EP2470572A1 - Polymères superabsorbants souples sous forme de particules et leur utilisation - Google Patents

Polymères superabsorbants souples sous forme de particules et leur utilisation

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Publication number
EP2470572A1
EP2470572A1 EP10740677A EP10740677A EP2470572A1 EP 2470572 A1 EP2470572 A1 EP 2470572A1 EP 10740677 A EP10740677 A EP 10740677A EP 10740677 A EP10740677 A EP 10740677A EP 2470572 A1 EP2470572 A1 EP 2470572A1
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EP
European Patent Office
Prior art keywords
superabsorbent
water
thermoplastic
acid
polymerization
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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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EP10740677A
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German (de)
English (en)
Inventor
Francisco Javier Lopez Villanueva
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BASF SE
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BASF SE
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Priority to EP10740677A priority Critical patent/EP2470572A1/fr
Publication of EP2470572A1 publication Critical patent/EP2470572A1/fr
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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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers

Definitions

  • the present invention relates to soft particulate superabsorbents, their use and products containing such superabsorbents and thermoplastics.
  • it also relates to the processing of superabsorbent-containing plastic mixtures by molding processes for thermoplastics such as extrusion.
  • Superabsorbents are known. Also, for such materials, terms such as “high swellable polymer” “hydrogel” (often used for the dry form), “hydrogel-forming polymer”, “water-absorbent polymer”, “absorbent gelling material”, “swellable resin”, “water-absorbent Resin “, water-absorbent polymer” or the like in common use.
  • crosslinked hydrophilic polymers in particular polymers of (co) polymerized hydrophilic monomers, graft (co) polymers of one or more hydrophilic monomers on a suitable graft, crosslinked cellulose or starch ethers, crosslinked carboxymethylcellulose, partially crosslinked polyalkylene oxide or in aqueous Liquid swellable natural products, such as guar derivatives, with superabsorbents based on partially neutralized acrylic acid are the most common.
  • the essential properties of superabsorbents are their ability to absorb a multiple of their own weight of aqueous liquids and to not release the liquid under some pressure.
  • the superabsorber which is used in the form of a dry powder, transforms into a gel when it absorbs liquid, with the usual absorption of water corresponding to a hydrogel.
  • Crosslinking is essential for synthetic superabsorbents and an important difference to conventional pure thickeners, as it leads to the insolubility of the polymers in water. Soluble substances would not be useful as superabsorbent.
  • the most important application of superabsorbers is the absorption of body fluids.
  • Superabsorbents are used, for example, in infant diapers, adult incontinence products or feminine hygiene products. Other fields of application are, for example, as water-retaining agents in agricultural horticulture, as water reservoirs for protection against fire, for liquid absorption in food packaging or, more generally, for the absorption of moisture.
  • Superabsorbents can absorb a multiple of their own weight of water and retain it under some pressure.
  • such a superabsorbent has a CRC ("Centrifuge Retention Capacity", measuring method see below) of at least 5 g / g, preferably at least 10 g / g and in a particularly preferred form at least 15 g / g.
  • CRC Chiptrifuge Retention Capacity
  • Swollen gel can hinder fluid transport to superabsorbers that are not yet swollen ("gel blocking") .
  • Good transport properties for liquids include, for example, hydrogels which have a high gel strength in the swollen state
  • Gels with only low gel strength are under an applied pressure (body pressure) deforms, clogs pores and prevents further absorption of liquid
  • Increased gel strength is usually achieved by a higher degree of cross-linking, which however reduces the absorption capacity of the product
  • An elegant method for increasing the gel strength is compared to increasing the degree of cross-linking on the surface of the superabsorbent particles
  • dried superabsorbent particles with average crosslinking density are usually additionally crosslinked in a thin surface ntik their particles subjected.
  • Acrylic acid-based superabsorbents which are most commonly used in the marketplace, are prepared by free-radical polymerization of acrylic acid in the presence of a crosslinker (the "internal crosslinker"), the acrylic acid before, after or partly before, partly after the polymerization
  • the polymer gel obtained in this way is comminuted (depending on the polymerization reactor used, this can be done simultaneously with the polymerization) and dried.
  • the dry powder obtained in this way (the "base polymer” or "polymer”) is neutralized to a certain degree.
  • Basispolymer is usually postcrosslinked on the surface of the particles by reacting with other crosslinkers such as organic crosslinkers or polyvalent cations, for example aluminum (usually as aluminum sulfate used) or both is implemented in order to produce a more crosslinked surface layer relative to the particle interior.
  • crosslinkers such as organic crosslinkers or polyvalent cations, for example aluminum (usually as aluminum sulfate used) or both is implemented in order to produce a more crosslinked surface layer relative to the particle interior.
  • No. 5,352,480 teaches methods for binding superabsorbents to fibers, inter alia with amino alcohols.
  • WO 03/104 543 A1 teaches that triethanolamine is preferably used to bind superabsorbents to fibers, with the triethanolamine simultaneously serving to increase the degree of neutralization of the superabsorbent.
  • WO 2009/060 062 A1 mentions the possible use of triethanolamine as a surface postcrosslinking agent for superabsorbents.
  • EP 725 084 A1 mentions triethanolamine as a possible polymerization regulator in the (optionally crosslinking) polymerization of ethylenically unsaturated monomers.
  • WO 99/44 648 A1 teaches the production of flexible superabsorbent foams in which a monomer mixture containing acrylic acid and triethanolamine as neutralizing agent is foamed and polymerized. According to the teaching of WO 00/52087 A1, this foaming takes place by injecting an inert gas into the monomer mixture and subsequent expansion.
  • WO 03/092 757 A1 discloses two possible uses of triethanolamine in superabsorbents.
  • triethanolamine is a plasticizer for a special case of superabsorbents, namely a mixture of a slightly crosslinked acid with a slightly crosslinked basic polymer, which are used according to this document in the form of a flexible layer.
  • the flexible layer may contain up to 20% by weight of a conventional SAP which is partially neutralized with common alkalis such as sodium hydroxide, potassium hydroxide or triethanolamine, the use of triethanolamine providing a plasticized conventional SAP which enhances the flexibility of the present invention
  • Absorber layer is not negatively influenced and may even contribute.
  • Such moldings can be produced by conventional methods of thermoplastic processing, such as extrusion, plastic injection molding, blow molding, deep drawing, calendering or pressing.
  • WO 03/022 316 indicates that certain particle size distributions of superabsorbents may be advantageous for individual applications, such as coextrusion with thermoplastics.
  • the superabsorbent itself is not a thermoplastic.
  • Superabsorbent particles are relatively hard or brittle when dry.
  • the brittle or, in any case, hard superabsorber particles in the mass plastified by heating during deformation disturb the processing of this mass.
  • One problem may be, for example, the abrasion of deformation tools. This occurs naturally especially where the thermoplastic composition is moved under pressure on a tool or by a tool.
  • Particularly susceptible are nozzles of all kinds, through which the thermoplastic composition is pressed, such as nozzles or mouthpieces of extruders.
  • a particulate superabsorbent based on at least one monoethylenically unsaturated monomer containing at least one acid group has been found, which is characterized in that at least 5 mol% of the acid groups have been neutralized with at least one tertiary alkanolamine.
  • This superabsorbent is characterized by the fact that it leads to fewer problems in processing as a component of thermoplastic materials and in particular to less abrasion of deformation tools. Furthermore, a process for the preparation of this superabsorbent was found, uses of this superabsorbent and moldings containing this superabsorber and process for their preparation.
  • the superabsorbers present in the mixture according to the invention can be prepared in different ways, for example by solution polymerization, suspension polymerization, dropwise or spray polymerization. Such methods are known.
  • To prepare conventional superabsorbents at least one monoethylenically unsaturated monomer containing at least one acid group is usually polymerized in the presence of a crosslinker.
  • An example of a currently commercially customary polymerization process for the preparation of acrylate superabsorbers is the aqueous solution polymerization of a monomer mixture containing a) at least one ethylenically unsaturated, acid group-carrying monomer, which is optionally present at least partially in the form of a salt,
  • 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 or their salts, such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, and itaconic acid or its salts. 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 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 monomer solution preferably contains at most 250 ppm by weight, preferably at most 130 ppm by weight, more preferably at most 70 ppm by weight and preferably at least 10 ppm by weight, more preferably at least 30 ppm by weight, in particular by 50% by weight.
  • hydroquinone half ethers based in each case on the unneutralized monomer a), wherein neutralized monomer a), ie a salt of the monomer a), is accounted for mathematically as an unneutralized monomer.
  • 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 radically copolymerized into the polymer chain, and functional groups which are covalenced with the acid groups of the monomer a). Furthermore, polyvalent metal salts which can form coordinative bonds with at least two acid groups of the monomer a) are also suitable as crosslinking agents 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 530 438 A1, di- and triacrylates, as in EP 547 847 A1, EP 559 476 A1 , EP 632 068 A1, WO 93/21237 A1, WO 2003/104299 A1, WO 2003/104300 A1, WO 2003/104301 A1 and DE 103 31 450 A1, mixed acrylates which, in addition to acrylate groups, contain further ethylenically unsaturated groups, such as in DE 103 31 456 A1 and
  • crosslinker mixtures such as in
  • Preferred crosslinkers b) are pentaerythritol triallyl ether, tetraallyloxyethane, methylenebismethacrylamide, trimethylolpropane triacrylate 10 to 20 times ethoxylated, trimethylolethane triacrylate 10 to 20 times ethoxylated, particularly preferably 15-times ethoxylated trimethylolpropane triacrylate, polyethylene glycol diacrylates having 4 to 30 ethylene oxide units in the polyethylene glycol chain , Trimethylolpropane triacrylate, di- and triacethene acrylates of the 3 to 30-fold ethoxylated glycerol, more preferably di- and triacrylate of the 10-20-fold ethoxylated glycerol, and triallylamine.
  • the polyesters which are not completely esterified with acrylic acid can also be present here as Michael adducts with themselves, as a result of which tetra-, penta- or even
  • 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 triacrylate of 3-times ethoxylated glycerol.
  • the amount of crosslinker b) is preferably from 0.05 to 1, 5 wt .-%, particularly preferably 0.1 to 1 wt .-%, most preferably 0.3 to 0.6 wt .-%, each based on Monomer a).
  • the centrifuge retention capacity (CRC) decreases and the absorbance increases under a pressure of 0.3 psi (AUL 0.3psi).
  • initiators c) it is possible to use all compounds which generate free radicals under the polymerization conditions, for example thermal initiators, redox initiators, photoinitiators.
  • Suitable redox initiators are sodium peroxodisulfate / ascorbic acid, hydrogen peroxide / ascorbic acid, sodium peroxodisulfate / sodium bisulfite and hydrogen peroxide / sodium bisulfite.
  • Preference is given to using mixtures of thermal initiators and redox initiators, such as sodium peroxodisulfate / hydrogen peroxide / ascorbic acid.
  • a reducing component but preferably a mixture of the sodium salt of 2-hydroxy-2-sulfinatoacetic acid, the disodium salt of 2-hydroxy-2-sulfonatoacetic acid and sodium bisulfite used (as Brüggolit ® FF6M or Brüggolit ® FF7, alternatively BRUGGOLITE ® FF6M or
  • acrylamide, methacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, maleic acid and maleic anhydride are ethylenically unsaturated, acid group-bearing monomers a) copolymerizable ethylenically unsaturated monomers d).
  • Water-soluble polymers e) may be polyvinyl alcohol, polyvinylpyrrolidone, starch, starch derivatives, modified cellulose, such as methylcellulose or hydroxyethylcellulose, Gelatin, polyglycols or polyacrylic acids, preferably starch, starch derivatives and modified cellulose.
  • an aqueous monomer solution is used.
  • the water content of the monomer solution is preferably from 40 to 75 wt .-%, particularly preferably from 45 to 70 wt .-%, most preferably from 50 to 65 wt .-%.
  • monomer suspensions i. to use supersaturated monomer solutions. With increasing water content, the energy expenditure increases during the subsequent drying and with decreasing water content, the heat of polymerization can only be sufficiently dissipated.
  • the monomer solution may be polymerized prior to polymerization by inerting, i. Flow through with an inert gas, preferably nitrogen or carbon dioxide, are freed of dissolved oxygen.
  • an inert gas preferably nitrogen or carbon dioxide
  • 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, most preferably less than 0.1 ppm by weight.
  • the monomer mixture may contain other components. Examples of other components used in such monomer mixtures include chelating agents to keep metal ions in solution.
  • Suitable polymerization reactors are, for example, kneading reactors or belt reactors.
  • the polymer gel formed in the polymerization of an aqueous monomer solution or suspension is comminuted continuously by, for example, counter-rotating stirring shafts, as described in WO 2001/38402 A1.
  • the polymerization on the belt is described, for example, in DE 38 25 366 A1 and US Pat. No. 6,241,928.
  • Polymerization in a belt reactor produces a polymer gel which must be comminuted in a further process step, for example in one
  • Meat grinder, extruder or kneader may also be prepared by suspension, spray or drop polymerization techniques.
  • the acid groups of the polymer gels obtained are usually partially neutralized.
  • the neutralization is preferably carried out at the stage of the monomers, in other words, salts of the acid group-carrying monomers or, strictly speaking, a mixture of acid group-carrying monomers and salts of the acid group-carrying monomers ("partially neutralized acid") are used as component a) in the polymerization usually by mixing the neutralizing agent as an aqueous solution or preferably also as a solid in the monomer mixture intended for the polymerization or preferably in the acid group-carrying monomer or a solution thereof.
  • At least 5 mol% preferably at least 10 mol% and more preferably at least 20 mol%, at least 40 mol% or at least 50 mol% and generally at most 95 mol%, preferably at most 85 mol -% and in a particularly preferred form at most 80 mol%.
  • the usual neutralizing agents can be used. These are preferably alkali metal hydroxides, alkali metal oxides, alkali metal carbonates or alkali metal bicarbonates and mixtures thereof. Instead of alkali metal salts and ammonium salts can be used. Sodium and potassium are particularly preferred as alkali metal cations, but most preferred are sodium hydroxide, sodium carbonate, sodium bicarbonate and primary, secondary and tertiary alkanolamines and mixtures of these neutralizing agents.
  • the superabsorbent according to the invention contains at least one tertiary alkanolamine in addition to or exclusively as a neutralizing agent. Generally, at least 5 mole percent of the acid groups in the superabsorbent are neutralized by tertiary alkanolamine, preferably at least 10 percent, and most preferably at least 20 mole percent.
  • the superabsorbent may contain additional neutralizing agent to adjust the overall desired degree of neutralization (i.e., the proportion of neutralized acid groups (in moles) of all acid groups).
  • the superabsorbent may be partially neutralized with alkanolamine and partially with alkali, such as sodium or potassium.
  • the overall degree of neutralization in the superabsorber according to the invention is generally at least 20 mol%, preferably at least 50 mol% and more preferably at least 60 mol% and generally at most 95 mol%, preferably at most 85 mol% and most preferably at most 80 mol%.
  • the superabsorbent contains substantially no neutralizing agent other than tertiary alkanolamine, i. with the exception of unavoidable impurities or insignificant amounts of other neutralizing agents is neutralized with tertiary alkanolamine.
  • the superabsorbent contains no neutralizing agent other than tertiary alkanolamine except for inevitable impurities.
  • tertiary alkanolamine can be partially neutralized at the monomer stage and the desired final degree of neutralization can be adjusted with primary or secondary alkanolamine or alkalis such as sodium hydroxide after polymerization, or this order of addition can be reversed.
  • the polymer gel is preferably mechanically comminuted, for example by means of an extruder, wherein the neutralizing agent can be sprayed on, sprinkled or poured and then mixed thoroughly.
  • the gel mass obtained can be extruded several times for homogenization.
  • This post-neutralization is preferably carried out before drying.
  • the monomer a) is a mixture of as much mol% salt of the acid group-carrying monomer as the desired degree of neutralization and the rest
  • the alkanolamines can be used in neutralization at the stage of the monomer or in the post-neutralization of the polymer neat or as a solution in solvents or solvent mixtures.
  • solvent for alkanolamines for example, water, methanol, ethanol, iso-propanol, or acetone may be used, with preference being given to water or use without a solvent.
  • the tertiary alkanolamines used may be monovalent, polyvalent or polyfunctional bases.
  • the alkanolamines may carry, in addition to their amino and hydroxyl groups, other functional groups such as esters, urethane, ethers, thioethers, urea, etc.
  • low molecular weight compounds such as triethanolamine, methyldiethanolamine, dimethylethanolamine, N-hydroxyethylmorpholine, dimethylaminodiglycol, N, N, N ', N'-tetra (hydroxyethyl) ethylenediamine, N, N, N', N'-tetra- (hydroxypropyl) ethylenediamine, dimethylaminotriglycol, diethylaminoethanol, 3-dimethylamino-1,2-propanediol, triisopropanolamine, diisopropylaminoethanol, choline hydroxide, choline carbonate or else oligomers or polymers such as, for example, amino-containing polymers or condensates reacted with ethylene oxide, propylene oxide, glycidol or other epoxides, Reaction products of at least bifunctional, lower molecular weight alkanolamines with at least bifunctional reagents capable of
  • Tertiary alkanolamines which are preferably used are triethanolamine, methyldiethanolamine, dimethylaminodiglycol, dimethylethanolamine and N, N, N ', N'-tetra- (hydroxyethyl) ethylenediamine. Triethanolamine is most preferred.
  • the content of iron is generally below 10 ppm by weight, preferably below 2 ppm by weight and most preferably below 1 ppm by weight. Just- Thus, a low content of chloride and anions of oxygen acids of the chlorine is desired.
  • the polymer gel obtained from the aqueous solution polymerization and optionally subsequent neutralization is then preferably dried with a belt dryer until the residual moisture content is preferably 0.5 to 15 wt .-%, particularly preferably 1 to 10 wt .-%, most preferably 2 to 8 wt .-%, is (measurement method for the residual moisture or water content, see below). If the residual moisture content is too high, the dried polymer gel has too low a glass transition temperature Tg and is difficult to process further. If the residual moisture content is too low, the dried polymer gel is too brittle and in the subsequent comminution steps undesirably large amounts of polymer particles with too small particle size ("fines") are produced. %, preferably from 30 to 80 wt .-%, particularly preferably from 35 to 70 wt .-%, most preferably from 40 to
  • a fluidized bed dryer or a heatable mixer with mechanical mixing element such as a paddle dryer or a similar dryer can be used with differently shaped mixing tools.
  • the dryer may be operated under nitrogen or other non-oxidizing inert gas, or at least a reduced partial pressure of oxygen, to prevent oxidative yellowing.
  • nitrogen or other non-oxidizing inert gas or at least a reduced partial pressure of oxygen, to prevent oxidative yellowing.
  • sufficient ventilation and removal of the water vapor also leads to an acceptable product.
  • Advantageous in terms of color and product quality is usually the shortest possible drying time.
  • a temperature of the gas used for drying of at least 50 0 C preferably at least 80 0 C and more preferably at least 100 0 C., and generally not exceeding 250 0 C, preferably at most Set 200 0 C and in a particularly preferred form of at most 180 0 C.
  • Common belt dryers often have multiple chambers, the temperature in these chambers may be different. For each type of dryer, the operating conditions must be selected as a whole in a known manner so that the desired drying result is achieved.
  • the residual monomer content in the polymer particles also decreases and the last residues of the initiator are destroyed.
  • the dried polymer gel is then ground and classified, wherein for grinding usually one- or multi-stage roller mills, preferably two- or three-stage roller mills, pin mills, hammer mills or vibratory mills can be used.
  • Oversized gel lumps which are often not dried in the interior, are rubber-elastic, lead to grinding problems and are preferably separated before grinding, which can easily be achieved by air classification or a sieve ("protective sieve" for the mill) is in the face of used mill to be chosen so that as possible no interference from oversized, rubbery particles occur.
  • a particulate superabsorber ie a superabsorber in the form of individual particles, is produced from the dried polymer gel (which may already be crumbly, depending on the polymerisation apparatus used and any comminution apparatuses used after the reactor).
  • the superabsorbent is usually subsequently classified to obtain a product of the desired particle size distribution. This is done by customary classification methods, for example air classification or sieving through screens of suitable mesh size. Typical sieve cuts for hygiene applications of superabsorbents are at most 1000 ⁇ m, preferably at most 900 ⁇ m, particularly preferably at most 850 ⁇ m and very particularly preferably at most 800 ⁇ m. For example, sieves with 700 ⁇ m, 650 ⁇ m or 600 ⁇ m mesh size are used.
  • the separated coarse-grained polymer particles (“oversize") can be fed back to the grinding and screening circuit for cost optimization or further processed separately.
  • Fine-particle polymer particles are therefore separated off in this classification. This can, if sieved, conveniently by a sieve with a mesh size of at most 300 microns, preferably at most 200 microns, more preferably at most 150 microns and most preferably not more than 100 microns.
  • the separated fine-grained polymer particles (“undersize” or “fines") can be fed back to the monomer stream, the polymerizing gel, or the polymerized gel before drying the gel for cost optimization.
  • the average particle size of the polymer particles separated as a product fraction is generally at least 200 .mu.m, preferably at least 250 .mu.m and preferably at least 300 .mu.m and generally at most 600 .mu.m and preferably at most 500 .mu.m for hygiene applications.
  • the proportion of particles having a particle size of at least 150 microns is generally at least 90 wt .-%, preferably at least 95 wt .-% and most preferably at least 98 wt .-%.
  • the proportion of particles with a particle size of at most 850 microns is generally at least 90 wt .-%, preferably at least 95 wt .-% and most preferably at least 98 wt .-%.
  • a different particle size distribution can be selected.
  • the same particle size is used for use in deformation process for thermoplastic mixtures containing the superabsorber as previously with non-inventive superabsorbent. This is often smaller than usual in hygiene applications.
  • a sieve cut of 5 to 50 ⁇ m or even 50 to 150 ⁇ m is often selected.
  • the particle size distribution is predetermined by the choice of process parameters.
  • particulate superabsorbents of the desired particle size are formed directly, so that milling and sieving steps can often be dispensed with, and in some processes (in particular in the case of spray or dropletization polymerization), a separate drying step can often be dispensed with.
  • a separate drying step can often be dispensed with.
  • the polymer produced as described so far has superabsorbent properties and falls under the term "superabsorbent.” Its CRC is typically comparatively high, while its AUL or SFC is comparatively low often called “base polymer” or “base polymer”.
  • the superabsorbent particles are postcrosslinked on their surface to further improve the properties, especially increase the AUL and SFC values (with the CRC value decreases).
  • Postcrosslinking of superabsorbents is known per se.
  • Suitable postcrosslinkers are compounds which contain groups which can form bonds with at least two functional groups of the superabsorbent particles.
  • Acrylic acid / sodium acrylate-based superabsorbents which are prevalent on the market are suitable surface postcrosslinker compounds which contain groups which can form bonds with at least two carboxylate groups.
  • Preferred postcrosslinkers are:
  • Di- or polyepoxides for example di- or polyglycidyl compounds, such as phosphonic acid diglycidyl esters, ethylene glycol diglycidyl ethers or bischlorohydrin ethers of polyalkylene glycols,
  • Polyaziridines compounds containing aziridine units based on polyethers or substituted hydrocarbons, for example bis-N-aziridino methane,
  • Polyols such as ethylene glycol, 1, 2-propanediol, 1, 4-butanediol, glycerol, methyltriglycol, polyethylene glycols having an average molecular weight Mw of 200 to 10,000, di- and polyglycerol, pentaerythritol, sorbitol, the ethoxylates of these polyols and their
  • Esters with carboxylic acids or carbonic acid such as ethylene carbonate or propylene carbonate, Carbonic acid derivatives such as urea, thiourea, guanidine, dicyandiamide, 2-oxazolidinone and its derivatives, bisoxazoline, polyoxazolines, di- and polyisocyanates,
  • Di- and poly-N-methylol compounds such as, for example, methylenebis (N-methylolmethacrylamide) or melamine-formaldehyde resins,
  • Particularly suitable postcrosslinkers are di- or polyglycidyl compounds such as ethylene glycol diglycidyl ether, the reaction products of polyamidoamines with epichlorohydrin, 2-oxazolidinone and N-hydroxyethyl-2-oxazolidinone.
  • the postcrosslinker is generally used in an amount of at least
  • 0.001 wt .-% preferably of at least 0.02 wt .-%, in a particularly preferred form of at least 0.05 wt.% And generally at most 2 wt .-%, preferably at most 1 wt .-%, in particularly preferred Form at most
  • wt .-% for example, at most 0.15 wt .-% or at most 0.095 wt .-% used, in each case based on the mass of the base polymer thus acted upon.
  • the postcrosslinking is usually carried out by spraying a solution of the postcrosslinker onto the dried base polymer particles. Subsequent to the spraying, the polymer particles coated with postcrosslinker are thermally dried, it being possible for the postcrosslinking reaction to take place both before and during the drying. If surface postcrosslinkers with polymerizable groups are used, the surface postcrosslinking can also be effected by free-radically induced polymerization of such groups by means of conventional free-radical formers or else by means of high-energy radiation such as UV light. This may be done in parallel or instead of using postcrosslinkers that form covalent or ionic bonds to functional groups on the surface of the base polymer particles.
  • the solvent used for the surface postcrosslinker is a customary suitable solvent, for example water, alcohols, DMF, DMSO and mixtures thereof. Particularly preferred are water and water / alcohol mixtures such as water / methanol, water / 1, 2-propanediol and water / 1, 3-propanediol.
  • the concentration of the postcrosslinker in the postcrosslinker solution is typically schate 1 to 20 wt .-%, preferably 1, 5 to 10 wt .-%, particularly preferably 2 to 5 wt .-%, based on the Nachvernetzerlinger.
  • the spraying of the postcrosslinker solution is preferably carried out in mixers with moving mixing tools, such as screw mixers, disk, paddle or paddle mixers or mixers with other mixing tools.
  • moving mixing tools such as screw mixers, disk, paddle or paddle mixers or mixers with other mixing tools.
  • vertical mixers particularly preferred are vertical mixers.
  • Suitable mixers are flocking for example as a plow mixer ® Gebr Lödige Maschinenbau GmbH, Elsener Street. 7 - 9, 33102 Paderborn, Germany, or ® as Schugi ® Flexomix mixer, Vrieco-Nauta ® mixer or blender Turbulizer® ® from Hosokawa Micron BV, Gildenstraat 26, 7000 AB Doetinchem, The Netherlands.
  • the anionic, cationic, nonionic and amphoteric surfactants are suitable as Deagglomerationstoskar, but are preferred for Hautver Strukturkeitshuntn nonionic and amphoteric surfactants.
  • the surfactant may also contain nitrogen.
  • sorbitan monoesters such as sorbitan monococoate and sorbitan monolaurate, or ethoxylated variants thereof, such as polysorbate 20® , are added.
  • deagglomerating assistants the ethoxylated and alkoxylated derivatives of 2-propylheptanol, which are marketed under the brand names Lutensol® XL ® and Lutensol XP ® (BASF SE, Carl-Bosch-Strckee 38, 67056 Ludwigshafen, Germany).
  • the deagglomerating assistant can be metered separately or added to the postcrosslinker solution.
  • the deagglomerating aid is simply added to the postcrosslinker solution.
  • the amount used of the deagglomerating assistant based on the base polymer is, for example, 0 to 0.1% by weight, preferably 0 to 0.01% by weight, particularly preferably 0 to 0.002% by weight.
  • the deagglomerating assistant is metered such that the surface tension of a ticassri- gen extract of the swollen base polymer and / or of the swollen postcrosslinked superabsorbent at 23 0 C of at least 0.060 N / m, preferably at least 0.062 N / m, more preferably at least 0.065 N / m, and advantageously at most 0.072 N / m.
  • the actual surface postcrosslinking by reaction of the surface postcrosslinker with functional groups on the surface of the base polymer particles is usually carried out by heating the base polymer wetted with surface postcrosslinker solution, usually called “drying" (but not to be confused with the above-described drying of the polymer gel from the polymerization) drying can be carried out in the mixer itself, by heating the jacket, by heat exchange surfaces or by blowing warm gases in. Simultaneous addition of the superabsorbent with surface postcrosslinker and drying can be carried out, for example, in a fluidized bed reactor. carried out dryer. However, the drying is usually carried out in a downstream dryer, such as a tray dryer, a rotary kiln, a paddle or disc dryer or a heated screw. Suitable dryers are, for example, as Solidair ® or Torusdisc ® -T Rockner from Bepex International LLC, 333 NE Taft Street, Minneapolis, MN 55413, USA, or as a paddle or
  • Paddle dryer or as a fluidized bed dryer from Nara Machinery Co., Ltd., branch office Europe, Europaallee 46, 50226 Frechen, Germany available.
  • Preferred drying temperatures are in the range 100 to 250 0 C, preferably 120 to 220 0 C, particularly preferably 130 to 210 ° C most preferably 150 to 200 0 C. by weight
  • the preferred residence time at this temperature in the reaction mixer or dryer is preferably at least 10 minutes , more preferably at least 20 minutes, most preferably at least 30 minutes, and usually at most 60 minutes.
  • the drying is conducted in such a way that the superabsorber has a residual moisture content of generally at least 0.1% by weight, preferably at least 0.2% by weight and in a particularly preferred form at least 0.5% by weight, and also Generally at most 15% by weight, preferably at most 10% by weight and in a particularly preferred form at most 8% by weight.
  • the hydrophilicity of the particle surface of the base polymers is modified by the formation of complexes.
  • the formation of the complexes on the outer shell of the particles is carried out by spraying solutions of divalent or polyvalent cations, wherein the cations can react with the acid groups of the polymer to form complexes.
  • divalent or polyvalent cations are polymers which are formally wholly or partially composed of vinylamine monomers, such as partially or completely hydrolyzed polyvinylamide (so-called "polyvinylamine”), whose amine groups are always partially protonated to ammonium groups, even at very high pH values, or metal cations such as Mg 2+ , Ca 2+ , Al 3+ , Sc 3+ , Ti 4+ , Mn 2+ , Fe 2+ / 3+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ , Y 3+ , Zr 4+ , La 3+ , Ce 4+ , Hf 4+ , and Au 3+ Preferred metal cations are Mg 2+ , Ca 2+ , Al 3+ , Ti 4+ , Zr 4+ and La 3+ , and particularly preferred metal cations are Al 3+ , Ti 4+ and Zr 4+
  • the metal cations can be used both alone and in admi
  • metal salts which have sufficient solubility in water are suitable
  • metal salts with weakly complexing anions such as chloride, nitrate and Sul fat, hydrogen sulfate, carbonate, bicarbonate, nitrate, phosphate, hydrogen phosphate, dihydrogen phosphate and carboxylate, such as acetate and lactate.
  • aluminum sulfate is used.
  • solvents for the metal salts water, alcohols, DMF, DMSO and mixtures of these components can be used.
  • water and water / alcohol mixtures such as water / methanol, water / 1, 2-propanediol and water / 1, 3-propanediol.
  • the treatment of the base polymer with solution of a di- or polyvalent cation is carried out in the same way as with surface postcrosslinkers, including the optional drying step.
  • Surface postcrosslinker and polyvalent cation can be sprayed in a common solution or as separate solutions.
  • the spraying of the metal salt solution onto the superabsorbent particles can be carried out both before and after the surface postcrosslinking.
  • the spraying of the metal salt solution is carried out in the same step by spraying the crosslinker solution, wherein both solutions are sprayed separately successively or simultaneously via two nozzles, or crosslinker and metal salt solution can be sprayed together via a nozzle ,
  • a drying step is carried out after the surface postcrosslinking and / or treatment with complexing agent, it is advantageous, but not absolutely necessary, to cool the product after drying.
  • the cooling can be continuous or discontinuous, conveniently the product is continuously conveyed to a dryer downstream cooler.
  • Any apparatus known for removing heat from powdered solids may be used for this purpose, in particular any apparatus mentioned above as a drying apparatus, unless it is supplied with a heating medium but with a cooling medium, such as cooling water, so that over the walls and depending on the construction no heat is also introduced into the superabsorber via the stirring elements or other heat exchange surfaces, but is removed therefrom.
  • coolers in which the product is moved ie cooled mixers, for example blade coolers, disk coolers or paddle coolers.
  • the superabsorbent can also be cooled in the fluidized bed by blowing in a cooled gas such as cold air. The conditions of the cooling are adjusted so that a superabsorbent is obtained with the temperature desired for further processing.
  • an average residence time in the condenser of generally at least 1 minute, preferably at least 3 minutes and more preferably at least 5 minutes and generally at most 6 hours, preferably at most 2 hours and more preferably at most 1 hour is set and the cooling capacity is so in that the product obtained has a temperature of generally at least 0 ° C, preferably at least 10 ° C and more preferably at least 20 ° C and generally at most 100 ° C, preferably at most 80 ° C and most preferably at most 60 0 C.
  • the surface-postcrosslinked superabsorbent or the mixture is optionally ground and / or sieved in a conventional manner. Milling is typically not required here, but mostly the setting of the desired particle size distribution of the product requires the screening of formed agglomerates or fine particles. Agglomerates and fine particles are either discarded or preferably recycled to the process in a known manner and at a suitable point; Agglomerates after Shredding.
  • the particle sizes desired for surface postcrosslinked superabsorbents are the same as for base polymers.
  • any known additives or coatings such as film-forming polymers, thermoplastic polymers, dendrimers, polycationic polymers (such as polyvinylamine, polyethylenimine or polyallylamine), water-insoluble polyvalent metal salts, such as magnesium carbonate, magnesium oxide, may optionally be applied to the surface of the SAP particles in any process step ,
  • Magnesium hydroxide, calcium carbonate, calcium sulfate or calcium phosphate all water-soluble mono- or polyvalent metal salts known to those skilled in the art, such as, for example, aluminum sulfate, sodium, potassium, zirconium or iron salts, or hydrophilic inorganic particles, such as clay minerals, fumed silica, colloidal silica sols such as Levasil ® , titanium dioxide, aluminum oxide and magnesium oxide, in addition to be applied.
  • alkali metal salts examples include sodium and potassium sulfate, sodium and potassium lactates, citrates, sorbates.
  • additional effects for example a reduced caking tendency of the end product or of the intermediate product in the respective process step of the production method, improved processing properties or a further increased liquid conductivity (SFC) can be achieved.
  • the additives are used and sprayed in the form of dispersions, then they are preferably used as aqueous dispersions, and it is preferably additionally applied a dedusting agent for fixing the additive on the surface of the superabsorbent.
  • the dedusting agent is then added either directly to the dispersion of the inorganic powder additive, optionally it may also be added as a separate solution before, during, or after the inorganic powdery additive has been applied by spraying.
  • the most convenient is the simultaneous spraying of Nachvernetzungsmittel, dedusting and powdery inorganic additive in the post-crosslinking.
  • the dedusting agent is added separately in the cooler, for example by spraying from above, below or from the side.
  • Particularly suitable dedusting agents which can also be used for fixing powdery inorganic additives to the surface of the SAP particles are polyethylene glycols having a molecular weight of 400 to 20 000 g / mol, polyglycerol, 3 to 100-fold ethoxylated polyols, such as trimethylolpropane, Glycerin, sorbitol and neopentyl glycol.
  • Particularly suitable are lolpropan 7- to 20-tuply ethoxylated glycerol or trimethylolpropane, for example Polyol TP 70 ® (Perstorp, SE). The latter have the particular advantage that they only insignificantly reduce the surface tension of an aqueous extract of the superabsorbent particles.
  • All coatings, solids, additives and auxiliaries can each be added in separate process steps, but usually the most convenient method is to use them. if they are not added during the displacement of the base polymer with surface postcrosslinking agent, add it to the superabsorber in the cooler, such as by spraying a solution or adding it in finely divided solid or in liquid form.
  • the superabsorbent according to the invention generally has a centrifuge retention capacity (CRC) of at least 5 g / g, preferably of at least 10 g / g and in a particularly preferred form of at least 20 g / g. Further suitable minimum values of the CRC are, for example, 25 g / g, 30 g / g or 35 g / g. Usually it is not above 40 g / g. A typical range of CRC for surface postcrosslinked superabsorbents is from 28 to 33 g / g.
  • the superabsorbent according to the invention typically has an absorption under pressure (AUL 0.7 psi, measuring method see below) of at least 18 g / g, preferably at least 20 g / g, more preferably at least 22 g / g, particularly preferably at least 23 g / g, very particularly preferably at least 24 g / g and usually not more than 30 g / g.
  • AUL 0.7 psi absorption under pressure
  • the superabsorbent according to the invention further has a saline flow conductivity (SFC measurement method s. Below) of at least 10x10 "7 cm 3 sec / g, preferably at least 30x10" 7 cm 3 sec / g, preferably at least 50x10 "7 cm 3 s / g, particularly preferably at least 80x10 "7 cm 3 sec / g, most preferably at least 100x10" 7 cm 3 s / g and usually not above 1000x10 "7 cm 3 s / g.
  • SFC measurement method s below
  • the superabsorbent according to the invention can be used for any purpose to which known superabsorbers are also used.
  • the superabsorbent mixture according to the invention can be used in particular in all fields of technology in which liquids, in particular water or aqueous solutions, are absorbed.
  • These areas are for example storage, packaging, transport (as components of packaging material for water or moisture sensitive articles, such as flower transport, as well as protection against mechanical effects); Animal hygiene (in cat litter); Food packaging (transport of fish, fresh meat, absorption of water, blood in fresh fish or meat packaging); Medicine (wound plasters, water-absorbing material for burn dressings or for other weeping wounds), cosmetics (carrier material for pharma- ceuticals and drugs, rheumatic patches, ultrasound gel, cooling gel, cosmetic thickener, sunscreen); Thickener for oil / water or water / oil emulsions; Textiles (moisture regulation in textiles, shoe inserts, for evaporative cooling, for example in protective clothing, gloves, headbands); chemical-technical applications (as a catalyst for organic reactions, for the immobilization of large functional molecules such as enzymes, as adhesives in agglomerations, heat storage, filtration aids, hydrophilic components in polymer laminates, dispersants, condenser); as an aid in
  • thermoplastic mixtures in particular of such thermoplastic mixtures, which are provided for deformation into moldings.
  • the thermoplastic mixtures according to the invention, processes for their processing and the molded articles produced therewith differ from known ones in that they contain the superabsorber according to the invention or that the superabsorber according to the invention is present.
  • thermoplastic mixtures containing superabsorbents are known per se. They usually contain a proportion of a thermoplastic polymer, for example polyolefins such as polyethylene or polypropylene, polystyrene, polyesters such as polyethylene terephthalate or polybutylene terephthalate, polyvinyl chloride, polyamide, polycarbonate or polyurethane or copolymers, for example ethylene-vinyl acetate copolymer or acrylonitrile-butadiene-styrene copolymer , or a mixture of such polymers and / or copolymers.
  • the proportion of thermoplastic in the mixture must be at least high enough so that the mass as a whole can be processed like a thermoplastic.
  • thermoplastic mixture also contains the superabsorbent according to the invention. Its content is at least high enough to achieve the desired water-absorbing properties.
  • the thermoplastic mixture may contain further fractions which impart desired properties to it and / or to the molded article produced therefrom.
  • fillers such as inorganic fillers, for example inorganic oxides such as silicon, aluminum, titanium or zirconium oxides, carbon blacks, elastomers, particulate elastomers such as rubber particles or any other additive known for such purposes.
  • the mixture according to the invention is prepared in the usual way and processed into moldings.
  • the thermoplastic mixture is generally produced, made deformable by heating and then deformed.
  • the thermoplastic mixture can be made before deformation but also during deformation. If the mixture is prepared before deformation, usually the thermoplastic is melted and the other components are mixed.
  • the mixture can then be directly deformed or cooled and formed into semifinished product.
  • Such semifinished product for example granules
  • the mixture can also be produced during the deformation, for example by feeding a thermoplastic to an extruder and feeding the other components at different points of the extruder. It is also possible to pre-mix parts of the intended final composition and to add the remaining components during deformation. All these are known measures of thermoplastic processing.
  • the final composition of the desired shaped article may also be possible and desirable to adjust the final composition of the desired shaped article only after deformation.
  • the superabsorber after the actual deformation - such as the production of a thermoplastic film - are applied to this.
  • thermoforming Deformation of the thermoplastic blend is accomplished by any known method of thermoforming. Examples include extrusion, spraying, blow molding, deep drawing, calendering or pressing. A method for which the superabsorbent according to the invention is particularly suitable is extrusion. By extrusion almost any shapes can be produced, including films.
  • Another object of the invention are moldings of a thermoplastic mixture, wherein a superabsorbent according to the invention is a constituent of the mixture.
  • the superabsorbent is tested using the test methods described below.
  • the "WSP” standard test methods described below are described in: “Standard Test Methods for the Nonwovens Industry", 2005 edition, co-edited by the Worldwide Strategy Partners EDANA (European Disposables and Nonwovens Association, Avenue Eugene Plasky). 157, 1030 Brussels, Belgium, www.edana.org) and INDA (Association of the Nonwoven Fabrics Industry, 1100 Crescent Green, Suite 1 15, Cary, North Carolina 27518, USA, www.inda.org). This publication is available from EDANA or INDA. All measurements described below should be performed at an ambient temperature of 23 ⁇ 2 ° C and a relative humidity of 50 ⁇ 10%, unless otherwise specified. The superabsorbent particles are thoroughly mixed before measurement, unless stated otherwise.
  • the centrifuge retention capacity of the superabsorbent is determined according to the standard test method no. WSP 241.5-02 "Centrifuge Retention Capacity".
  • the absorption under a pressure of 4826 Pa (0.7 psi) of the superabsorbent is determined analogously to the standard test method no. WSP 242.2-05 "absorption under pressure", but a weight of 49 g / cm 2 (leads to a pressure of 0.7 psi) instead of a weight of 21 g / cm 2 (leading to a pressure of 0.3 psi) is used.
  • GLP Gel Layer Permeability
  • AGM a swollen gel layer of superabsorbent particles
  • Fluid transfer is calculated as follows:
  • Moisture content of the superabsorber (residual moisture, water content)
  • the water content of the superabsorbent particles is determined according to the standard test method no. WSP 230.2-05 "Moisture Content”.
  • the particle size of the product fraction is determined according to the standard test method no. WSP 220.2-05 "Particle Size Distribution".

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Abstract

L'invention concerne des polymères superabsorbants sous forme de particules à base d'au moins un monomère monoéthyléniquement insaturé contenant au moins un groupe acide, dans lesquels au moins 5% en mole des groupes acides sont neutralisés par au moins un alcanolamine tertiaire. Ces polymères superabsorbants conviennent en particulier comme constituants superabsorbants dans des mélanges thermoplastiques qui sont façonnés en corps moulés contenant des superabsorbants par des procédés de formage connus pour thermoplastiques.
EP10740677A 2009-08-25 2010-08-11 Polymères superabsorbants souples sous forme de particules et leur utilisation Withdrawn EP2470572A1 (fr)

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WO2011023536A1 (fr) 2011-03-03
US20120157634A1 (en) 2012-06-21
CN102482370A (zh) 2012-05-30

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