the atmosphere.
  • Aqueous polymer dispersions having a polymer solids content of> 1 and ⁇ 70% by weight, frequently> 5 and ⁇ 60% by weight and often> 10 and ⁇ 50% by weight are obtainable by the process according to the invention.
  • the polymer particles of the aqueous polymer dispersions obtainable by the process according to the invention generally have average particle diameters, which are between 10 and 900 nm, often between 50 and 700 nm and often between 100 and 500 nm.
  • the determination of the average particle diameter (Sauter diameter d3.2) or the particle size distribution was carried out in the context of this document by means of the method of static light scattering (ISO WD 13320).
  • the Mastersizer S was used by Malvern Instruments GmbH,dorfberg, Germany.
  • PI polydispersity index
  • D 9 o, 3, Di O , 3 and D 5 o, 3 denote particle diameter, for which applies:
  • Dgo, 3 90 wt .-% of the total mass of all polymer particles has a particle diameter less than or equal to Dgo, 3;
  • D 50, 3:50 wt .-% of the total mass of all polymer particles has a particle diameter less than or equal to D 5 o, 3 and
  • the particle size distribution can be determined in a manner known per se, for example by means of the static light scattering method or the analytical ultracentrifuge (see, for example, W. Gurchtle, Makromolekulare Chemie 185 (1984), pages 1025 to 1039), from which the D 9 o, 3, D 5 o, 3 and Di 0 , 3 values are taken and the polydispersity indices are determined.
  • the polydispersity indices are in the range from 0.1 to 4, preferably in the range from 0.3 to 3 and particularly preferably in the range from 0.5 to 1.5.
  • aqueous polymer dispersions of the chemically most diverse polymers can be obtained in a simple manner.
  • the method is technically easy to carry out and the average particle sizes of the aqueous polymer dispersions can be adjusted specifically by the choice of microporous membranes and the fürleit devis the crude emulsion through the membrane (pressure, temperature, flow per time, etc.).
  • the polymer particles of the resulting aqueous polymer dispersions usually have narrow particle size distributions.
  • the inventive method has a total of one low energy input, which is why aqueous polymer dispersions can be produced with low coagulum.
  • the microporous membranes used as main components in the process according to the invention have no moving and therefore repair-prone parts, resulting in low maintenance costs.
  • 500 g of granular polybutene-1 DP 8510 (Fa. BASELL GmbH) were initially charged at room temperature (20 to 25 0 C) in a 3 l pressure vessel (dissolving tank) under a nitrogen atmosphere and then 1000 g of raffinate II liquid (composition: 39, 3 wt .-% butene-1, 23.7 wt .-% trans-butene-2, 13.0 wt .-% cis-butene-2, 18.6 wt .-% n-butane, 3.3 wt .-% isobutane, 1, 8 wt .-% isobutene and 0.3 wt .-% of other compounds) introduced via a feed line.
  • raffinate II liquid composition: 39, 3 wt .-% butene-1, 23.7 wt .-% trans-butene-2, 13.0 wt .-% cis-butene-2, 18.6 wt
  • the polymer solution from the dissolving tank was passed through a dip tube - with pressure equalization between the two containers - in the emulsifying and stirred the resulting mixture for 15 minutes at 1400 revolutions per minute (rpm) to form a crude emulsion.
  • the aqueous polymer dispersion obtained was stable for many months and had a solids content of about 15% by weight.
  • the median polymer particle diameter was determined to be 290 nm.
  • the solids content was determined by (ca. 5 g) at 180 0 C in a drying oven until a constant weight was dried, a defined amount of the aqueous poly merdispersion. Two separate measurements were carried out in each case. The value given in the example represents the mean value of the two measurement results.
  • the comparative example was carried out analogously to Example 1 with the difference that the crude emulsion formed was not pumped through the membranes via the external circuit.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un procédé de production d'une dispersion aqueuse de polymère au moyen de membranes microporeuses.
EP06763799A 2005-06-21 2006-06-20 Procede de production d'une dispersion aqueuse de polymere Withdrawn EP1904536A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005028989A DE102005028989A1 (de) 2005-06-21 2005-06-21 Verfahren zur Herstellung einer wässrigen Polymerdispersion
PCT/EP2006/063354 WO2006136555A1 (fr) 2005-06-21 2006-06-20 Procede de production d'une dispersion aqueuse de polymere

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EP1904536A1 true EP1904536A1 (fr) 2008-04-02

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US (1) US20080200605A1 (fr)
EP (1) EP1904536A1 (fr)
JP (1) JP2008544055A (fr)
BR (1) BRPI0612249A2 (fr)
DE (1) DE102005028989A1 (fr)
WO (1) WO2006136555A1 (fr)

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WO2012140181A1 (fr) 2011-04-15 2012-10-18 Basf Se Procédé destiné à préparer des dispersions aqueuses de polycarbonates aliphatiques
WO2013068363A1 (fr) 2011-11-09 2013-05-16 Basf Se Utilisation dans des revêtements de papier d'un mélange d'une dispersion polymère secondaire et d'une dispersion primaire d'un polymère en émulsion
US9047838B2 (en) * 2012-03-14 2015-06-02 Apple Inc. Systems and methods for liquid crystal display column inversion using 3-column demultiplexers
CN109071828A (zh) 2016-02-29 2018-12-21 米切尔曼公司 可生物降解聚合物的水基的水解稳定分散体

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BRPI0612249A2 (pt) 2016-09-06
JP2008544055A (ja) 2008-12-04
WO2006136555A1 (fr) 2006-12-28
DE102005028989A1 (de) 2007-01-04
US20080200605A1 (en) 2008-08-21

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