EP1877449A1 - Procede de fabrication de polymeres par precipitation par l'intermediaire de polymerisation par pulverisation - Google Patents

Procede de fabrication de polymeres par precipitation par l'intermediaire de polymerisation par pulverisation

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Publication number
EP1877449A1
EP1877449A1 EP06754812A EP06754812A EP1877449A1 EP 1877449 A1 EP1877449 A1 EP 1877449A1 EP 06754812 A EP06754812 A EP 06754812A EP 06754812 A EP06754812 A EP 06754812A EP 1877449 A1 EP1877449 A1 EP 1877449A1
Authority
EP
European Patent Office
Prior art keywords
solvent
monomer
polymerization
acid
solution
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
EP06754812A
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German (de)
English (en)
Inventor
Dennis LÖSCH
Christian Hubert Weidl
Volker Seidl
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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 EP1877449A1 publication Critical patent/EP1877449A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/10—Making granules by moulding the material, i.e. treating it in the molten state
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/14—Organic medium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium

Definitions

  • the present invention relates to a process for the preparation of precipitation polymers by spray polymerization of a monomer solution comprising at least one ethylenically unsaturated monomer and at least one solvent, wherein the monomer is soluble in the solvent, and the polymer is insoluble in the solvent, and the use of Polymers for thickening liquids.
  • EP-A-0 328 725 and EP-A-0 814 101 describe the preparation of thickeners by precipitation polymerization of acrylic acid.
  • US-A-3,644,305 discloses a spray polymerization process capable of producing low molecular weight polymers. The polymerization is carried out at elevated pressure.
  • the spray polymerization is carried out in such a way that monomer solutions are sprayed into a heated, substantially static atmosphere.
  • the object of the present invention was to provide an improved process for the preparation of polymeric thickeners.
  • the polymeric thickeners should consist of small primary particles, preferably less than 1 micron, so that the thickened products have no tangible granular structure. Such polymeric thickeners are considered to be structureless and are preferred, for example, in the cosmetics industry.
  • polymeric thickeners should not contain any surfactants, as is the case, for example, with thickeners produced by emulsion polymerization.
  • the surfactants may cause undesirable clouding when used.
  • the object was achieved by a method for spray polymerization of a monomer solution containing a) at least one ethylenically unsaturated monomer, b) at least one solvent, c) optionally at least one crosslinker and d) optionally at least one initiator,
  • the solubility of the monomer a) in the solvent b) at 23 ° C. is preferably at least 20 g / 100 g, more preferably at least 50 g / 100 g, most preferably at least 100 g / 100 g.
  • the solubility of the polymer in solvent b) at 23 ° C. is preferably at most 10 g / 100 g, more preferably at most 5 g / 100 g, most preferably at most 1 g / 100 g.
  • Ethylenically unsaturated monomers a) are, for example, ethylenically unsaturated C3-C6-carboxylic acids. These compounds are, for example, acrylic acid, methacrylic acid, ethacrylic acid, .alpha.-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, acontic acid and fumaric acid and the alkali metal or ammonium salts of these acids.
  • polymerizable monomers a) are acrylamidopropanesulfonic acid, vinylphosphonic acid and / or alkali metal or ammonium salts of vinylsulfonic acid.
  • the other acids may also be used either in unneutralized form or in partially neutralized form in the polymerization.
  • monoethylenically unsaturated sulfonic or phosphonic acids for example allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, allylphosphonic acid, styrenesulfonic acid and 2-acrylamido-2-one methyIpropansulfonkla.
  • allylsulfonic acid for example allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulf
  • Further monomers a) are, for example, acrylamide, methacrylamide, crotonic acid amide, acrylonitrile, methacrylonitrile, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate, dimethylaminobutyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoneopentyl acrylate and dimethylaminoneopentyl methacrylate and their quaternization products, for example with methyl chloride , Hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.
  • monomers a) are monomers obtainable by reaction of nitrogen-containing heterocycles and / or carboxamides, such as vinylimidazole, vinylpyrazole and vinylpyrrolidone, vinylcaprolactam and vinylformamide, with acetylene, which may also be quaternized, for example with methyl chloride, and monomers , which are obtainable by reaction of nitrogen-containing compounds, such as Diallyldimethy- lammoniumchlorid, with allyl alcohol or allyl chloride.
  • nitrogen-containing heterocycles and / or carboxamides such as vinylimidazole, vinylpyrazole and vinylpyrrolidone, vinylcaprolactam and vinylformamide
  • acetylene which may also be quaternized, for example with methyl chloride
  • vinyl and allyl esters and also vinyl and allyl ethers such as vinyl acetate, allyl acetate, methyl vinyl ether and methyl allyl ether, can also be used as monomers a).
  • the monomers a) can be used alone or mixed with one another, for example mixtures containing two, three, four or more monomers a).
  • Preferred monomers a) are acrylic acid, methacrylic acid and the alkali metal or ammonium salts of these acids, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, itaconic acid, vinylformamide, vinylpyrrolidone, vinylimidazole, quaternized vinylimidazole, vinyl acetate, sodium vinyl sulfoate, vinylphosphonic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate , 2-acrylamido-2-methylpropanesulfonic acid, diallyldimethylammonium chloride and mixtures thereof.
  • Very particularly preferred monomers a) are acrylic acid, acrylic acid salts, vinylpyrrolidone, quaternized vinylimidazole, acrylamide, quaternized dimethylaminoethyl acrylate and / or diallyldimethylammonium chloride.
  • acrylic acid salts the alkali metal or ammonium salts are preferred, in particular sodium acrylate and potassium acrylate.
  • the concentration of the monomers a) in the monomer solution is usually from 2 to 80% by weight, preferably from 5 to 70% by weight, particularly preferably from 10 to 60% by weight.
  • the monomers a) are preferably stabilized with a commercially available polymerization inhibitor, particularly preferably with a polymerization inhibitor which acts only together with oxygen, for example hydroquinone monomethyl ether.
  • polymerization inhibitors which, for reasons of product safety, are used as storage stabilizers in the respective monomers.
  • storage stabilizers are hydroquinone, hydro- quinone monomethyl ether, 2,5-di-tert-butylhydroquinone and 2,6-di-tert-butyl-4-methylphenol.
  • the preferred polymerization inhibitors require dissolved oxygen for optimum performance.
  • the polymerization inhibitors may be prepared by inerting, i. Flow through with an inert gas, preferably nitrogen, to be freed of dissolved oxygen.
  • an inert gas preferably nitrogen
  • the oxygen content of the monomer solution before polymerization is reduced to less than 1 ppm by weight, more preferably less than 0.5 ppm by weight.
  • solvent b) it is possible to use virtually all water-immiscible liquids which do not intervene in the polymerization, ie contain no polymerizable groups.
  • Immiscible with water means that the solubility of the solvent b) in water is less than 5 g / 100 g, preferably less than 1 g / 100 g, more preferably less than 0.5 g / 100 g.
  • Aliphatic and aromatic hydrocarbons or mixtures of aliphatic and aromatic hydrocarbons are preferably used for this purpose.
  • Suitable aliphatic hydrocarbons are, for example, pentane, hexane, heptane, octane, nonane, decane, cyclohexane, decalin, methylcyclohexane, isooctane and ethylcyclohexane.
  • Aromatic hydrocarbons which can be used as the hydrophobic liquid are, for example, benzene, toluene and xylene.
  • organic solvents such as ketones, esters, ethers and saturated alcohols.
  • toluene or hydrocarbons in a boiling range of 60 to 17O 0 C.
  • solvent b By selecting a hydrocarbon having a suitable boiling point as solvent b) it is possible to decouple the polymerization / precipitation and the drying. A sufficiently high boiling point of the solvent b) prevents the drops from drying until polymerization and precipitation of the polymer have proceeded far enough.
  • the water content of the solvent b) is preferably less than 3 wt .-%, more preferably less than 0.5 wt .-%, most preferably less than 0.1 wt .-%.
  • the monomers a) are preferably polymerized in the presence of a crosslinker c) or a combination of different crosslinkers.
  • Crosslinkers are compounds having at least two polymerizable groups.
  • Suitable crosslinkers c) are, for example, (meth) acrylic esters of polyhydric alcohols which may be alkoxylated with up to 100, usually up to 50, ethylene oxide and / or propylene oxide units.
  • Suitable polyhydric alcohols are, in particular, C2-C10- Alkanepolyols having 2 to 6 hydroxyl groups, such as ethylene glycol, glycerol, trimethylolpropane, pentaerythritol or sorbitol.
  • Preferred crosslinkers are polyethylene glycol diacrylate and polyethylene glycol dimethacrylates, each of which is derived from polyethylene glycols (which can be thought of as ethoxylated ethylene glycol) having a molecular weight of from 200 to 2,000.
  • Further crosslinkers c) which may be used are methylenebisacrylamide, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, hexanediol dimethacrylate or diacrylates and dimethacrylates of block copolymers of ethylene oxide and propylene oxide.
  • crosslinkers c) are diallyl carbonate, allyl carbonates or allyl ethers of polyhydric alcohols which may be alkoxylated with up to 100, usually up to 50, ethylene oxide and / or propylene oxide units, and allyl esters of polybasic carboxylic acids.
  • A is the radical of a polyhydric alcohol which may be alkoxylated with 0 to 100, usually 0 to 50, ethylene oxide and / or propylene oxide units and n is the valence of the alcohol, for example an integer from 2 to 10, preferably 2 to 5, stands.
  • a particularly preferred example of such a compound is ethylene glycol di (allyl carbonate).
  • polyethylene glycol di (allyl carbonates) are derived from polyethylene glycols having a molecular weight of from 200 to 2,000.
  • allyl ethers polyethylene glycol diallyl ether, which are derived from polyethylene glycols having a molecular weight of from 200 to 2,000; Pentraerythritol triallyl ether or trimethylolpropane diallyl ether. Also suitable are reaction products of ethylene glycol diglycidyl ether or polyethylene glycol glycidyl ether with 2 mol of allyl alcohol and / or pentaerythritol triallyl ether.
  • a suitable allyl ester of a polybasic carboxylic acid is dialyl phthalate, for example.
  • the monomers are preferably polymerized together in the presence of initiators d).
  • the initiators d) are used in customary amounts, for example in amounts of from 0.001 to 5% by weight, preferably from 0.01 to 1% by weight, based on the monomers to be polymerized.
  • initiators d it is possible to use all compounds which decompose into free radicals under the polymerization conditions, for example peroxides, hydroperoxides, hydrogen peroxide, persulfates, azo compounds and the so-called redox initiators. Preference is given to the use of water-soluble initiators. In some cases it is advantageous to use mixtures of different initiators, for example mixtures of hydrogen peroxide and sodium or potassium peroxodisulfate. Mixtures of hydrogen peroxide and sodium peroxodisulfate can be used in any proportion.
  • Suitable organic peroxides are, for example, acetylacetone peroxide, methyl ethyl ketone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl pheohexanoate, tert-butyl perisobutyrate, tert-butyl per-2-ethylhexanoate, tert.
  • Preferred initiators d) are azo compounds such as 2,2'-azobis isobutyronitrile, 2,2-azobis I (2,4-dimethylvaleronitrile) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), particularly water-soluble azo initiators, for example 2,2'-azobis ⁇ 2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane ⁇ dihydrochloride, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2, 2'-Azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride and 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride.
  • 2,2'-azobis isobutyronitrile
  • 2,2-azobis I 2,4-dimethylvaleronitrile
  • the redox initiators contain as oxidizing component at least one of the abovementioned peroxo compounds and as reducing component, for example, ascorbic acid, glucose, sorbose, ammonium or alkali metal hydrogen sulfite, sulfite, thiosulfate, hyposulfite, pyrosulfite, sulfide or sodium hydroxymethyl sulfoxylate.
  • reducing component of the redox catalyst is particularly used ascorbic acid or sodium pyrosulfite. Based on the nomeren used in the polymerization amount of Mo is used, for example, 1 x 10- 5 to 1 mol% of the reducing component of the redox catalyst.
  • the polymerization is particularly preferably initiated by the action of high-energy radiation, customarily using so-called photoinitiators as the initiator.
  • photoinitiators may be, for example, so-called ⁇ -splitters, H-abstracting systems or azides.
  • examples of such initiators are benzophenone derivatives such as Michler's ketone, phenanthrene derivatives, fluorene derivatives.
  • azides are 2- (N 1 N-dimethylamino) ethyl-4-azidocinnamate, 2- (N, N-dimethylamino) ethyl-4- azidonaphthylketon, 2- (N, N-dimethylamino) ethyl 4-azidobenzoate, 5-azido-1-naphthyl-2 '- (N, N-dimethylamino) ethylsulfone, N- (4-sulfonylazidophenyl) maleimide, N-acetyl-4-sulfonylazidoaniline, 4-sulfonylazidoaniline, 4-azidoaniline, 4 -Azidophenacylbromid, p-Azidobenzoeklare, 2,6-bis (p-azidobenzylidene) cyclohexanone and 2,6-bis (p-azidobenz
  • Particularly preferred initiators d) are azo initiators, such as 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride and 2,2'-azobis [2- (5-methyl-2-imidazoline-2 - yl) propane] dihydrochoride, and photoinitiators, such as 2-hydroxy-2-methylpropiophenone and 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, redox initiato such as sodium persulfate / hydroxymethylsulfinic acid, ammonium peroxodisulfate / hydroxymethylsulfinic acid, hydrogen peroxide / hydroxymethylsulfinic acid, sodium persulfate / ascorbic acid, ammonium peroxodisulfate / ascorbic acid and hydrogen peroxide / ascorbic acid, photoinitiators, such as 1- [4- (2-hydroxyethoxy) -pheny
  • the reaction is preferably carried out in apparatuses which are also suitable for spray drying.
  • apparatuses which are also suitable for spray drying.
  • Such reactors are described, for example, in K. Masters, Spray Drying Handbook, 5th Edition, Longman, 1991, pages 23-66.
  • the reaction temperature is preferably 70 to 250 ° C., particularly preferably 100 to 200 ° C., very particularly preferably 120 to 180 ° C.
  • one or more spray nozzles can be used.
  • the applicable spray nozzles are subject to no restriction.
  • the liquid to be sprayed can be supplied under pressure.
  • the division of the liquid to be sprayed can take place in that it is relaxed after reaching a certain minimum speed in the nozzle bore.
  • single-substance nozzles such as, for example, slot nozzles or twist chambers (full cone nozzles) for the purpose according to the invention (for example, by Düsen-Schlick GmbH, DE, or by Spraying Systems GmbH, DE).
  • Full cone nozzles are preferred according to the invention. Of these, those with an opening angle of the spray cone of 60 to 180 ° are preferred.
  • Opening angles of 90 to 120 ° are particularly preferred.
  • the average droplet diameter which occurs during spraying is typically less than 1000 .mu.m, preferably less than 200 .mu.m, preferably less than 100 .mu.m, and usually greater than 10 .mu.m, preferably greater than 20 .mu.m, preferably greater than 50 .mu.m, and can be prepared by conventional methods such as light scattering , or determined from the characteristics available from the nozzle manufacturers.
  • the throughput per spray nozzle is suitably 0.1 to 10 m 3 / h, often 0.5 to 5 nfVh.
  • the droplet diameter which is obtained during the spraying is suitably from 10 to 1000 .mu.m, preferably from 10 to 500 .mu.m, particularly preferably from 10 to 150 .mu.m, very particularly preferably from 10 to 45 .mu.m.
  • the reaction can also be carried out in apparatus in which the monomer solution can fall freely in the form of monodisperse drops.
  • apparatuses as described, for example, in US Pat. No. 5,269,980, column 3, lines 25 to 32.
  • the dripping is preferred over the spray, especially when using photoinitiators.
  • the reaction can be carried out in overpressure or under reduced pressure, a negative pressure of up to 100 mbar relative to the ambient pressure is preferred.
  • the reaction may be carried out in the presence of an inert carrier gas, wherein inert means that the carrier gas can not react with the constituents of the monomer solution.
  • the inert carrier gas is preferably nitrogen.
  • the oxygen content of the inert carrier gas is advantageously less than 1% by volume, preferably less than 0.5% by volume, more preferably less than 0.1% by volume.
  • the inert carrier gas can be passed through the reaction space in cocurrent or in countercurrent to the freely falling drops of the monomer solution, preferably in cocurrent.
  • the carrier gas is after a passage at least partially, preferably at least 50%, more preferably at least 75%, as Circulating gas is returned to the reaction space.
  • a subset of the carrier gas is discharged after each pass, preferably at least 10%.
  • the gas velocity is preferably set so that the flow in the reactor is directed, for example, there are no convection vortices opposite the general flow direction, and is for example 0.02 to 1.5 m / s, preferably 0.05 to 0.4 m / s.
  • the rate of polymerization can be adjusted by the type and amount of initiator system used.
  • azo compounds or redox initiators are used as initiators.
  • the light-off behavior of the polymerization can be controlled better with azo compounds or redox initiators by selecting the initiator, initiator concentration and reaction temperature than, for example, with pure peroxide initiators.
  • photoinitiators When photoinitiators are used, the rate of drying over the temperature can be adjusted to the desired value without, at the same time, significantly affecting the formation of free radicals.
  • the carrier gas is advantageously up to 200 0 C, particularly preferably 120 to 180 ° C, preheated upstream of the reactor to the reaction temperature of 70 to 250 0 C 1 is preferably one hundredth
  • the reaction offgas i. the carrier gas leaving the reaction space can be cooled, for example, in a heat exchanger.
  • solvent b) and unreacted monomer a) condense.
  • the reaction gas can be at least partially reheated and recycled as recycle gas in the reactor.
  • Part of the reaction offgas can be discharged and replaced by fresh carrier gas, wherein the solvent contained in the reaction offgas b) and unreacted monomers a) can be separated and recycled.
  • a heat network that is, a portion of the waste heat during cooling of the exhaust gas is used to heat the circulating gas.
  • the reactors can be accompanied by heating.
  • the heat tracing is adjusted so that the wall temperature is at least 5 0 C above the reactor internal temperature and the condensation on the reactor walls is reliably avoided.
  • the reaction product can be withdrawn from the reactor in the usual way, preferably at the bottom via a screw conveyor, and optionally to the Desired residual moisture and dried to the desired residual monomer content.
  • the inventive method advantageously combines the production and drying of a polymeric thickener in a process step, wherein the heat of polymerization can be used simultaneously for drying.
  • the process according to the invention can be used to prepare polymeric thickeners which dissolve rapidly owing to their small particle size and the associated large surface area.
  • the polymer thickeners which can be prepared by the process according to the invention are suitable for thickening liquids, in particular aqueous systems.
  • aqueous solutions are treated with the thickeners obtainable by the process according to the invention, it is advantageous, in particular for thickeners based on acrylic acid as monomer a), to adjust the pH of the solution to be thickened to the desired value with a suitable base, such as sodium hydroxide solution , for example 7.
  • a suitable base such as sodium hydroxide solution , for example 7.
  • the primary particles produced in a solvent droplet form during drying agglomerates which have a raspberry-like morphology.
  • the polymeric thickeners obtainable by the process according to the invention are water-soluble, u.U. also slightly cloudy colloidal solutions can be obtained.
  • the thickened liquids produced with the polymeric thickeners produced by the process according to the invention contain no particulate structures.
  • water is thickened with a polymer thickener prepared by the process according to the invention and the thickened solution is adjusted to a viscosity of less than 100 mPas (measured in accordance with DIN 51562) by addition of water, filtration through a filter having a pore width of about 5 ⁇ m remains (For example, by means of a filter paper S & S 589 Schwarzband Schleicher & Schull) no detectable residue.
  • the amount of residue can be determined by rinsing with water, drying and reweighing.
  • the polymeric thickeners which can be prepared by the process according to the invention can be used for aqueous systems, for example as an additive to paper coating slips, as thickeners for pigment printing pastes and as an additive to aqueous paints, such as facade paints. They can also be used in cosmetics, for example in hair cosmetic preparations such as conditioners or hair fixatives, or as thickeners for cosmetic formulations and for the surface treatment of leather.
  • the viscosity of 1% strength by weight aqueous solutions containing polymers prepared by the process according to the invention is at least 5,000 mPas, preferably at least 10,000 mPas, particularly preferably at least 20,000 mPas, at 23 ° C.
  • the resulting powder was dissolved in water and the pH of the solution was adjusted to 7 with sodium hydroxide solution.
  • the 0.5% strength by weight solution had a viscosity of 6,000 mPas and the 1% strength by weight solution had a viscosity of 35,000 mPas.
  • the 0.5% strength by weight solution had a viscosity of 8,000 mPas and the 1% strength by weight solution had a viscosity of 40,000 mPas.
  • the resulting powder was dissolved in water and the pH of the solution was adjusted to 7 with sodium hydroxide solution.
  • the 0.5% strength by weight solution had a viscosity of 7,000 mPas and the 1% strength by weight solution had a viscosity of 35,000 mPas.
  • the resulting powder was dissolved in water and the pH of the solution was adjusted to 7 with sodium hydroxide solution.
  • the 0.5 wt .-% solution had a viscosity of 10,000 mPas and the 1 wt .-% solution had a viscosity of 45,000 mPas.
  • Example 5 The 0.5 wt .-% solution had a viscosity of 10,000 mPas and the 1 wt .-% solution had a viscosity of 45,000 mPas.
  • the resulting powder was dissolved in water and the pH of the solution was adjusted to 7 with sodium hydroxide solution.
  • the 0.5 wt .-% solution had a viscosity of 13,000 mPas and the 1 wt .-% solution had a viscosity of 50,000 mPas.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Cosmetics (AREA)

Abstract

L'invention concerne un procédé de fabrication de polymères par précipitation par l'intermédiaire de polymérisation par pulvérisation d'une solution monomère contenant au moins un monomère à insaturation éthylénique et au moins un solvant. Selon l'invention, le monomère est soluble dans le solvant et le polymère obtenu par polymérisation du monomère n'est pas soluble dans le solvant. L'invention concerne également l'utilisation du polymère pour l'épaississement de liquides.
EP06754812A 2005-04-25 2006-04-24 Procede de fabrication de polymeres par precipitation par l'intermediaire de polymerisation par pulverisation Withdrawn EP1877449A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005019398A DE102005019398A1 (de) 2005-04-25 2005-04-25 Verfahren zur Herstellung von Fällungspolymeren durch Sprühpolymerisation
PCT/EP2006/061785 WO2006114404A1 (fr) 2005-04-25 2006-04-24 Procede de fabrication de polymeres par precipitation par l'intermediaire de polymerisation par pulverisation

Publications (1)

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EP1877449A1 true EP1877449A1 (fr) 2008-01-16

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US (1) US20080194778A1 (fr)
EP (1) EP1877449A1 (fr)
JP (1) JP2008538793A (fr)
CN (1) CN101163721A (fr)
DE (1) DE102005019398A1 (fr)
TW (1) TW200643035A (fr)
WO (1) WO2006114404A1 (fr)

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MY152868A (en) * 2006-07-19 2014-11-28 Basf Se Method for producing water-absorbent polymer particles with a higher permeability by polymerising droplets of a monomer solution
CN101489596B (zh) 2006-07-19 2013-05-15 巴斯夫欧洲公司 通过聚合单体溶液液滴生产具有较高吸收的后固化的吸水性聚合物颗粒的方法
DE502007006381D1 (de) 2006-07-19 2011-03-10 Basf Se Verfahren zur herstellung wasserabsorbierender polymerpartikel mit hoher permeabilität durch polymerisation von tropfen einer monomerlösung
WO2008009612A1 (fr) 2006-07-19 2008-01-24 Basf Se Procédé de production de particules absorbant l'eau présentant une perméabilité élevée grâce à la polymérisation de goutellettes d'une solution monomère
CN101522719A (zh) 2006-10-05 2009-09-02 巴斯夫欧洲公司 通过聚合单体溶液液滴生产吸水性聚合物颗粒的方法
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DE102005019398A1 (de) 2006-10-26
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US20080194778A1 (en) 2008-08-14
WO2006114404A1 (fr) 2006-11-02
TW200643035A (en) 2006-12-16

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