WO2006134085A1 - Polymeres formant des hydrogels, presentant une permeabilite amelioree et une capacite d'absorption elevee - Google Patents

Polymeres formant des hydrogels, presentant une permeabilite amelioree et une capacite d'absorption elevee Download PDF

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WO2006134085A1
WO2006134085A1 PCT/EP2006/063085 EP2006063085W WO2006134085A1 WO 2006134085 A1 WO2006134085 A1 WO 2006134085A1 EP 2006063085 W EP2006063085 W EP 2006063085W WO 2006134085 A1 WO2006134085 A1 WO 2006134085A1
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hydrogel
process according
forming polymer
weight
hydrophobic
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PCT/EP2006/063085
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Norbert Herfert
Vernon L. Adey
Peter W. Carrico
William G-J Chiang
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Basf Aktiengesellschaft
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Priority claimed from EP05013404A external-priority patent/EP1736508A1/fr
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Publication of WO2006134085A1 publication Critical patent/WO2006134085A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3063—Treatment with low-molecular organic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/18—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing inorganic materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/48—Surfactants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/405—Compounds of aluminium containing combined silica, e.g. mica
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Definitions

  • Hydrogel-forming polymers with increased permeability and high absorption capacity Hydrogel-forming polymers with increased permeability and high absorption capacity
  • the present invention concerns hydrogel-forming polymers with increased permeability and high absorption capacity, a process for preparing such hydrogel-forming polymers and also their use.
  • Hydrogel-forming polymers are swellable and known as superabsorbent polymers
  • SAPs superabsorbents
  • hydrogels in non-gel form and even in their dried state.
  • Swellable hydrogel-forming polymers are in particular polymers of (co)polymerized hydrophilic monomers with crosslinking comonomers, graft (co)polymers of one or more hydrophilic monomers on a suitable grafting base, crosslinked cellulose ethers, crosslinked starch ethers, crosslinked carboxymethylcellulose, partially crosslinked polyalkylene oxide or natural products which are capable of swelling in aqueous fluids, such as guar derivatives for example.
  • Such hydrogels are used as products capable of absorbing aqueous solutions to manufacture diapers, tampons, sanitary napkins and other hygiene articles, but also as water-retaining agents in market gardening or to thicken all kinds of wastes, especially medical wastes.
  • Swellable hydrogel-forming polymers are preferably capable of absorbing at least 10 times their own weight and preferably 20 times their own weight, based on the polymer used, of 0.9% by weight sodium chloride solution. This absorption is preferably achieved even under a pressure of 0.7 psi for example.
  • Swellable hydrogel-forming polymers are typically surface or gel postcrossl inked to improve their performance characteristics.
  • This postcrosslinking is known per se to one skilled in the art and preferably takes place in an aqueous gel phase or as surface postcrosslinking of the ground and classified polymeric particles.
  • Adding hydrophobic silica as anti-caking agent to dried superabsorbent powder is a well-known means for improving powder handling, which also may help to improve liquids transport in a swollen hydrogel bed.
  • WO 2005/042 039 A2 US 2002/0 128 618 A1 and US 5 847 031 disclose superabsorbents obtained by mixing dried poly(sodium)acrylate with hydrophobic particles such as hydrophobic silica and optionally other additives.
  • Inorganic particles are also well known-fillers for various polymeric substances.
  • JP 04/359 915 A1 discloses zinc oxide-containing oil-resisting rubber vulcanizates.
  • Adding hydrophilic silica derivatives to superabsorbents is also known.
  • DE 100 13 217 A1 discloses that adding an alumosilicate such as saponite or zeolithes to a superabsorbent improves liquids transport in the swollen hydrogel bed and reduces odours which may occur during the use of diapers containing superabsorbents.
  • WO 00/31157 A1 discloses adding a alkali silicate of the general formula M 2 O x n SiO 2 to the monomer or wet polymer gel.
  • EP 516 925 A1 discloses a suspension polymerisation process for preparing polyacrylate superabsorbents in the form of wrinkled particles, in which water-phase droplets containing sodium acrylate, acrylic acid and a crosslinker are dispersed in an organic phase comprising a surfactant and hydrophobic silica as dispersing agents.
  • EP 949 290 A2 discloses a process for producing superabsorbents, in which water phase droplets containing superabsorbent polymer and crosslinker are suspended in a surfactant-free organic phase containing hydrophobic silica. The silica serves as substitute for surfactants and is recovered.
  • the present invention therefore had for its object to develop a specific superabsorbent which is optimally suitable for high absorbancy and increased permeability.
  • hydrophobic compounds are in particular hydrophobicized pyrogenic silicas or hydrophobicized mixtures of pyrogenic silicas and pygrogenic aluminas.
  • Other useful hydrophobic compounds are in particular hydrophobicized precipitated silicas or hydrophobicized mixtures of precipitated silicas and precipitated aluminas. If in the following description pyrogenic silicas or pyrogenic aluminas are mentioned, it is to be understood that also precipitated silicas or precipitated aluminas can be used.
  • Useful superabsorbent materials in the present invention's process are hydrogels or hydrogel mixtures.
  • the water content of the hydrogels is preferably less than 20% by weight, more preferably less than 10% by weight and most preferably less than 5% by weight.
  • Dried hydrogel-forming polymer is such where the water content is 0%.
  • a SAP with 15 weight-% water contains 85 weight-percent dry SAP.
  • hydrophobic and hydrophilic describe the wetting behavior of a surface with water.
  • the contact angle of a water droplet is smaller than 90° on hydrophobic surfaces, preferred smaller than 80°, more preferred smaller than 70°, specially preferred smaller than 60° and most preferred smaller than 50°.
  • the contact angle is described for example in Colloid Polym. Sci., volume 259 (1981), pages 391 to 394. On rough surfaces the apparent contact angle will be measured. If powders are measured, they shall be smoothed out by a smooth stemp with a pressure of 0.5 bar.
  • hydroxyl groups on the particle surface of pyrogenic silicas. These hydroxyl groups are capable of forming hydrogen bonds. Pyrogenic silicas are hydrophilic as a result.
  • Reaction of pyrogenic silicas with trimethylchlorosilane for example can be used to convert the free hydroxyl groups into silyl ether groups.
  • the silyl ether groups are no longer capable of forming hydrogen bonds.
  • the pyrogenic silica has been rendered hydrophobic.
  • the amounts of hydrophobic particles are advantageously chosen such that not only an increased rate of permeability of the superabsorbents is achieved, but also the process of manufacture of the superabsorbents is has not to be altered substantially.
  • the amount of hydrophobic particles used is to be individually adjusted with regard of the recipe used in the production.
  • the present invention provides a process for preparing a hydrogel-forming polymer, comprising the steps of:
  • the hydrophobic compounds are preferably used in the form of particles.
  • the average particle size is typically in the range from 0.001 to 10 ⁇ m, preferably in the range from 0.002 to 5 ⁇ m, more preferably in the range from 0.005 to 1 ⁇ m and most preferably in the range from 0.01 to 0.1 ⁇ m.
  • the method of measurement for the particle size distribution is based on the analysis of diffraction spectra according to Fraunhofer. The analyses are standardly carried out using a Mastersizer S, a laser instrument from Malvern.
  • polymethylmethacrylats particularly preference is given to polymethylmethacrylats, hydrophobic aluminas, hydrophobic silicas or mixtures thereof.
  • mixtures of hydrophobic silicas with greater than 0% to 20% by weight of hydrophobic alumina and also to hydrophobic silicas.
  • the average primary particle size is preferably in the range from 5 to 50 nm and more preferably in the range from 10 to 20 nm, and the specific surface area is preferably in the range from 10 to 1000 m 2 /g and more preferably in the range from 80 to 380 m 2 /g.
  • hydrophobic compounds are: hydrophobic and/or hydrophobicized clay minerals, hydrophobicized aluminas and/or hydrophobicized silicas, more preferably hydrophobicized aluminas and/or hydrophobicized silicas, such as for example Aerosil® R 812, Aerosil® R 974 or Aerosil® R 8200, Sipernat D 17® (Degussa Aktiengesellschaft, Germany).
  • Hydrophobicized aluminas and/or silicas are obtainable for example by reaction of hydrophilic aluminas and/or silicas with hexamethyldisilazane or dimethyldichlorosilane.
  • the hydrophobic compounds are preferably mixed with the monomer solution before polymerizing to obtain the water-absorbing hydrogel.
  • the hydrophobic compounds can also be mixed with the resulting wet gel.
  • Wet gel means in the context of this invention a hydrogel-forming polymer with an water content of more than 1 part water per part dry polymer, preferable more than 2 parts, more preferable more than 5 parts, most preferable more than 10 parts water per part dry polymer.
  • the wet gel can contain as much water as it can absorb without any pressure. Additional water to the wet gel does not interfere with the possibility to process wet gel with hydrophobic compounds according to this invention.
  • the type of mixing is not subject to any restrictions. It can be done in meat-choppers or other machines know to the person skilled in the art of mixing.
  • reaction mixers or mixing and drying ranges such as for example L ⁇ dige ® mixers, BEPEX ® mixers, NAUTA ® mixers, SCHUGI ® mixers, NARA ® dryers and PROCESSALL ® mixers. Fluidized bed dryers can also be used moreover.
  • the mixing is advantageously carried out using a residence time from 1 to 180 minutes, preferably from 2 to 20 minutes and more preferably from 5 to 20 minutes and a speed from 10 to 1000 rpm, preferably from 50 to 300 rpm and more preferably from 50 to 250 rpm.
  • the invention further provides a process for aftertreating absorbent hydrogels.
  • the aftertreating can be done before, after or simultaneously to the postcrosslinking step.
  • the aftertreating of absorbent hydrogels comprises the steps of:
  • multivalent metal ions such as for example Al 3+ , Fe 2+ , Fe 3+ , Ti 3+ , Ti 4+ , Co 2+ , Ni 2+ , Cr 3+ , Mn 2+ , Zn 2+ , Mg 2+ , Ca 2+ , Zr 3+ , Zr 4+ , more preferably Al 3+ .
  • hydrophilic or hydrophobic compound preferably hydrophobic and/or hydrophobicized clay minerals, hydrophobicized aluminas and/or hydrophobicized silicas, more preferably hydrophobicized aluminas and/or hydrophobicized silicas, such as for example Aerosil ® R 812, Aerosil ® R 974 or Aerosil ® R 8200 (Degussa Aktiengesellschaft, Germany).
  • a nonionic surfactant such as for example sorbitan esters having an HLB value from 2 to 18, particular preference being given to Span ® 80 (Uniqema, Netherlands).
  • the counterions to the multivalent metal ions are not subject to any restriction, but when a solvent is used there is a preference for counterions which ensure adequate solubility, preference being given to sulfate.
  • the metal ions are preferably metered as a solution. Water is a particularly preferred solvent.
  • the concentration of the multivalent metal ion in the aqueous solution is typically from 1% to 20% by weight and preferably from 2% to 10% by weight.
  • the amount of the multivalent metal ion used is typically in the range from 0.05% to 4% by weight, preferably in the range from 0.1% to 2% by weight and more preferably in the range from 0.2% to 1% by weight based on the absorbing hydrogel.
  • the surfactants are preferably metered as a solution.
  • Water or a mixture of water and propylene glycol is a particularly preferred solvent.
  • the concentration of the surfactant in the solution is typically in the range from 5% to 70% by weight, preferably in the range from 10% to 50% by weight and more preferably in the range from 20% to 30% by weight.
  • the amount of surfactant used is typically in the range from 0.01% to 4% by weight, preferably in the range from 0.05% to 2% by weight and more preferably in the range from 0.1% to 1% by weight based on the absorbing hydrogel.
  • the order in which the aftertreating agents are metered is not subject to any restriction, but preference is given to the order multivalent metal ions, solutions of multivalent metal ions, water-soluble cationic polymers and/or solutions of water-soluble polymers, hydrophobic or hydrophilic compounds together or separately in any order, - surface-active compounds, such as surfactants for example, and also solutions thereof,
  • the dissolved aftertreating agents are preferably sprayed onto the dried water- absorbing hydrogel and mixed.
  • the type of mixing is not subject to any restrictions, but preference is given to using reaction mixers or mixing and drying ranges, such as for example L ⁇ dige ® mixers, BEPEX ® mixers, NAUTA ® mixers, SCHUGI ® mixers, NARA ® dryers and PROCESSALL ® mixers. Fluidized bed dryers can also be used moreover.
  • the mixing is advantageously carried out using a residence time from 1 to 180 minutes and preferably from 2 to 15 minutes and a speed from 10 to 1000 rpm, preferably from 50 to 300 rpm and more preferably from 50 to 250 rpm.
  • the last step may be followed by drying. Drying may take place in the mixer itself, by heating the jacket or introducing a stream of warm air. It is similarly possible to use a downstream dryer, such as for example a tray dryer, a rotary tube oven or a heatable screw. But it is also possible for example to utilize an azeotropic distillation as a drying process.
  • Preferred drying temperatures in the process of the present invention are in the range from 50 to 250 0 C, preferably in the range from 50 to 200 0 C and more preferably in the range from 50 to 150°C.
  • the residence time at this temperature in the reaction mixer or dryer is advantageously below 30 minutes and preferably below 10 minutes.
  • the drying is preferably carried out at reduced pressure, preferably at less than 500 mbar and more preferably at less than 200 mbar and optionally supported by a dry gas stream, preferably nitrogen, in an amount from 20 to 1000 l/kgh and preferably from 100 to 250 l/kgh.
  • a dry gas stream preferably nitrogen
  • the absorbent hydrogels are additionally aftertreated with a hydrophilic organic compound in the process of the present invention.
  • Hydrophilic organic compounds improve the fixing of the particulate aftertreating agents on the superabsorbent.
  • Useful hydrophilic organic compounds include for example lower water-soluble polyols having an average molecular weight in the range from 100 to 6000 g/mol, preferably in the range from 200 to 3000 g/mol and more preferably in the range from 250 to 1000 g/mol.
  • Preferred hydrophilic organic compounds are dendritic polymers, highly branched polymers such as for example polyglycerols, polyethylene glycols, polypropylene glycols, random or block copolymers of ethylene oxide and propylene oxide.
  • Useful compounds for this purpose further include polyethoxylates or polypropoxylates of polyhydroxy compounds, such as glycerol, sorbitol, trimethylolpropane, trimethylolethane, pentaerythritol.
  • polyhydroxy compounds such as glycerol, sorbitol, trimethylolpropane, trimethylolethane, pentaerythritol.
  • examples thereof are n-tuply ethoxylated trimethylolpropane or glycerol, n being an integer between 1 and 100.
  • Further examples are block copolymers of fully n-tuply ethoxylated and then m-tuply propoxylated trimethylolpropane or glycerol, n being an integer between 1 and 40 and m being an integer between 1 and 40.
  • the order of the blocks can also be the other way around.
  • the hydrophilic organic compound can be added before, during or after each of the aftertreating steps, preferably before the aftertreatment with the hydrophobic organic compound and more preferably together with the multivalent metal ion.
  • the hydrophilic organic compound is liquid at 23°C and has a 23°C viscosity of less than 3000 mPas, preferably less than 1500 mPas, more preferably less than 1000 mPas, even more preferably less than 500 mPas and most preferably less than 300 mPas.
  • the hydrophilic organic compound is used in an amount based on the dried hydrogel that is in the range from 0.01% to 2% by weight, preferably in the range from 0.1% to 1% by weight and more preferably in the range from 0.35% to 0.75% by weight.
  • the invention further provides crosslinked water-absorbing polymers which, for example, are obtainable by the process of the present invention, especially absorbing hydrogels having an absorbance under load of 0.9psi of at least 10 g/g, preferably of at least 14 g/g, more preferably of at least 16 g/g, even more preferably of at least 18 g/g and particularly preferably of at least 20 g/g, a FS GBP of at least 50 Darcies, preferably of at least 65 Darcies, more preferably of at least 75 Darcies, even more preferably of at least 100 Darcies and particularly preferably of at least 140 Darcies.
  • the present invention further provides hygiene articles comprising the superabsorbent of the present invention.
  • the swellable hydrogel-forming polymers which can be used in the process of the present invention are in particular polymers of crosslinked (co)polymerized hydrophilic monomers, polyaspartic acid, graft (co)polymers of one or more hydrophilic monomers on a suitable grafting base, crosslinked cellulose ethers, crosslinked starch ethers or natural products which are swellable in aqueous fluids, such as guar derivatives for example.
  • the polymer to be crosslinked is a polymer which comprises structure units which derive from acrylic acid or esters thereof or which were obtained by graft copolymerization of acrylic acid or acrylic esters on a water-soluble polymeric matrix.
  • These hydrogels will be known to one skilled in the art and are described for example in US 4,286,082, DE-C 27 06 135, US 4,340,706, DE-C 37 13 601 ,
  • hydrophilic monomers suitable for preparing these swellable hydrogel- forming polymers are acids which are capable of addition polymerization, such as acrylic acid, methacrylic acid, vinylsulfonic acid, vinylphosphonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanephosphonic acid and also their amides, hydroxyalkyl esters and amino- or ammonio-containing esters and amides and also the alkali metal and/or ammonium salts of the acid-functional monomers. It is further possible to use water-soluble N-vinylamides such as N-vinylformamide or else diallyldimethylammonium chloride.
  • Preferred hydrophilic monomers are compounds of the general formula I
  • R 1 is hydrogen, methyl, ethyl or carboxyl
  • R 2 is -COOR 4 , hydroxysulfonyl or phosphonyl, a phosphonyl group esterified with a CrC 4 -alkanol, or a group of the formula Il
  • R 3 is hydrogen, methyl or ethyl
  • R 4 is hydrogen, Ci-C 4 -aminoalkyl, Ci-C 4 -hydroxyalkyl, alkali metal ion or ammonium ion
  • R 5 is a sulfonyl group, a phosphonyl group or a carboxyl group or a respective alkali metal or ammonium salt.
  • Ci-C 4 -alkanols are methanol, ethanol, n-propanol, isopropanol or n-butanol.
  • hydrophilic monomers are acrylic acid and methacrylic acid and also their alkali metal or ammonium salts, for example sodium acrylate, potassium acrylate or ammonium acrylate.
  • Suitable grafting bases for hydrophilic hydrogels which are obtainable by graft copolymerization of olefinically unsaturated acids or their alkali metal or ammonium salts can be of natural or synthetic origin. Examples are starch, cellulose or cellulose derivatives and also other polysaccharides and oligosaccharides, polyalkylene oxides, especially polyethylene oxides and polypropylene oxides, and also hydrophilic polyesters.
  • Suitable polyalkylene oxides have for example the formula III
  • R 6 , R 7 are independently hydrogen, alkyl, alkenyl or aryl,
  • R 8 is hydrogen or methyl, and n is an integer from 1 to 10 000.
  • R 6 and R 7 are each preferably hydrogen, Ci-C 4 -alkyl, C ⁇ Ce-alkenyl or phenyl.
  • Preferred hydrogels are in particular polyacrylates, polymethacrylates and also the US 4,931 ,497, US 5,011 ,892 and US 5,041 ,496 graft polymers.
  • the swellable hydrogel-forming polymers have preferably been crosslinked, i.e., they comprise compounds having at least two double bonds which have been polymerized into the polymeric network.
  • Suitable crosslinkers are in particular N,N'-methylenebisacrylamide and N,N'-methylenebismethacrylamide, esters of unsaturated mono- or polycarboxylic acids of polyols, such as diacrylate or triacrylate, for example butanediol or ethylene glycol diacrylate or methacr ⁇ late and also trimethylolpropane triacrylate and allyl compounds such as allyl (meth)acr ⁇ late, triallyl cyanurate, diallyl maleate, polyallyl esters, tetraallyloxyethane, triallylamine, tetraallylethylenediamine, allyl esters of phosphoric acid and also vinylphosphonic acid derivatives as described for example in EP-A 343 427.
  • the process of the present invention can further utilize hydrogels which are prepared using polyallyl ethers as a crosslinker and by acidic homopolymerization of acrylic acid.
  • Suitable crosslinkers are pentaerythritol triallyl and tetraallyl ethers, polyethylene glycol diallyl ether, ethylene glycol diallyl ether, glycerol dially ether, glycerol triallyl ether, polyallyl ethers based on sorbitol, and also ethoxylated variants thereof.
  • base polymers which are prepared in a kneader, as described for example in WO 01/38402, or on a belt reactor, as described for example in EP-A 955 086.
  • the water-absorbing polymer is preferably a polymeric acrylic acid or a polyacrylate.
  • This water-absorbing polymer can be prepared by a process known from the literature. Preference is given to polymers which comprise crosslinking comonomers in amounts from 0.001 to 10 mol% and preferably 0.01 to 1 mol%, but very particular preference is given to polymers which were obtained by free-radical polymerization and where a polyfu notional ethylenically unsaturated free-radical crosslinker was used which additionally bears at least one free hydroxyl group (such as for example pentaerythritol triallyl ether or trimethylolpropane diallyl ether).
  • the swellable hydrogel-forming polymers are preparable by addition polymerization processes known per se. Preference is given to addition polymerization in aqueous solution conducted as a gel polymerization. It involves for example 15% to 50% by weight aqueous solutions of one or more hydrophilic monomers and optionally of a suitable grafting base being addition polymerized in the presence of a free-radical initiator by utilizing the Trommsdorff-Norrish effect (Makromol. Chem. 1 , 169 (1947)), preferably without mechanical mixing.
  • the addition polymerization reaction may be carried out in the temperature range between 0 and 15O 0 C and preferably between 10 and 100 0 C, not only at atmospheric pressure but also at superatmospheric or reduced pressure.
  • the polymerization can also be carried out in a protective gas atmosphere, preferably under nitrogen.
  • the addition polymerization may be induced using high-energy electromagnetic rays or the customary chemical addition polymerization initiators, for example organic peroxides, such as benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, azo compounds such as azodiisobutyronitrile and also inorganic peroxo compounds such as (NH 4 J 2 S 2 O 8 or K 2 S 2 O 8 or H 2 O 2 .
  • reducing agents such as sodium hydrogensulfite and iron(ll) sulfate or redox systems
  • the reducing component included is an aliphatic or aromatic sulfinic acid, such as benzenesulfinic acid and toluenesulfinic acid or derivatives of these acids, such as Mannich adducts of sulfinic acids, aldehydes and amino compounds, as described in DE-A 13 01 566.
  • the performance characteristics of the polymers can be further improved by postheating the polymer gels in the temperature range from 50 to 13O 0 C and preferably from 70 to 100°C for several hours.
  • the gels obtained are neutralized for example to 0 to 100 mol% preferably 25 to 80 mol% and more preferably to 50 to 75 mol%, based on monomer used, for which the customary neutralizing agents can be used, preferably alkali metal hydroxides or ammonium hydroxide, alkali metal oxides alkali metal carbonates, ammonium carbonate and alkali metal bicarbonates, but more preferably sodium hydroxide, sodium carbonate and sodium bicarbonate.
  • Neutralization is typically achieved by mixing the neutralizing agent to the monomer solution before polymerization.
  • neutralization is achieved by mixing the neutralizing agent as an aqueous solution or else preferably as a solid into the gel.
  • the gel is mechanically comminuted, for example by means of a meat grinder, and the neutralizing agent is sprayed on, scattered on or poured on and then carefully mixed in.
  • the gel mass obtained can then be repeatedly passed through the meat grinder for homogenization.
  • the neutralized gel mass is then dried with a belt or can dryer until the residual moisture content is preferably below 10% by weight and especially below 5% by weight.
  • the dried hydrogel is subsequently ground and sieved, and the grinding can typically be carried out using roll mills, pin mills or swing mills.
  • the particle size of the sieved hydrogel is preferably in the range from 45 to 1000 ⁇ m, more preferably in the range from 45 to 850 ⁇ m, even more preferably in the range from 100 to 800 ⁇ m and yet more preferably in the range from 100 to 700 ⁇ m.
  • the postcrosslinking of hydrogels and superabsorbents is typically carried out by spraying a solution of the surface postcrosslinker onto the dry base polymer powder.
  • the polymeric powder After spraying, the polymeric powder is thermally dried, and the crosslinking reaction can take place not only before but also during the drying.
  • the spraying with a solution of the crosslinker is preferably carried out in reaction mixers or mixing and drying ranges, such as for example L ⁇ dige® mixers, BEPEX® mixers, NAUTA® mixers, SCHUGGI® mixers, NARA® dryers and PROCESSALL®.
  • Fluidized bed dryers can be used as well in addition.
  • Drying may take place in the mixer itself, by heating the jacket or introducing a stream of warm air. It is similarly possible to use a downstream dryer, such as for example a tray dryer, a rotary tube oven or a heatable screw. But it is also possible for example to utilize an azeotropic distillation as a drying process.
  • Preferred drying temperatures are in the range from 50 to 250°C, preferably in the range from 50 to 200°C and more preferably in the range from 50 to 150°C.
  • the preferred residence time at this temperature in the reaction mixer or dryer is below 30 minutes and more preferably below 10 minutes.
  • the crosslinker is preferably dissolved in solvents which are not self-reactive, preferably in lower alcohols, such as for example methanol, ethanol, propanediol, ethylene glycol, most preferably in aqueous solutions of such suitable alcohols, in which case the alcohol content of the solution is in the range from 10% to 90% by weight and more preferably in the range from 40% to 60% by weight.
  • the crosslinker is used in an amount from 0.01% to 1% by weight, based on the polymer used, and the crosslinker solution itself is used in an amount from 1% to 20% by weight and preferably from 5% to 15% by weight, based on the polymer used.
  • the AUL 0.9psi value [g/g] of the postcrossl inked water-absorbing polymers of the present invention is preferably greater than 10, especially greater than 15, more preferably greater than 20, especially greater than 25 and especially preferably greater than 30.
  • the present invention's aftertreated hydrogels capable of absorbing aqueous fluids are particularly useful for thickening aqueous solutions and/or suspensions, preferably for thickening aqueous waste solutions and/or waste suspensions, such as for example medical and/or radioactive wastes, most preferably for thickening medical waste solutions and/or waste suspensions.
  • the present invention's aftertreated hydrogels capable of absorbing aqueous fluids are also useful for absorbing blood and/or body fluids in hygiene articles, such as for example incontinence articles, napkins, tampons, liners.
  • the present invention's aftertreated hydrogels capable of absorbing aqueous fluids can be processed with fibers, such as cellulose for example, and also fibrous web to form absorbing composites.
  • An aftertreatment with hydrophobic and hydrophilic materials ensures a uniform distribution of the superabsorbent in the container when treating at least partially liquid wastes, especially at least partially liquid medical wastes, in that at least a portion of the superabsorbent will initially float on the surface of the solution.
  • the present invention further provides mixtures of products prepared by the present invention's process with biocidal, antimicrobial and/or antibacterial materials and/or perfume or scent materials, stabilizers, dyes, pH indicators and/or other auxiliaries.
  • the dried hydrogel is tested by test methods described hereinbelow:
  • Edana is the EUROPEAN DISPOSABLES AND NONWOVENS ASSOCIATION at Avenue Eugene Plasky, 157 - 1030 Brussels - Belgium - www.edana.org
  • Particle size distribution is measured according to Edana 420.2-02.
  • Moisture content (dryness) is measured according to Edana 430.2-02.
  • Free swell capacity is measured according to Edana 440.2-02.
  • Centrifuge retention capacity (CRC) is measured according to Edana 441.2-02.
  • Absorption under pressure (AUL) is measured according to Edana 442.2-02 and is adopted accordingly for different pressure.
  • Free-Swell Gel Bed Permeability (FS-GBP): The procedure is disclosed in U.S. Patent 6,387,495 which is incorporated herein by refence in a manner that is consistent herewith. The results are expressed in Darcies.
  • Patentapplication 10/631916 which is incorporated herein by refence in a manner that is consistent herewith. The results are expressed in Darcies.
  • a SAP base polymer was produced by polymerizing a monomer solution containing 26.0 weight-% acrylic acid, 0.50 weight-% based on acrylic acid of pentaerytrit- triallyester (P30), the resulting gel was neutralized to a neutralization degree of 72% by using 50 weight-% NaOH.
  • the polymerization was basically performed as follows:
  • the dryed base polymer was postcrossl inked 4.0weight-% based on SAP of a 3.75 weight% of Denacol solution in 1 :1 propyleneglycohwater at 120 0 C for 1 hour.
  • the CRC, 0.9psi AUL, FSGBP and 0.3 psi GBP were measured.
  • Example 1 was repeated, but different Silica were added to the monomer solution:
  • Example 6 Example 7 Example 8 Example 9 Example 10
  • Example 6 Example 7 Example 8 Example 9 Example 10 polymer
  • the process is a high solid (>50%), low degree of neutralization ( ⁇ 60%) and pre- neutralization process:
  • Hydrophobic Silica (Sipemat D17) should be added separately at this point to the fines recycle stream. It also can be pre-blended with the fines recycle stream depended on equipment set-up. At this point you can add the thermal initiators (V-50 and sodium persulfate)and or Vz of the redox initiator package (FF6 and hydrogen peroxide). Feed the mixture onto suitable polybelt reaction surface while incorporating the balance of the initiator package (FF6 and hydrogen peroxide). Allow monomer mixture to react and polymerize. Allow polymer slab to cool and become conditioned in order to tear into dryable chunks.
  • a suitable direct or non- direct contact dryer fluid bed dryer (Carrier, for example), thermal screw dryer (Nara, Bepex, or Holoflite for example) to reduce residual moisture content.
  • Mill Fitz-mills, cage mills, roll-mills, for example
  • sized Rostex, Minox, Kason for example
  • Denacol EX-810 0.08% ⁇ 0.50 wt-% based on polymer
  • Coating ratio 4 wt-% based on polymer
  • Aluminum sulfate 1 wt-% dry based on polymer or 3.58 wt-% Alum solution.
  • Curing and drying condition Dry at lab oven at 135 0 C for 60 minutes.

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Abstract

La présente invention concerne des polymères formant des hydrogels, présentant une perméabilité améliorée et une capacité d'absorption élevée, un procédé de préparation de tels polymères, ainsi que leur utilisation.
PCT/EP2006/063085 2005-06-14 2006-06-12 Polymeres formant des hydrogels, presentant une permeabilite amelioree et une capacite d'absorption elevee WO2006134085A1 (fr)

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WO2010040466A1 (fr) * 2008-10-07 2010-04-15 Evonik Stockhausen Gmbh Procédé continu pour la production d’un polymère superabsorbant
WO2010040467A1 (fr) * 2008-10-07 2010-04-15 Evonik Stockhausen Gmbh Procédé pour la production d’un polymère superabsorbant
WO2010040465A1 (fr) * 2008-10-07 2010-04-15 Evonik Stockhausen Gmbh Procédé pour la fabrication d'un polymère superabsorbant
US8048942B2 (en) 2008-10-08 2011-11-01 Evonik Stockhausen Gmbh Process for the production of a superabsorbent polymer
US8063121B2 (en) 2008-10-08 2011-11-22 Evonik Stockhausen Gmbh Process for the production of a superabsorbent polymer
US8357766B2 (en) 2008-10-08 2013-01-22 Evonik Stockhausen Gmbh Continuous process for the production of a superabsorbent polymer
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JP2012505274A (ja) * 2008-10-07 2012-03-01 エボニック シュトックハウゼン ゲゼルシャフト ミット ベシュレンクテル ハフツング 超吸収性ポリマーの製造のための方法
WO2010040465A1 (fr) * 2008-10-07 2010-04-15 Evonik Stockhausen Gmbh Procédé pour la fabrication d'un polymère superabsorbant
WO2010040466A1 (fr) * 2008-10-07 2010-04-15 Evonik Stockhausen Gmbh Procédé continu pour la production d’un polymère superabsorbant
CN102177182B (zh) * 2008-10-07 2014-01-15 赢创德固赛有限公司 超吸聚合物的制备方法
CN102176926A (zh) * 2008-10-07 2011-09-07 赢创施托克豪森有限责任公司 超吸聚合物的连续制备方法
CN102177182A (zh) * 2008-10-07 2011-09-07 赢创施托克豪森有限责任公司 超吸聚合物的制备方法
TWI500663B (zh) * 2008-10-07 2015-09-21 Evonik Degussa Gmbh 用於製造超吸性聚合物的連續方法
TWI454488B (zh) * 2008-10-07 2014-10-01 Evonik Degussa Gmbh 用於製造超吸性聚合物的方法
KR101630470B1 (ko) 2008-10-07 2016-06-14 에보니크 데구사 게엠베하 초흡수성 중합체의 제조 방법
WO2010040467A1 (fr) * 2008-10-07 2010-04-15 Evonik Stockhausen Gmbh Procédé pour la production d’un polymère superabsorbant
KR20110088501A (ko) * 2008-10-07 2011-08-03 에보닉 스톡하우젠 게엠베하 초흡수성 중합체의 제조 방법
US8653210B2 (en) 2008-10-08 2014-02-18 Evonik Degussa Gmbh Continuous process for the production of a superabsorbent polymer
US8063121B2 (en) 2008-10-08 2011-11-22 Evonik Stockhausen Gmbh Process for the production of a superabsorbent polymer
US9085648B2 (en) 2008-10-08 2015-07-21 Evonik Degussa Gmbh Superabsorbent polymer process
US8048942B2 (en) 2008-10-08 2011-11-01 Evonik Stockhausen Gmbh Process for the production of a superabsorbent polymer
US8357766B2 (en) 2008-10-08 2013-01-22 Evonik Stockhausen Gmbh Continuous process for the production of a superabsorbent polymer
US8962910B2 (en) * 2008-10-20 2015-02-24 Evonik Corporation Superabsorbent polymer containing clay particulate, and method of making same
US20150157759A1 (en) * 2008-10-20 2015-06-11 Evonik Corporation Superabsorbent polymer and method for making same

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