EP2504038A1 - Verfahren zur herstellung wasserabsorbierender polymerer schäume - Google Patents

Verfahren zur herstellung wasserabsorbierender polymerer schäume

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Publication number
EP2504038A1
EP2504038A1 EP10782259A EP10782259A EP2504038A1 EP 2504038 A1 EP2504038 A1 EP 2504038A1 EP 10782259 A EP10782259 A EP 10782259A EP 10782259 A EP10782259 A EP 10782259A EP 2504038 A1 EP2504038 A1 EP 2504038A1
Authority
EP
European Patent Office
Prior art keywords
monomer
alkyl
water
hydrogen
photoinitiator
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.)
Withdrawn
Application number
EP10782259A
Other languages
German (de)
English (en)
French (fr)
Inventor
Francisco Javier Lopez Villanueva
Markus LINSENBÜHLER
Matthias Weismantel
Bernd Siegel
Timo Baumgärtner
Michael Fastner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP10782259A priority Critical patent/EP2504038A1/de
Publication of EP2504038A1 publication Critical patent/EP2504038A1/de
Withdrawn legal-status Critical Current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
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/10—Aqueous solvent
    • 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
    • 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
    • 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
    • C08F2/18—Suspension polymerisation
    • 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
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/14—Water soluble or water swellable polymers, e.g. aqueous gels
    • 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
    • C08J2333/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Definitions

  • the present invention relates to a process for the preparation of water-absorbing polymeric foams by polymerization of a foamed aqueous monomer solution or suspension comprising an ethylenically unsaturated, acidic group-containing monomer which may be at least partially neutralized, a crosslinker, a photoinitiator and a surfactant.
  • Water-absorbent polymers are used as aqueous solution-absorbing products for the production of diapers, tampons, sanitary napkins, panty liners, wound dressings and other hygiene articles, but also as water-retaining agents in agricultural horticulture.
  • the water-absorbing polymers are also referred to as superabsorbents.
  • Water-absorbing polymeric foams based on monomers containing crosslinked acid groups are known, for example from EP 0 858 478 B1, US Pat.
  • They are prepared, for example, by foaming a polymerizable aqueous mixture containing at least 50 mol% of neutralized, acid group-containing ethylenically unsaturated monomers, crosslinkers and at least one surfactant, and then polymerizing the foamed mixture.
  • the foaming of the polymerizable mixture may be carried out by dispersing fine bubbles of a radical-inert gas or by dissolving such a gas under elevated pressure in the polymerizable mixture and depressurizing the mixture.
  • the foams are used, for example, in hygiene articles for the acquisition, distribution and storage of body fluids.
  • the object of the present invention was to provide water-absorbing polymer foams having an improved profile of properties, such as a high centrifuge retention capacity (CRC) and a low washout loss (AWV). Furthermore, the water-absorbing foams should contain little residual monomer and few residual crosslinkers and should be as white as possible and not release any odors.
  • the object was achieved by a process for producing water-absorbing polymeric foams by polymerization of a foamed aqueous monomer solution or suspension containing a) at least one ethylenically unsaturated, acid group-carrying monomer which may be at least partially neutralized,
  • R 1 , R 2 , R 3 , R 4 and R 5 independently of one another are hydrogen or C 1 -C 5 -alkyl, preferably independently of one another, hydrogen or C 1 -C 4 -alkyl, more preferably independently of one another, hydrogen or C 1 -C 2 -alkyl, where Cs-alkyl may be branched or unbranched,
  • X is hydrogen, OR 6 or Ci-Cs-alkyl, preferably OR 6 or
  • C 1 -C 4 -alkyl particularly preferably OR 6 or C 1 -C 2 -alkyl, where C 3 -C 8 -alkyl can be branched or unbranched,
  • R 6 is Ci-Cs-alkyl or Ci-Cs-hydroxyalkyl, preferably Ci-C4-alkyl or Ci-C4-hydroxyalkyl, particularly preferably Ci-C2-alkyl or
  • C 1 -C 2 -hydroxyalkyl where C 3 -C 5 -alkyl or C 3 -C -hydroxyalkyl can be branched or unbranched,
  • R 7 and R 8 independently of one another are C 1 -C 5 -alkyl or C 6 -C 12 -aryl, preferably C 1 -C 4 -alkyl or C 6 -C 10 -aryl, more preferably independently of one another C 1 -C 2 -alkyl or C 6 -C 8 -alkyl Aryl, where C3-Cs-alkyl or C9-Ci2-aryl can be branched or unbranched, mean.
  • the amount of photoinitiator c) is preferably 0.001 to 2 wt .-%, particularly preferably 0.01 to 1 wt .-%, most preferably 0.05 to 0.2 wt .-%, each based on the unneutralized monomer a ).
  • the monomers a) are preferably water-soluble, i. the solubility in water at 23 ° C. is typically at least 1 g / 100 g of water, preferably at least 5 g / 100 g of water, more preferably at least 25 g / 100 g of water, most preferably at least 35 g / 100 g of water.
  • Suitable monomers a) are, for example, ethylenically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, and itaconic acid. Particularly preferred monomers are acrylic acid and methacrylic acid. Very particular preference is given to acrylic acid.
  • Suitable monomers a) are, for example, ethylenically unsaturated sulfonic acids, such as styrenesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid (AMPS).
  • sulfonic acids such as styrenesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid (AMPS).
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • a suitable monomer a) is, for example, an acrylic acid purified according to WO 2004/035514 A1 with 99.8460% by weight of acrylic acid, 0.0950% by weight of acetic acid, 0.0332% by weight of water, 0.0203% by weight.
  • Propionic acid 0.0001% by weight furfurale, 0.0001% by weight maleic anhydride
  • the amount of monomer a) is preferably 20 to 90 wt .-%, particularly preferably 30 to 85 wt .-%, most preferably 35 to 75 wt .-%, each based on the unneutralized monomer a) and on the Monomer solution or suspension. Based on the unneutralized monomer a) in the context of this invention, that for the calculation of the proportion of the monomer a) is used prior to neutralization, ie the contribution of neutralization is disregarded.
  • the acid groups of the monomers a) are usually neutralized to 25 to 95 mol%, preferably 40 to 85 mol%, preferably 50 to 80 mol%, particularly preferably 55 to 75 mol%, wherein the customary neutralizing agents can be used, for example, alkali metal hydroxides, alkali metal oxides, alkali metal carbonates or alkali metal bicarbonates and mixtures thereof.
  • the neutralization can also be carried out with ammonia, amines or alkanolamines, such as ethanolamine, diethanolamine or triethanolamine.
  • 10 to 90 mol%, preferably 20 to 80 mol%, particularly preferably 30 to 70 mol%, very particularly preferably 40 to 60 mol%, of the neutralized monomers a) by means of an alkanolamine were neutralized.
  • the proportion of acrylic acid and / or salts thereof in the total amount of monomers a) is preferably at least 50 mol%, particularly preferably at least 90 mol%, very particularly preferably at least 95 mol%.
  • the monomers a) usually contain polymerization inhibitors, preferably hydroquinone half ethers, as a storage stabilizer.
  • the monomer solution preferably contains up to 250 ppm by weight, preferably at most 130 ppm by weight, more preferably at most 70 ppm by weight, preferably at least 10 ppm by weight, more preferably at least 30 ppm by weight, in particular by 50% by weight .-ppm, hydroquinone, in each case based on the unneutralized monomer a).
  • an ethylenically unsaturated, acid group-carrying monomer having a corresponding content of hydroquinone half-ether can be used to prepare the monomer solution.
  • Preferred hydroquinone half ethers are hydroquinone monomethyl ether (MEHQ) and / or alpha-tocopherol (vitamin E).
  • Suitable crosslinkers b) are compounds having at least two groups suitable for crosslinking. Such groups are, for example, ethylenically unsaturated groups which can be incorporated in the polymer chain by free-radical polymerization, and functional groups which can form covalent bonds with the acid groups of the monomer a). Furthermore, polyvalent metal salts containing at least two acid groups of the monomer a) can form coordinative bonds, suitable as crosslinker b).
  • Crosslinkers b) are preferably compounds having at least two polymerizable groups which can be incorporated in the polymer network in free-radically polymerized form.
  • Suitable crosslinkers b) are, for example, ethylene glycol dimethacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, allyl methacrylate, trimethylolpropane triacrylate, triallylamine, tetraallylammonium chloride, tetraallyloxyethane, as described in EP 0 530 438 A1, di- and triacrylates, as in EP 0 547 847 A1, EP 0 559 476 A1,
  • WO 2003/104301 A1 and DE 103 31 450 A1 mixed acrylates which, in addition to acrylate groups, contain further ethylenically unsaturated groups, as described in DE 103 31 456 A1 and DE 103 55 401 A1, or crosslinker mixtures, as described, for example, in DE 195 43 368 A1, DE 196 46 484 A1, WO 90/15830 A1 and WO 2002/032962 A2.
  • Preferred crosslinkers b) are pentaerythritol triallyl ether, tetraalloxyethane, methylenebis methacrylamide, 15-times ethoxylated trimethylolpropane triacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate and triallylamine.
  • Very particularly preferred crosslinkers b) are the polyethoxylated and / or propoxylated glycerols esterified with acrylic acid or methacrylic acid to form di- or triacrylates, as described, for example, in WO 2003/104301 A1.
  • Particularly advantageous are di- and / or triacrylates of 3- to 10-fold ethoxylated glycerol.
  • diacrylates or triacrylates of 1 to 5 times ethoxylated and / or propoxylated glycerol.
  • Most preferred are the triacrylates of 3 to 5 times ethoxylated and / or propoxylated glycerol, in particular the triacylate of 3-times ethoxylated glycerol.
  • the amount of crosslinker b) is preferably 0.5 to 15 wt .-%, more preferably 2 to 10 wt .-%, most preferably 3 to 8 wt .-%, each based on the unneutralized monomer a).
  • the centrifuge retention capacity decreases and the absorption under a pressure of 21.0 g / cm 2 (AUL 0.3 psi) passes through a maximum.
  • the monomer solution or suspension may contain further initiators. This can be used under the polymerization in radical-generating compounds, such as thermal initiators, redox initiators.
  • Thermal initiators are, for example, peroxides, hydroperoxides, hydrogen peroxide, persulfates and azo initiators.
  • Suitable azo initiators are, for example 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (N, N-dimethylene) isobutyramidine dihydrochloride, 2- (carbamoylazo) isobutyronitrile, 2,2'-azo bis [2] (2'-imidazolin-2-yl) propane] dihydrochloride and 4,4'-azobis (4-cyanovaleric acid).
  • combinations of photoinitiator c) and azo initiator are used.
  • the surfactants d) are of crucial importance for the preparation and stabilization of the foamed monomer solution or suspension.
  • Usable nonionic surfactants are, for example, addition products of alkylene oxides, in particular ethylene oxide, propylene oxide and / or butylene oxide with alcohols, amines, phenols, naphthols or carboxylic acids.
  • the surfactants used are advantageously addition products of ethylene oxide and / or propylene oxide with alcohols containing at least 10 carbon atoms, the addition products containing 3 to 200 moles of ethylene oxide and / or propylene oxide per mole of alcohol.
  • the addition products contain the alkylene oxide units in the form of blocks or in random distribution.
  • nonionic surfactants which can be used are the addition products of 7 mol of ethylene oxide and 1 mol of tallow fatty alcohol, reaction products of 9 mol of ethylene oxide with 1 mol of tallow fatty alcohol and adducts of 80 mol of ethylene oxide and 1 mol of tallow fatty alcohol.
  • Other useful commercial nonionic surfactants consist of reaction products of Oxoal- koholen or Ziegler alcohols with 5 to 12 moles of ethylene oxide per mole of alcohol, especially with 7 moles of ethylene oxide.
  • Other useful commercial nonionic surfactants are obtained by ethoxylation of castor oil. For example, 12 to 80 moles of ethylene oxide are added per mole of castor oil.
  • Further commercial products which can be used are, for example, the reaction products of 18 mol of ethylene oxide with 1 mol of tallow fatty alcohol, the addition products of 10 mol of ethylene oxide with 1 mol of a Ci3 / Ci5-oxoalcohol, or the reaction products of 7 to 8 mol of ethylene oxide with 1 mol of a Ci3 / Cis oxo alcohol.
  • Further suitable nonionic surfactants are phenol alkoxylates, such as, for example, p-tert-butylphenol which has been reacted with 9 mol of ethylene oxide, or methyl ethers of reaction products of 1 mol of a C12-bis
  • Cis-alcohol and 7.5 moles of ethylene oxide Cis-alcohol and 7.5 moles of ethylene oxide.
  • the nonionic surfactants described above can be converted, for example, by esterification with sulfuric acid into the corresponding sulfuric acid half esters.
  • the sulfuric acid half esters are used in the form of the alkali metal or ammonium salts as anionic surfactants.
  • Suitable anionic surfactants are, for example, example, alkali metal or ammonium salts of sulfuric monoesters of addition products of ethylene oxide and / or propylene oxide with fatty alcohols, alkali metal or ammonium salts of alkylbenzenesulfonic acid or alkylphenol ether sulfates. Products of the type mentioned are commercially available. For example, the sodium salt of a sulfuric monoester of one reacted with 106 moles of ethylene oxide
  • Ci3 / Ci5-oxoalcohols the triethanolamine salt of dodecylbenzenesulfonic acid, the sodium salt of Alkylphenolethersulfaten and the sodium salt of the sulfuric monoester of a reaction product of 106 moles of ethylene oxide with 1 mole of tallow fatty alcohol commercially available anionic surfactants.
  • anionic surfactants are sulfuric monoesters of C 13 / C 15 -oxo alcohols, paraffin-sulfonic acids, such as
  • the polymerizable aqueous mixture may contain combinations of a nonionic surfactant and an anionic surfactant or combinations of nonionic surfactants or combinations of anionic surfactants. Also cationic surfactants are suitable.
  • Examples thereof are the dimethyl sulfate-quaternized reaction products of 6.5 mol of ethylene oxide with 1 mol of oleylamine, distearyldimethylammonium chloride, lauryltrimethylammonium chloride, cetylpyridinium bromide and dimethyl sulfate-quaternized stearic acid triethanolamine ester, which is preferably used as cationic surfactant.
  • the amount of surfactant, based on the unneutralized monomer a) is preferably 0.01 to 10 wt .-%, particularly preferably 0.1 to 6 wt .-%, most preferably 0.8 to 3 wt .-%.
  • Examples of ethylenically unsaturated monomers e) which can be copolymerized with the ethylenically unsaturated monomers having acid groups are acrylamide, methacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate.
  • Solubilizers f) are water-miscible organic solvents, for example dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone, monohydric alcohols, glycols, polyethylene glycols or monoethers derived therefrom, the monoethers having no
  • Suitable ethers are methyl glycol, butyl glycol, butyl diglycol, methyl diglycol, butyl triglycol, 3-ethoxy-1-propanol and glyceryl monomethyl ether. If solubilizers f) are used, their content in the monomer solution or suspension is preferably up to 50% by weight, particularly preferably 1 to
  • the monomer solution or suspension may contain thickeners, foam stabilizers, fillers, fibers and / or cell nucleating agents g). Thickeners are used, for example, to optimize the foam structure and to improve foam stability. This ensures that the foam shrinks only slightly during the polymerization. Suitable thickeners are all known natural and synthetic polymers which greatly increase the viscosity of an aqueous system. These may be water-swellable or water-soluble synthetic and natural polymers.
  • Suitable water-swellable or water-soluble synthetic polymers which are suitable as thickeners are, for example, high molecular weight polyethylene glycols or copolymers of ethylene glycol and propylene glycol and high molecular weight polysaccharides such as starch, guar gum, locust bean gum or derivatives of natural substances such as carboxymethylcellulose, hydroxyethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose and cellulose mixed ethers.
  • Another group of thickeners are water-insoluble products, such as finely divided silica, zeolites, bentonite, cellulose powder or other finely divided powders of crosslinked polymers.
  • the monomer solution or suspension may contain the thickeners in amounts of up to 30% by weight. If such thickening agents are used at all, they are contained in amounts of 0.1 to 10 wt .-%, preferably 0.5 to 20 wt .-% in the monomer solution or suspension.
  • hydrocarbons having at least 5 C atoms in the molecule are, for example, pentane, cyclopentane, hexane, cyclohexane, heptane, octane, isooctane, decane and dodecane.
  • the aliphatic hydrocarbons contemplated may be straight chain, branched or cyclic and have a boiling temperature which is above the temperature of the aqueous mixture during foaming. The aliphatic hydrocarbons increase the service life of the not yet polymerized foamed aqueous reaction mixture.
  • the hydrocarbons act as cell nucleating agents and at the same time stabilize the already formed foam. In addition, they can cause further foaming when polymerizing the monomer solution or suspension. You can then also have the function of a propellant.
  • chlorinated or fluorinated hydrocarbons as cell nucleating agents and / or foam stabilizers, such as dichloromethane, trichloromethane, 1,2-dichloroethane, trichlorofluorocarboxylic acid. methane or 1, 1, 2-trichlorotrifluoroethane.
  • hydrocarbons are used, for example, in amounts of 0.1 to 20 wt .-%, preferably 0.1 to 10 wt .-%, based on the monomer solution or suspension.
  • one or more fillers may be added, for example chalk, talc, "Gay", titanium dioxide, magnesium oxide, alumina, precipitated silicas in hydrophilic or hydrophobic modifications, dolomite and / or calcium sulfate be contained in the monomer solution or suspension in amounts up to 30 wt .-%.
  • the aqueous monomer solutions or suspensions described above are first foamed.
  • an inert gas such as nitrogen, carbon dioxide or air
  • nitrogen, carbon dioxide or air can be dissolved in the aqueous monomer solution or suspension under a pressure of, for example, 2 to 400 bar, and then be allowed to relax to atmospheric pressure.
  • the gas solubility increases with decreasing temperature, the gas saturation and the subsequent foaming should be carried out at the lowest possible temperature, whereby undesirable precipitation should be avoided.
  • the aqueous monomer solutions or suspensions can also be foamed by another method by dispersing therein fine bubbles of an inert gas.
  • the foaming of the aqueous monomer solutions or suspensions can be carried out in the laboratory, for example, by foaming the aqueous monomer solution or suspension in a food processor equipped with a whisk. Furthermore, it is possible to foam the aqueous monomer solutions or suspensions with carbon dioxide by using carbonates or bicarbonates for neutralization.
  • the generation of foam is preferably carried out in an inert gas atmosphere and with inert gases, for example by adding nitrogen or noble gases under atmospheric pressure or elevated pressure, for example up to 25 bar, and then releasing.
  • inert gases for example by adding nitrogen or noble gases under atmospheric pressure or elevated pressure, for example up to 25 bar, and then releasing.
  • the consistency of the monomer foams, the size of the gas bubbles and the distribution of the gas bubbles in the monomer foam can be varied within a wide range, for example by selecting the surfactants d), solubilizers f), foam stabilizers, cell nucleating agents, thickeners and fillers g). This makes it easy to adjust the density, the degree of off-set and the wall thickness of the monomer foam.
  • the aqueous monomer solution or suspension is preferably foamed at temperatures below the boiling point of its constituents, for example at ambient temperature up to 100 ° C, preferably at 0 to 50 ° C, more preferably at 5 to 20 ° C.
  • temperatures below the boiling point of the component with the lowest boiling point by foaming the aqueous monomer solution or suspension in a pressure-tight container. This gives monomer foams which are flowable and are stable over a longer period of time.
  • the density of the monomer foams at a temperature of 20 ° C, for example, 0.01 to 0.9 g / cm 3 .
  • the obtained monomer foam can be polymerized on a suitable support.
  • the polymerization is carried out in the presence of the photoinitiators c).
  • the radicals can be generated for example by heating (thermal polymerization) or by irradiation with light of a suitable wavelength (UV polymerization).
  • Polymeric foams having a layer thickness of up to about 5 millimeters are produced, for example, by one-sided or two-sided heating or, in particular, by irradiation of the monomer foams on one or both sides. If thicker polymeric foams are to be produced, for example polymeric foams with thicknesses of several centimeters, the heating of the monomer foam with the aid of microwaves is particularly advantageous because in this way a relatively uniform heating can be achieved.
  • the proportion of unreacted monomer a) and crosslinker b) in the resulting polymeric foam increases.
  • the thermal polymerization takes place, for example, at temperatures of 20 to 180 ° C, preferably in the range of 40 ° C to 160 ° C, in particular at temperatures of 65 to 140 ° C.
  • the monomer foam can be heated on both sides and / or irradiated, for example by means of contact heating or by irradiation or in a drying oven.
  • the resulting polymeric foams are open-celled.
  • the proportion of open cells is for example at least 80%, preferably it is above 90%. Particularly preferred are polymeric foams having an open cell content of 100%.
  • the proportion of open cells in the polymeric foam is determined, for example, by means of scanning electron microscopy (Scanning Electron Microscopy).
  • drying of the polymeric foam takes place. This removes water and other volatile components.
  • suitable drying methods are thermal convection drying, such as forced-air drying, thermal contact drying, such as drum drying, radiation drying, such as infrared drying, dielectric drying, such as microwave drying, and freeze-drying.
  • the drying temperatures are usually in the range 50 to 200 ° C, preferably 60 to 150 ° C, more preferably 80 to 120 ° C, most preferably 90 to 1 10 ° C.
  • the preferred residence time at this temperature in the dryer is preferably at least 1 minute, more preferably at least 2 minutes, most preferably at least 5 minutes, and usually at most 20 minutes.
  • a particularly suitable drying process is the (vacuum) belt drying.
  • the polymeric foam usually contains less than 15% by weight of water.
  • the water content of the polymeric foam can be arbitrarily adjusted by wetting with water or steam.
  • the water-absorbent polymeric foams can be surface postcrosslinked to further improve the properties.
  • Suitable surface post-crosslinkers are compounds which contain groups which can form covalent bonds with at least two carboxylate groups of the polymer particles. Suitable compounds are, for example, polyfunctional amines, polyfunctional amidoamines, polyfunctional epoxides, as described in EP 0 083 022 A2, EP 0 543 303 A1 and EP 0 937 736 A2, di- or polyfunctional alcohols, as described in DE 33 14 019 A1,
  • Preferred surface postcrosslinkers are ethylene carbonate, ethylene glycol diglycidyl ether, reaction products of polyamides with epichlorohydrin and mixtures of propylene glycol and 1,4-butanediol.
  • Very particularly preferred surface postcrosslinkers are 2-hydroxyethyloxazolidin-2-one, oxazolidin-2-one and 1,3-propanediol.
  • surface postcrosslinkers which contain additional polymerizable ethylenically unsaturated groups, as described in DE 37 13 601 A1
  • the amount of surface postcrosslinker is preferably 0.001 to 2 wt .-%, more preferably 0.02 to 1 wt .-%, most preferably 0.05 to 0.2 wt .-%, each based on the water-absorbing polymeric foam.
  • polyvalent cations are applied to the water-absorbent polymeric foam before, during or after the surface postcrosslinking in addition to the surface postcrosslinkers.
  • the polyvalent cations which can be used in the process according to the invention are, for example, divalent cations, such as the cations of zinc, magnesium, calcium, iron and strontium, trivalent cations, such as the cations of aluminum, iron, chromium, rare earths and manganese, tetravalent cations, such as the cations of Titanium and zirconium.
  • divalent cations such as the cations of zinc, magnesium, calcium, iron and strontium
  • trivalent cations such as the cations of aluminum, iron, chromium, rare earths and manganese
  • tetravalent cations such as the cations of Titanium and zirconium.
  • chloride, bromide, sulfate, hydrogensulfate, carbonate, hydrogencarbonate, nitrate, phosphate, hydrogenphosphate, dihydrogenphosphate and carboxylate, such as acetate and lactate are possible.
  • Aluminum sulfate is preferred.
  • the amount of polyvalent cation used is, for example, 0.001 to 1.5% by weight, preferably 0.005 to 1% by weight, particularly preferably 0.02 to 0.8% by weight. each based on the water-absorbent polymeric foam.
  • the surface postcrosslinking is usually carried out so that a solution of the surface postcrosslinker is sprayed onto the water absorbing polymeric foams.
  • the surface-postcrosslinker-coated polymeric foams are thermally dried, whereby the surface postcrosslinking reaction can occur both before and during drying.
  • Preferred drying temperatures are in the range 50 to 250 ° C, preferably 70 to 150 ° C, more preferably 85 to 120 ° C, most preferably 90 to 1 10 ° C.
  • the preferred residence time at this temperature in the dryer is preferably at least 1 minute, more preferably at least 2 minutes, most preferably at least 5 minutes, and usually at most 20 minutes.
  • polymeric foams can be coated or rewetted to improve the properties.
  • Suitable coatings for improving the swelling rate (FSR) and the liquid transfer (SFC) are, for example, inorganic inert substances, such as water-insoluble metal salts, organic polymers, cationic polymers and di- or polyvalent metal cations, such as aluminum sulfate and aluminum sulfate. did.
  • Suitable coatings against the unwanted tendency to cake are, for example, fumed silica, such as Aerosil® 200, and surfactants, such as Span® 20.
  • Suitable coatings for reducing the content of unreacted monomers (residual monomers) are, for example, reducing agents, such as the salts of sulfurous acid, the hypophosphorous Acid and / or organic sulfinic acid.
  • the reducing agent used is preferably a mixture of the sodium salt of 2-hydroxy-2-sulfinatoacetic acid, the disodium salt of 2-hydroxy-2-sulfonatoacetic acid and sodium hydrogen sulfite.
  • Such mixtures are available as Brüggolite® FF6 and Brüggolite® FF7 (Brüggemann Chemicals; Heilbronn; DE).
  • water-absorbent polymeric foams having a high centrifuge retention capacity (CRC) and a low elution loss (AWV) can be produced.
  • Further objects of the present invention are the water-absorbent polymeric foams obtainable by the process according to the invention and water-absorbent polymeric foams having a centrifuge retention capacity (CRC) of at least 5 g / g and a content of residual monomers of less than
  • the water-absorbing polymeric foams according to the invention have a centrifuge retention capacity (CRC) of typically at least 5 g / g, preferably at least 6 g / g, preferably at least 7 g / g, more preferably at least 8 g / g, most preferably at least 9 g / g, on.
  • CRC centrifuge retention capacity
  • the centrifuge retention capacity (CRC) of the water-absorbent polymeric foams is usually less than 20 g / g.
  • the water-absorbing polymeric foams according to the invention have a content of residual monomer of typically less than 0.15% by weight, preferably less than 0.12% by weight, preferably less than 0.1% by weight, more preferably less than 0.075 wt .-%, most preferably less than 0.05 wt .-%, on.
  • the water-absorbing polymeric foams according to the invention have a content of residual crosslinker of typically less than 0.002% by weight, preferably less than 0.001% by weight, preferably less than 0.0005% by weight, more preferably less than 0.0002% by weight. %, most preferably less than
  • a further subject of the present invention are hygiene articles which contain water-absorbing polymeric foams according to the invention.
  • the hygiene articles are in particular disposable diapers, tampons, sanitary napkins, panty liners and wound coverings.
  • Measurements should be taken at an ambient temperature of 23 ⁇ 2 ° C and a relative humidity of 50 ⁇ 10%, unless otherwise specified.
  • the water-absorbing polymer particles are thoroughly mixed before the measurement.
  • the residual monomers of the water-absorbing polymeric foam are determined analogously to the EDANA-recommended test method no. WSP 210.2-05 "Residual Monomers".
  • Residual Crosslinker The residual crosslinker content of the water-absorbent polymeric foam polymer particles is determined by HPLC using a ZORBAX® Eclipse XDB C18 reverse phase column (Agilent Technologies, US) followed by UV / VI S detection and external standard calibration.
  • the mobile phase used is acetonitrile / water with a gradient.
  • the centrifuge retention capacity (CRC) of the water-absorbent polymeric foam is determined analogously to the EDANA-recommended test method no. WSP 241.2-05 "Centrifuge Retention Capacity”.
  • the leaching loss (AWV) of the water-absorbing polymeric foam is determined analogously to the EDANA-recommended test method No. WSP 270.2-05 "Extractables", wherein the average molecular weight of the optionally partially neutralized monomer a) is used for the molecular weight M acr .
  • the EDANA test methods are available, for example, from EDANA, Avenue Eugene Plasky 157, B-1030 Brussels, Belgium. Examples
  • Example 1 209.1 g of acrylic acid, 81.3 g of a 37.3% strength by weight aqueous sodium acrylate solution, 16.8 g of Sartomer® SR-344 (diacrylate of a polyethylene glycol having a molecular weight of about 400 g / mol), 25 , 6 g of a 15 wt .-% aqueous solution of Lutensol® AT80 (addition product of 80 moles of ethylene oxide to 1 mole of a linear saturated C16-C18 fatty alcohol, BASF SE, Ludwigshafen, DE) and 26.6 g of water were in a Beaker mixed. Subsequently, 240.5 g of triethanolamine was added dropwise with cooling, the temperature remaining below 15 ° C.
  • the resulting homogeneous solution was transferred to a pressure vessel and saturated there with carbon dioxide for 25 minutes at a pressure of 12 bar. Under pressure, 8.0 g of a 3% strength by weight aqueous solution of Wako® V-50 (2,2'-azobis (2-amidinopropane) dihydrochloride) and 0.24 g of Irgacure® 2959 (1) were added. [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one) was added and mixed in with a strong stream of carbon dioxide. Carbon dioxide was then passed through the reaction mixture for a further 5 minutes. The carbon dioxide-saturated reaction mixture was then squeezed out through a nozzle with a diameter of 1.0 mm at a pressure of 12 bar, forming a fine-celled, readily flowable foam.
  • the bottom of a DIN A3 glass plate with 3 mm high edges was covered with a transparent polyester film.
  • the obtained monomer foam was applied to the glass plate and covered with a second transparent polyester film and a second glass plate.
  • the foam sample was irradiated synchronously from both sides for 4 minutes with UV light, from the top with a UVA / IS emitter UVASPOT 1000 / T (Dr Hönle AG, Gräfelfing, DE), from below with 2 UVA / IS emitters UVASPOT 400 / T (Dr. Hönle AG, Gräfelfing, DE).
  • the distance of the upper lamp to the monomer foam was 39 cm and the distance of the lower lamps to the monomer foam was 13 cm.
  • the resulting polymeric foam was dried for 10 minutes in a convection oven at 100 ° C and analyzed.
  • the foam had a residual monomer content of 0.13 wt%, a residual crosslinker content of 0.0003 wt%, a centrifuge retention capacity (CRC) of 8.4 g / g, and the elution loss (AWV) 55% by weight.
  • Example 2 comparative example
  • Example 2 The procedure was as in Example 1.
  • the initiator used was 16.0 g of a 3% strength by weight aqueous solution of Wako® V-50 (2,2'-azobis (2-amidinopropane) dihydrochloride).
  • the foam had a residual monomer content of 0.72% by weight, a residual crosslinker content of 0.14% by weight, a centrifuge retention capacity (CRC) of 9.6 g / g, and the elution loss (AWV) was 42% by weight .-%.
  • Example 2 The procedure was as in Example 1.
  • the initiator used was 0.48 g of Irgacure® 2959 (1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methylpropan-1-one).
  • the resulting polymeric foam was difficult to dissolve from the lower polyester film.
  • the foam had a residual monomer content of 0.068% by weight, a residual crosslinker content of less than 0.0001% by weight, a centrifuge retention capacity (CRC) of 8.8 g / g, and the elution loss (AWV) was 52% by weight .-%.
  • CRC centrifuge retention capacity
  • AAV elution loss
  • Example 4 The procedure was as in Example 1. The initiator used was 0.48 g of Lucirin® TPO-L
  • the resulting polymeric foam was difficult to dissolve from the lower polyester film.
  • the foam had a residual monomer content of 0.37 wt%, a residual crosslinker content of less than 0.0001 wt%, a centrifuge retention capacity (CRC) of 10.1 g / g, and the elution loss (AWV) 59% by weight.
  • Example 2 The procedure was as in Example 1. 0.48 g of Irgacure® 184 (1-hydroxycyclohexylphenyl ketone) was used as the initiator. The foam had a content
  • Example 6 comparative example
  • Example 7 The procedure was as in Example 1.
  • the initiator used was 0.48 g of Irgacure® 250 ((4-methylphenyl) [4- (2-methylpropyl) phenyl] iodonium hexafluorophosphate).
  • the resulting polymeric foam smelled unpleasant and did not peel off the polyester films.
  • the foam had a residual monomer content of 1.6% by weight, a residual crosslinker content of 0.074% by weight, a centrifuge retention capacity (CRC) of 7.7 g / g, and the elution loss (AWV) was 62% by weight. %.
  • Example 7 comparativative example
  • Example 2 The procedure was as in Example 1.
  • the initiator used was 0.48 g of 2-amino-9-fluorenone.
  • the foam had a residual monomer content of 3.1% by weight, a residual crosslinker content of 1.1% by weight, a centrifuge retention capacity (CRC) of 8.8 g / g, and the elution loss (AWV) was 80% by weight .-%.
  • CRC centrifuge retention capacity
  • AAV elution loss
  • Example 2 The procedure was as in Example 1.
  • the initiator used was 0.48 g of Darocur® 1 173 (2-hydroxy-2-methyl-1-phenylpropan-1-one).
  • the foam had 0.045 wt% residual monomer content, less than 0.0001 wt% residual crosslinker, 9.0 g / g CRC and 63 wt% washout loss .-%.

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  • Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
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  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Materials For Medical Uses (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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US20120296297A1 (en) * 2011-05-18 2012-11-22 Achille Di Cintio Feminine hygiene absorbent articles comprising water-absorbing polymeric foams
KR101960041B1 (ko) * 2015-04-28 2019-03-19 주식회사 엘지화학 고흡수성 수지의 제조방법
KR102086053B1 (ko) * 2016-12-13 2020-03-06 주식회사 엘지화학 고흡수성 수지 및 이의 제조 방법
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WO2011061282A1 (de) 2011-05-26
US20120232176A1 (en) 2012-09-13

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