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WO2011032876A1 - Superabsorbant à stabilité de couleur - Google Patents

Superabsorbant à stabilité de couleur Download PDF

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Publication number
WO2011032876A1
WO2011032876A1 PCT/EP2010/063199 EP2010063199W WO2011032876A1 WO 2011032876 A1 WO2011032876 A1 WO 2011032876A1 EP 2010063199 W EP2010063199 W EP 2010063199W WO 2011032876 A1 WO2011032876 A1 WO 2011032876A1
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WO
WIPO (PCT)
Prior art keywords
acid
superabsorber
superabsorbent
water
weight
Prior art date
Application number
PCT/EP2010/063199
Other languages
German (de)
English (en)
Inventor
Virginie Bette
Norbert Herfert
Iran Otero Martinez
Original Assignee
Basf Se
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Priority to BR112012005901A priority Critical patent/BR112012005901A2/pt
Priority to JP2012529215A priority patent/JP2013504674A/ja
Priority to CN2010800414261A priority patent/CN102597082A/zh
Publication of WO2011032876A1 publication Critical patent/WO2011032876A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates

Definitions

  • the present invention relates to a color-stable superabsorber, a process for its preparation and its use and hygiene articles containing it.
  • a color-stable superabsorber is to be understood as meaning a superabsorber which does not discolor or only in a comparatively small extent when stored under elevated temperature and atmospheric humidity.
  • 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”, These are crosslinked hydrophilic polymers, in particular polymers of (co) polymerized hydrophilic monomers, graft (co) polymers of one or more hydrophilic monomers on a suitable graft base, crosslinked cellulose or starch ethers, crosslinked carboxymethylcellulose partially cross-linked polyalkylene oxide or natural products swellable in aqueous liquids, such as guar derivatives, with water-absorbing polymers based on partially neutralized acrylic acid being the most widespread.
  • the essential properties of superabsorbents are their ability to multiply their own weight of aqueous liquid absorb the fluid and even under some pressure not to give the liquid again.
  • the superabsorber which is used in the form of a dry powder, transforms into a gel when it absorbs liquid, and accordingly turns into a hydrogel during normal water absorption.
  • 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 superabsorbents 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, the water-retaining agents in agricultural horticulture, as water storage 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 superabsorber 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
  • AUL absorption under load
  • AAP absorption against pressure
  • Swollen gel can hinder liquid transport to superabsorbers that have 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 in the superabsorbent / cellulose fiber absorbent body and thus prevents further absorption of fluid.
  • a higher 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 represents the increase in the degree of crosslinking on the surface of the superabsorbent particles in relation to the interior of the particles.
  • dried superabsorbent particles having an average crosslinking density are usually introduced he subjected additional crosslinking in a thin surface layer of their particles.
  • Surface postcrosslinking increases the crosslink density in the shell of the superabsorbent particles, raising the absorption under pressure to a higher level. While the absorption capacity in the surface layer of the superabsorbent particles decreases, their core has an improved absorption capacity compared to the shell due to the presence of mobile polymer chains, so that the shell construction ensures improved fluid transfer without gel blocking occurring. It is also known to produce super-crosslinked superabsorbers overall and to subsequently reduce the degree of crosslinking in the interior of the particles compared to an outer shell of the particles.
  • 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.
  • a common problem with superabsorbents is discoloration, which occurs when storing under higher temperature or higher humidity. Such conditions often occur during storage of superabsorbers in tropical or subtropical countries. Under such conditions, superabsorbents tend to yellow, they may even take on brown or almost black coloring. This discoloration of the actually colorless superabsorbent powder is unsightly and undesirable because it is particularly visible in the desired thin hygiene products and
  • WO 2008/055856 A1 teaches the avoidance of discolorations of a superabsorber which are caused by excessively high iron content of the sodium hydroxide solution used to partially neutralize the acrylic acid in the preparation of the superabsorber by adding phosphoric acid or phosphate salts.
  • JP 05/086 251 A teaches the use of phosphoric acid derivatives or salts thereof, in particular 1-hydroxyethylidene-1, 1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) or their alkali metal or ammonium salts as stabilizers of superabsorbers against discoloration.
  • WO 03/059 962 A1 or the equivalent patent application US 2005/0085604 A1 discloses the use of The use of metal chelating agents in any step of the superabsorbent production and the addition of a reducing or oxidizing agent before drying of the aqueous polymer as measures against discoloration.
  • WO 03/014 172 A2 relates to the production of superabsorbers from highly pure acrylic acid, which has been freed to prevent discoloration of the superabsorbent in particular of aldehydes.
  • WO 00/55245 A1 teaches the stabilization of superabsorbents against discoloration by treatment with an inorganic reducing agent and optionally a metal salt, such as an alkaline earth salt, which is added after the polymerization.
  • the inorganic reducing agent is typically a hypophosphite, phosphite, bisulfite or sulfite.
  • the metal salt is typically a colorless (the property "colorless” is often simply called “white”), phosphate, acetate or lactate, but not a halide. According to the teaching of WO 2006/058 682, discolorations of superabsorbents are avoided when the drying and the post-crosslinking reaction are carried out in an atmosphere which is substantially free of oxidizing gases.
  • EP 505 163 A1 discloses the use of a combination of surface-active substance and a compound which adds to double bonds, for example unsubstituted or substituted alkyl- or arylsulfinic acids or salts thereof for reducing residual monomers in superabsorbers.
  • EP 668 080 A2 and the divisional application EP 1570 869 A1 relate to the use of organic acids, including sulfinic acids, but exclusively of salts of organic acids or sulfinic acids, or of polyamino acids or their salts to reduce residual surface postcrosslinkers, in particular of surface postcrosslinkers Epoxy compounds, after surface postcrosslinking.
  • EP 386 897 A2 discloses the use of a combination of surface-active substance and a compound which adds to double bonds, for example unsubstituted or substituted alkyl- or arylsulfinic acids or salts thereof for reducing residual monomers in superabsorbers.
  • EP 441 975 A1 and EP 605 215 A1 teach the use of sulfites, hydrogen sulfites or thiosulfates for reducing residual monomers from the polymerization.
  • EP 1 645 596 A1 teaches the stabilization of superabsorbers against discoloration by addition of an inorganic salt, an aminocarboxylic acid chelating agent and an organic antioxidant.
  • an inorganic salt sulfites, bisulfites, pyrosulfites, dithionites, trithionates, tetrathionates, thiosulfates or nitrites are used.
  • EP 1 577 349 A1 teaches the use of these salts for the same purpose, but the content of the superabsorbent treated with iron is kept below 1 ppm by weight.
  • WO 2009/060062 or earlier International Patent Application Serial No. PCT / EP2009 / 059793 teach the addition of sulfinic acid derivatives to superabsorbents to stabilize them against discoloration.
  • WO 2008/092 842 A1 teaches the addition of a basic salt of a divalent metal cation to superabsorbers, inter alia, in order to increase the stability against discoloration.
  • WO 2008/092 843 A1 discloses the use of carboxylic acid salts and / or basic salts of trivalent metal cations for the same purpose.
  • WO 2005/054 356 A1 teaches the use of steric Hindered phenols instead of the technically usual para-methoxyphenol ("methyl hydroquinone", "MEHQ") as stabilizers for acrylic acid against polymerization, which have the advantage of less discoloration of the polymer.
  • Another object is to find other or even better superabsorbers which are stabilized against discoloration, in particular against yellowing or browning when stored under elevated temperature and / or elevated air humidity.
  • Useful properties of the superabsorber in particular its ability to absorb liquid, even under pressure, as well as its ability to convey liquid, should not be impaired or at least not significantly impaired.
  • other properties should not be affected, such as odor, which may be a problem with sulfur-containing reducing agents in the presence of moisture, or its flowability, which may be a problem with sodium hypophosphite additive, or dusting, which can be a problem when adding insoluble calcium salts .
  • Further objects of the invention are finding a method for producing such a superabsorbent and uses of this superabsorbent.
  • the object was achieved by a superabsorber containing at least one stabilizer against discoloration, which consists of phenols, phosphonic acid (HP (0) (OH) 2),
  • the superabsorbers according to the invention show surprisingly good stability against discoloration without their use properties such as CRC, AUL or SFC being significantly impaired.
  • at least one stabilizer against discoloration is added to the SAP.
  • the stabilizer can be added in any form. Usually it is preferred to add it in predominantly undissolved form. "Predominantly undissolved” means that in general at least 50% by weight, preferably at least 70% by weight and in a particularly preferred form at least 90% by weight of the amount of stabilizer added does not occur at the time of addition
  • the stabilizer is added either as a dry powder or as a suspension in a suspending agent
  • the stabilizer can be added to the superabsorbent at any time during preparation Preferably, it is not added to the monomer mixture for polymerization or to a monomer but instead only when crosslinked polymer is present is, at the earliest during the polymerization.
  • the stabilizer can be added, for example, during the polymerization, during a surface postcrosslinking or after the surface postcrosslinking.
  • the stabilizer is added to the monomer mixture or to a monomer, it is additionally added to any stabilizer against undesired or premature polymerization.
  • the stabilizer is a sterically hindered phenol, it is preferred to add it at the earliest during the polymerization.
  • the stabilizer is soluble or insoluble.
  • the stabilizer is insoluble in water, i. its solubility in water at 25 ° C is at most 5 g / l, preferably at most 1 g / l.
  • the stabilizer (or stabilizers) is made from phenols, phosphonic acid
  • Hindered phenols are understood as meaning phenols which have a single or double-branched substituent, preferably a double-branched substituent, at least in the 2-position and optionally also in the 6-position on the phenyl ring.
  • Branched substituents are understood to mean substituents which bear at least two radicals other than hydrogen on the atom bonded to the phenyl ring of the phenol, apart from the C atom of the phenyl ring to which they are attached.
  • sterically hindered phenols are also those which carry a sterically demanding unbranched substituent at least in the 2-position and optionally also in the 6-position.
  • substituents which comprise at least 6, preferably at least 8, and in a particularly preferred form at least 12 atoms other than hydrogen, but only one on the atom bound to the phenyl ring of the phenol other than the C atom of the phenyl ring to which they are attached of hydrogen other residue.
  • the simplest examples of singly branched substituents are secondary alkyl radicals such as 2-propyl, 2-butyl, 2-pentyl, 3-pentyl, ethylhexyl or cycloalkyl radicals such as cyclobutyl, cyclopentyl, cyclohexyl or aromatic radicals such as phenyl.
  • di-branched substituents are tertiary alkyl radicals such as tert-butyl, tert-pentyl or norbornyl.
  • unbranched radicals are hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl, but also neo-pentyl, neo-hexyl or dodecylthiomethyl. All of these radicals can also be substituted or contain atoms other than carbon and hydrogen.
  • the phenyl ring of the phenol may optionally carry further substituents in addition to the substituent in the 2-position and optionally in the 6-position.
  • Examples of preferred sterically hindered phenols are 2-tert-butylphenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methyl-phenol (also referred to as 2,6-di-tert tert-butyl-para-cresol or 3,5-di-tert-butyl-4-hydroxytoluene), 3,5-di-tert-butyl-4- hydroxyphenylacetic acid, 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid and the esters of these acids with alcohols and polyols, for example their simple or multiple esters with glycol, glycerol, 1, 2- or 1, 3-propanediol, trimethylolpropane or Pentaerythritol, such as pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) or oc
  • Phosphonic acid HP (0) (OH) 2
  • phosphorous acid H3PO3
  • Phosphonic acid is tautomeric with phosphorous acid, the latter does not exist as free acid.
  • Genuine derivatives of phosphorous acid are only their triesters, commonly referred to as phosphites.
  • the tautomeric phosphonic acid derivatives are commonly referred to as phosphonates.
  • all primary and secondary phosphonates of the alkali metals, including ammonium, and the alkaline earth metals are suitable.
  • aqueous solutions of phosphonic acid which contain primary and / or secondary phosphonations and at least one cation selected from sodium, potassium, calcium, strontium.
  • phosphites or phosphonates examples include calcium bis [monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate], tris (2,4-di-tert-butylphenyl) phosphite, 3.9- Bis (octa-decyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane and bis (2,4-di-tert-butylphenol) pentaerythritol diphosphite.
  • Stabilizers may simultaneously be phosphonates or phosphites and hindered phenols.
  • the stabilizers are, unless they are dissolved, naturally particulate, they are therefore predominantly in powder form when applied.
  • the average particle size is typically in the range of at least 0.001 ⁇ , preferably at least 0.002 ⁇ , more preferably at least 0.005, and most preferably at least 0.01 ⁇ , and generally at most 500 ⁇ , preferably at most 200 ⁇ , more preferably Form at most 100 ⁇ and in a very particularly preferred form of at most 50 ⁇ .
  • the particles themselves may be aggregates or agglomerates of smaller primary particles.
  • the particle size can be determined by means of sieve analysis, but it is simpler and therefore preferred to determine the particle size by means of laser diffraction technology. These methods are well known and routinely performed on suitable and commercially available equipment.
  • the anti-discoloration stabilizers mentioned above, when added, are generally present in amounts of at least 0.0001% by weight, preferably at least 0.001% by weight, and most preferably at least 0.025% by weight, and in the formula Generally at most 3% by weight, in a preferred form at most 2% by weight and in a particularly preferred form at most 0.5% by weight, in each case based on the total weight of the superabsorbent according to the invention.
  • each superabsorber can be mixed with the stabilizer.
  • such superabsorbents are crosslinked hydrophilic polymers, in particular polymers of (co) polymerized hydrophilic monomers, graft (co) polymers of one or more hydrophilic monomers on a suitable graft base, crosslinked cellulose or starch ethers, crosslinked carboxymethylcellulose, partially crosslinked polyalkylene oxide or in aqueous Liquid swellable natural products such as guar derivatives.
  • a superabsorbent based on partially neutralized acrylic acid is used.
  • Superabsorbents are characterized above all by their ability to absorb and retain liquids.
  • An inventive and preferred superabsorbent is prepared, for example, by aqueous solution polymerization of a monomer mixture comprising: a) at least one ethylenically unsaturated monomer bearing at least one acid group, which is optionally present at least partially as 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 or its salts, maleic anhydride and itaconic acid or their 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).
  • Impurities can have a significant influence on the polymerization. Therefore, the raw materials used should have the highest possible purity. It is therefore often advantageous to purify the monomers a) specifically. Suitable purification processes are described, for example, in WO 2002/055469 A1, WO 2003/078378 A1 and WO 2004/035514 A1.
  • 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 of furfurals, 0.0001% by weight of maleic anhydride, 0.0003% by weight of diacrylic acid and 0.0050% by weight of hydroquinone monomethyl ether.
  • 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.
  • ppm, hydroquinone half ethers based in each case on the unneutralized monomer a), where neutralized monomer a), ie a salt of the monomer a) is mathematically taken into account as 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.
  • 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 can form covalent bonds 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, as in DE 103 31 456 A1 and US Pat DE 103
  • Preferred crosslinkers b) are pentaerythritol triallyl ether, tetraallyloxyethane, methylene bismethacrylamide, trimethylolpropane triacrylate 15 to 20 times ethoxylated, 15-20 times ethoxylated glycerol triacrylate, polyethylene glycol diacrylate having between 4 and 45 - Ch Ch O units in the molecular chain, 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 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 absorption increases under a pressure of 0.3 psi
  • initiators c) it is possible to use all compounds which generate 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.
  • the reducing component but is preferably the mixture of the sodium salt of 2-hydroxy-2-sulfinatoacetic acid described in greater detail below, the acid disodium salt of 2-hydroxy-2-sulfonatoessig- and sodium bisulfite (Brüggolit ® FF6M or Brüggolit ® FF7).
  • Suitable ethylenically unsaturated monomers d) 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, maleic acid or its salts and maleic anhydride.
  • water-soluble polymers e it is possible to use 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.
  • At least one water-soluble alkaline earth salt selected from the salts of calcium, strontium or barium is added to the superabsorbent according to the invention.
  • Mixtures of salts of all possible combinations of two of these elements or all three of these elements can be used.
  • calcium salts are usually preferred.
  • alkaline earth salt-containing superabsorbent a smaller amount of stabilizers according to the invention is necessary against discoloration than without alkaline earth salt.
  • the anions of the alkaline earth salts can basically be chosen freely, with the restriction that they must not lead to negative effects in the superabsorber and / or in its application.
  • suitable anions of the alkaline earth metal salts are halides, in particular chloride, hydroxide, carbonate, carboxylate, such as formate, acetate, propionate or lactate, nitrate or sulfate. Mixtures can also be used.
  • water-soluble alkaline earth salts are used or those which, although themselves relatively poorly soluble in water, react rapidly with the acid groups of the superabsorbent or the monomers.
  • Such salts have the advantage, in particular in the customary preparation of the superabsorber from water-containing monomer mixtures, that an equivalent amount of the neutralizing agent otherwise used can be saved.
  • the anions of the alkaline earth metal salt are selected accordingly, preference is given to hydroxide, carbonate or lactate.
  • Total preferred alkaline earth salts are calcium hydroxide, strontium hydroxide, barium hydroxide, calcium carbonate, strontium carbonate, barium carbonate, calcium lactate, strontium lactate, barium lactate, calcium sulfate, strontium sulfate, barium sulfate or mixtures thereof. Particularly preferred are calcium hydroxide, calcium carbonate, calcium lactate and calcium sulfate.
  • the alkaline earth salt is generally used in an amount of at least 0.1% by weight, preferably at least 0.5% by weight and more preferably at least 1% by weight and generally at most 20% by weight, preferably at most 10 wt .-% and in a particularly preferred form of at most 5 wt .-% added, in each case based on the total amount of ethylenically unsaturated, at least one acid group-carrying monomers. These are calculated as free acid, any total or partial neutralization of the acid groups is not taken into account in the calculation. Some alkaline earth salts may contain water of crystallization. This is also not taken into account in the calculation.
  • the alkaline earth salt (or mixture of alkaline earth salts) is added to the monomer mixture before or during the polymerization or, if the polymerization is followed by a separate drying step, to the polymer before drying, or partially before or during the polymerization and partly to the polymer before drying.
  • the aim is a uniform distribution of the alkaline earth salt in the superabsorbent.
  • the alkaline earth salt is mixed by method and time as described below for the neutralizing agent.
  • the simplest and therefore preferred is the addition into the monomer mixture before the polymerization.
  • the alkaline earth metal salt can also be introduced into the resulting polymer gel during the polymerization or after the polymerization, but it is in any case introduced before the drying.
  • the addition during the polymerization is particularly easy in the methods in which the polymerizing composition is mixed, for example, in polymerization in a kneader.
  • the addition after the polymerization and before the drying is easy, above all, in the processes in which the polymerized mass from the polymerization is passed into a separate drying step, ie in particular in all processes in which polymerization and drying are carried out in separate apparatuses become.
  • the alkaline earth salt may in this case be mixed into the polymer gel by any known mixing method and apparatus.
  • the alkaline earth salt is added as a dry substance or as a solution or dispersion in a solvent.
  • the solvent used is preferably water.
  • the monomer solution can be freed of dissolved oxygen prior to the polymerization by inertization, ie by flowing through with an inert gas, preferably nitrogen or carbon dioxide.
  • an inert gas preferably nitrogen or carbon dioxide.
  • the oxygen the monomer solution before polymerization to less than 1 ppm by weight, more preferably to less than 0.5 ppm by weight, most preferably to less than 0.1 ppm by weight, lowered.
  • 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.
  • the acid groups of the polymer gels obtained from the polymerization 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") as component a) in the polymerization
  • This is usually done 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
  • the degree of neutralization is preferably from 25 to 95 mol%, particularly preferably from 50 to 80 mol%, very particularly preferably from 65 to 72 mol%, it being possible to use the customary neutralizing agents, preferably alkali metal hydroxides, alkali metal oxides, alkali metal carbonates or alkali metal bicarbonates and mixtures thereof ammonium salts can also be
  • the polymer gel is at least partially neutralized after the polymerization, the polymer gel is preferably comminuted mechanically, for example by means of an extruder, wherein the neutralizing agent can be sprayed, sprinkled or poured on and then thoroughly mixed in. For this purpose, the gel mass obtained can be extruded several times for homogenization.
  • the monomer a) used is a mixture of from 25 to 95 mol%, particularly preferably from 50 to 80 mol%. , very particularly preferably from 65 to 72 mol% salt of the acid group carrier the monomers and the remainder used to 100 mol% acid group-carrying monomer.
  • This mixture is, for example, a mixture of sodium acrylate and acrylic acid or a mixture of potassium acrylate and acrylic acid.
  • a neutralizing agent is used for neutralization, 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.
  • a suitable neutralizing agent is, for example, the 50% strength by weight sodium hydroxide solution or potassium hydroxide solution, which is usually sold as "membrane grade", even purer and equally suitable, but also more expensive is the 50% by weight conventionally sold as "amalgam grade” or "mercury process". % sodium hydroxide solution or potassium hydroxide solution.
  • the alkaline earth salt used is a water-soluble or a relatively poorly soluble, yet relatively fast-reacting alkaline earth metal salt
  • the amount of neutralizing agent added can be reduced by adding an amount of alkaline earth metal ions.
  • the alkaline earth salt may also serve as a neutralizing agent at the same time, the divalent alkaline earth ion replacing two monovalent alkali ions.
  • alkaline earth metal hydroxides, carbonates and lactates are suitable.
  • 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 EP 955 086 A2, DE 38 25 366 A1 and US Pat. No. 6,241,928.
  • a polymer gel must be comminuted in a further process step, for example in one Meat grinder, extruder or kneader.
  • WO 2009/027 356 A1 Also known are methods in which the monomer mixture is applied to a substrate such as a nonwoven web and polymerized, as described for example in WO 02/94 328 A2 and WO 02/94 329 A1.
  • 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.
  • 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, but usually results in a drier or similar dryer also adequate ventilation and drainage of the water steam to an acceptable product.
  • Advantageous in terms of color and product quality is usually the shortest possible drying time.
  • 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 often not dried on the inside, are rubber-elastic, cause grinding problems and are preferably used before grinding
  • Grind separation which can be done easily by air classification or a sieve ("protective sieve" for the mill) .
  • the mesh size of the sieve is to be chosen in view of the mill used so that as possible no interference from oversized, rubbery particles occur.
  • coarse-grained polymer particles are separated from the product. This is done by conventional classification methods, such as air classification or sieving through a sieve with a mesh size of at most 1000 ⁇ , preferably at most 900 ⁇ , more preferably at most 850 ⁇ and most preferably at most 800 ⁇ . For example, screens are used with 700 ⁇ , 650 ⁇ or 600 ⁇ mesh size.
  • the separated coarse-grained polymer particles (“oversize") can be fed back to the grinding and screening circuit for cost optimization or further processed separately.
  • SFC permeability
  • also fine-grained polymer particles are separated in this classification. This can, if sieved, conveniently by a sieve with a mesh size of at most 300 ⁇ , preferably at most 200 ⁇ , more preferably used at most 150 ⁇ and most preferably not more than 100 ⁇ .
  • 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 mean particle size of the polymer particles separated off as product fraction is generally at least 200 ⁇ m, preferably at least 250 ⁇ m, and preferably at least 300 ⁇ m, and generally at most 600 ⁇ m, and more preferably at most 500 ⁇ m.
  • the proportion of particles having a particle size of at least 150 ⁇ m is generally at least 90% by weight, preferably at least 95% by weight and most preferably at least 98% by weight.
  • the proportion of particles with a particle size of at most 850 ⁇ m is generally at least 90% by weight, preferably at least 95% by weight and more preferably at least 98% by weight.
  • 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 screening steps can often be omitted.
  • a separate drying step can often be dispensed with.
  • the polymer produced in this way has superabsorbent properties and is referred to as "superabsorbent.” Its CRC is typically comparatively high, while its AUL or SFC is comparatively low. Called base polymer “or" base polymer ".
  • 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 amide acetals or carbamates of the general formula (I)
  • R 1 is Ci-Ci2-alkyl, C 2 -C 2 hydroxyalkyl, C 2 -C 2 -alkenyl or C 6 -C 2 aryl,
  • R 3 is hydrogen, Ci-Ci 2 -alkyl, C 2 -C 2 hydroxyalkyl, C 2 -C 2 -alkenyl or C 6 -C 2 aryl, or X,
  • R 4 Ci-Ci 2 -alkyl, C 2 -C 2 hydroxyalkyl, C 2 -C 2 -alkenyl or C 6 -C 2 aryl,
  • R 5 is hydrogen, Ci-Ci 2 -alkyl, C 2 -C 2 hydroxyalkyl, C 2 -C 2 -alkenyl, Ci-Ci2 acyl or
  • R 6 Ci-Ci 2 -alkyl, C 2 -C 2 hydroxyalkyl, C 2 -C 2 -alkenyl or C 6 -C 2 aryl, and
  • X is a carbonyl oxygen common to the radicals R 2 and R 3 , where R 1 and R 4 and / or R 5 and R 6 may be a bridged C 2 -C 6 alkanediyl, and where the abovementioned radicals R 1 to R 6 are still may have at least one to two free valences and may be connected to these free valencies with at least one suitable base, or polyhydric alcohols, wherein the polyhydric alcohol preferably has a molecular weight of less than 100 g / mol, preferably less than 90 g / mol , more preferably less than 80 g / mol, most preferably less than 70 g / mol, per hydroxy group and no vicinal, geminal, secondary or tertiary hydroxy groups, and polyhydric alcohols either diols of general formula (IIa) HO R 7 - OH (IIa) where R 7 is either an unbranched alkylene radical of the formula - (CH 2) n
  • radicals R 8 , R 9 , R 10 , R 11 independently of one another denote hydrogen, hydroxyl, hydroxymethyl, hydroxyethyloxymethyl, 1-hydroxyprop-2-yloxymethyl, 2-hydroxypropyloxymethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-hexyl, 1, 2-dihydroxyethyl, 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl and a total of 2, 3, or 4, preferably 2 or 3, hydroxy groups are present, and not more than one of R 8 , R 9 , R 10 , or R 11 is hydroxyl, are, or cyclic carbonates of the general formula (III)
  • R 12 , R 13 , R 14 , R 15 , R 16 and R 17 are independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or isobutyl, and n is either 0 or Is 1, or bisoxazolines of the general formula (IV) wherein R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 and R 25 are independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or isobutyl, and R 26 represents a single bond, a linear, branched or cyclic C 2 -C 12 -alkylene radical, or a polyalkoxydiyl radical which is composed of one to ten ethylene oxide and / or propylene oxide units, such as, for example, polyglycol dicarboxylic acids.
  • Preferred postcrosslinkers of the general formula (I) are 2-oxazolidones, such as 2-oxazolidone and N- (2-hydroxyethyl) -2-oxazolidone, N-methyl-2-oxazolidone, N-acyl-2-oxazolidones, such as N-acetyl -2-oxazolidone, 2-oxotetrahydro-1,3-oxazine, bicyclic amidacetals such as 5-methyl-1 -aza-4,6-dioxa-bicyclo [3.3.0] octane, 1-aza-4,6 -dioxabicyclo [3.3.0] octane and 5-isopropyl-1 -aza-4,6-dioxa-bicyclo [3.3.0] octane, bis-2-oxazolidones and poly-2-oxazolidones.
  • 2-oxazolidones such as 2-oxazolidone and N- (2-hydroxy
  • Particularly preferred postcrosslinkers of the general formula (I) are 2-oxazolidone, N-methyl-2-oxazolidone, N- (2-hydroxyethyl) -2-oxazolidone and N-hydroxypropyl-2-oxazolidone.
  • Preferred postcrosslinkers of the general formula (IIa) are 1, 3-propanediol, 1, 5-pentanediol, 1, 6-hexanediol and 1, 7-heptanediol. Further examples of postcrosslinkers of the formula (IIa) are 1, 3-butanediol, 1, 8-octanediol, 1, 9-nonanediol and 1, 10-decanediol.
  • the diols are preferably water-soluble, wherein the diols of the general formula (IIa) at 23 ° C to at least 30 wt .-%, preferably at least 40 wt .-%, particularly preferably at least 50 wt .-%, most preferably at least 60 wt .-%, in water, such as 1, 3-propanediol and 1, 7-heptanediol. Even more preferred are those postcrosslinkers which are liquid at 25 ° C.
  • Preferred postcrosslinkers of the general formula (IIb) are butane-1, 2,3-triol, butane-1, 2,4-triol, glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, per molecule 1 to 3 times ethoxylated glycerol, trimethylolethane or Trimethylolpropane and per molecule 1 - to 3-fold propoxylated glycerol, trimethylolethane or trimethylolpropane.
  • 2-fold ethoxylated or propoxylated neopentyl glycol Particularly preferred are 2-fold and 3-fold ethoxylated glycerol, neopentyl glycol, 2- Methyl 1, 3-propanediol and trimethylolpropane.
  • Preferred polyhydric alcohols (IIa) and (IIb) have a viscosity at 23 ° C. of less than 3000 mPas, preferably less than 1500 mPas, preferably less than 1000 mPas, more preferably less than 500 mPas, very particularly preferably less than 300 mPas, on.
  • Particularly preferred postcrosslinkers of the general formula (III) are ethylene carbonate and propylene carbonate.
  • a particularly preferred postcrosslinker of the general formula (IV) is 2,2'-bis (2-oxazoline).
  • the preferred postcrosslinkers minimize side reactions and subsequent reactions which lead to volatile and thus malodorous compounds.
  • the superabsorbers produced with the preferred postcrosslinkers are therefore odorless even when moistened.
  • the postcrosslinker is generally used in an amount of at least 0.001% by weight, preferably at least 0.02% by weight, more preferably at least 0.05% by weight, and generally at most 2% by weight, preferably at most 1% by weight, in a particularly preferred form at most 0.3% by weight, for example at most 0.15% by weight or at most 0.095% by weight, in each case based on the mass of the base polymer (for example the relevant Sieve fraction).
  • 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, wherein the postcrosslinking reaction can take place both before and during the drying.
  • 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 can 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 spraying of Nachvernetzerpears is preferably carried out in mixers with moving mixing tools, such as screw mixers, disc, paddle or paddle mixers or mixers with other mixing tools. However, particularly preferred are vertical mixers. However, it is also possible to spray the postcrosslinker solution in a fluidized bed.
  • 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 applicable spray nozzles are subject to no restriction. Suitable nozzles and atomization systems are described, for example, in the following references: Atomization of Liquids, Expert-Verlag, Vol. 660, series Kunststoff & Meeting, Thomas Richter (2004) and in atomization technology, Springer-Verlag, VDI series, Günter Wozniak (2002 ). Applicable are mono- and polydisperse spray systems. Among the polydisperse systems are single-fluid pressure nozzles (jet or lamella-forming), rotary atomizers, two-component atomizers, ultrasonic atomizers and impact nozzles. In the two-component atomizers, the mixture of the liquid and the gas phase can take place both internally and externally.
  • the spray pattern of the nozzles is not critical and can take any shape, such as omnidirectional, fan-beam, wide-angle omnidirectional or circular ring spray pattern. It is advantageous to use a non-oxidizing gas, if two-component atomizers are used, particularly preferably nitrogen, argon or carbon dioxide. Such nozzles, the liquid to be sprayed can be supplied under pressure. The division of the liquid to be sprayed can take place in that it is relaxed after reaching a certain minimum speed in the nozzle bore.
  • single-substance nozzles such as, for example, slot nozzles or twist chambers (full-cone nozzles) can also be used for the purpose according to the invention (for example, by Düsen-Schlick GmbH, DE, or by Spraying Systems GmbH, DE).
  • Such nozzles are also described in EP 0 534 228 A1 and EP 1 191 051 A2.
  • the postcrosslinkers are typically used as an aqueous solution. If only water is used as the solvent, the postcrosslinker solution or the base polymer is advantageously added with a surfactant or deagglomerization aid. This improves the wetting behavior and reduces the tendency to clog.
  • anionic, cationic, nonionic and amphoteric surfactants are suitable as Deagglomerationstoskar, but are preferred for skin compatibility reasons non-ionic and amphoteric surfactants.
  • the surfactant may also contain nitrogen.
  • sorbitan monoesters such as sorbitan monococoate and sorbitan tanmonolaurate, or ethoxylated variants thereof, such as polysorbate 20 ® 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 hafen, Germany).
  • the Deagglomerationstosmittel can be metered separately or the Nachvernetzerlosung be added.
  • 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 aid is metered so that the surface tension of an aqueous extract of the swollen base polymer and / or the swollen postcrosslinked water-absorbing polymer at 23 ° C at least 0.060 N / m, preferably at least 0.062 N / m, more preferably at least 0.065 N / m, and advantageously not more than 0.072 N / m.
  • the aqueous Nachvernetzerlosung may also contain a cosolvent in addition to the at least one postcrosslinker.
  • a cosolvent in addition to the at least one postcrosslinker.
  • the penetration depth of the postcrosslinker can be adjusted in the polymer particles.
  • cosolvents are C 1 -C 6 -alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol or 2-methyl-1-propanol, C 2 -C 5 -diols, such as Ethylene glycol, 1, 2
  • ketones such as acetone
  • carboxylic acid esters such as ethyl acetate.
  • a disadvantage of some of these cosolvents is that they have typical odors.
  • the co-solvent itself is ideally not a postcrosslinker under the reaction conditions. However, in the limiting case and depending on residence time and temperature, it may happen that the cosolvent partially contributes to crosslinking.
  • postcrosslinker is relatively inert and therefore can itself form its cosolvent, such as when using cyclic carbonates of the general formula (III), diols of the general formula (IIa) or polyols of the general formula (IIb) .
  • Such postcrosslinkers can also be used as cosolvents in a mixture with more reactive secondary crosslinkers since the actual postcrosslinking reaction can then be carried out at lower temperatures and / or shorter residence times than in the absence of the more reactive crosslinker. Since co-solvent is used in relatively large amounts and also remains partially in the product, it must not be toxic.
  • the diols of the general formula (IIa), the polyols of the general formula (IIb) and the cyclic carbonates of the general formula (III) are also suitable as cosolvents. They fulfill this function in the presence of a reactive postcrosslinker of the general formula (I) and / or (IV) and / or a di- or triglycidyl compound.
  • preferred cosolvents in the process according to the invention are, in particular, the diols of the general formula (IIa), especially when the hydroxyl groups are hindered sterically by neighboring groups on a reaction.
  • diols are in principle also suitable as postcrosslinkers, they require significantly higher reaction temperatures or optionally higher amounts of use than sterically unhindered diols.
  • Particularly preferred combinations of less reactive postcrosslinker as cosolvent and reactive postcrosslinker are combinations of preferred polyhydric alcohols, diols of general formula (IIa) and polyols of general formula (IIb), with amide acetals or carbamates of general formula (I).
  • Suitable combinations are, for example, 2-oxazolidone / 1, 2-propanediol and N- (2-hydroxyethyl) -2-oxazolidone / 1, 2-propanediol and ethylene glycol diglycidyl ether / 1, 2-propanediol.
  • Very particularly preferred combinations are 2-oxazolidone / 1,3-propanediol and N- (2-hydroxyethyl) -2-oxazolidone / 1,3-propanediol.
  • ethylene glycol diglycidyl ether or glycerol or triglycidyl ether with the following solvents, cosolvents or co-crosslinkers: isopropanol, 1,3-propanediol, 1,2-propylene glycol or mixtures thereof.
  • 2-oxazolidone or (2-hydroxyethyl) -2-oxazolidone in the following solvents, cosolvents or co-crosslinkers: isopropanol, 1, 3-propanediol, 1, 2-propylene glycol, ethylene carbonate, propylene carbonate or mixtures thereof.
  • the concentration of cosolvent in the aqueous postcrosslinker solution is from 15 to 50% by weight, preferably from 15 to 40% by weight, more preferably from 20 to 35% by weight, based on the postcrosslinker solution.
  • concentration of the at least one postcrosslinker in the aqueous postcrosslinker solution is typically from 1 to 20% by weight, preferably from 1 to 5% by weight, particularly preferably from 2 to 5% by weight, based on the postcrosslinker solution.
  • the total amount of Nachvernetzerlosung based on the base polymer is usually from 0.3 to 15 wt .-%, preferably from 2 to 6 wt .-%.
  • 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 take place, for example, in a fluidized-bed dryer but is usually carried out in a downstream dryer, such as a hopper dryer, a rotary kiln, a paddle or disc dryer or a heated screw ielsweise 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 of Nara Machinery Co., Ltd., branch Europa, Europa Allee 46, 50226 Frechen, Germany available.
  • a downstream dryer such as a hopper dryer, a rotary kiln, a paddle or disc dryer or a heated screw ielsweise 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
  • the polymer particles can already be heated in the post-crosslinking mixer with steam.
  • the base polymer used may still have a temperature of 10 to 120 ° C from previous process steps, the Nachvernetzerlosung may have a temperature of 0 to 70 ° C.
  • the postcrosslinker solution can be heated to reduce the viscosity.
  • Preferred drying temperatures are in the range 100 to 250 ° C, preferably 120 to 220 ° C, more preferably 130 to 210 ° C, most preferably 150 to 200 ° C.
  • 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.
  • Postcrosslinking can take place under normal atmospheric conditions. Normal atmospheric conditions means that no technical precautions are taken to reduce the partial pressure of oxidizing gases such as atmospheric oxygen in the apparatus in which the postcrosslinking reaction predominantly takes place (the "postcrosslinking reactor", typically the dryer), but it is preferred Oxidizing gases are substances which have a vapor pressure of at least 1013 mbar at 23 ° C.
  • oxygen, nitrogen oxide and nitrogen dioxide in particular oxygen less than 140 mbar, preferably less than 100 mbar, particularly preferably less than 50 mbar, very particularly preferably less than 10 mbar, if the thermal postcrosslinking is carried out at ambient pressure, ie at a total pressure of around 1013 mbar,
  • the total partial pressure of the oxidizing gases is determined by their volume fraction.
  • the proportion of oxidizing gases is preferably less than 14% by volume, preferably less than 10% by volume, particularly preferably less than 5% by volume, very particularly preferably less than 1% by volume.
  • the post-crosslinking can be carried out under reduced pressure, ie at a total pressure of less than 1013 mbar.
  • the total pressure is typically less than 670 mbar, preferably less than 480 mbar, more preferably less than 300 mbar, most preferably less than 200 mbar. If drying and postcrosslinking are carried out under air with an oxygen content of 20.8% by volume, the oxygen partial pressures corresponding to the abovementioned total pressures are 139 mbar (670 mbar), 100 mbar (480 mbar), 62 mbar (300 mbar) and 42 m mbar (200 mbar), with the respective total pressures in parentheses. Another way to reduce the partial pressure of oxidizing gases, the introduction of non-oxidizing gases, especially inert gases in the apparatus used for post-crosslinking.
  • Suitable inert gases are gaseous substances at the postcrosslinking temperature and given pressure in the postcrosslinking dryer which, under these conditions, do not oxidize to the constituents of the drying polymer particles, for example nitrogen, carbon dioxide, argon, water vapor, with nitrogen being preferred.
  • the amount of inert gas is generally from 0.0001 to 10 m 3 , preferably from 0.001 to 5 m 3 , more preferably from 0.005 to 1 m 3 , and most preferably from 0.005 to 0.1 m 3 , based on 1 kg of superabsorbent.
  • the inert gas if it does not contain water vapor, can be injected via nozzles into the postcrosslinking dryer, more preferably the inert gas is added to the polymer particle stream via nozzles via the nozzles in or just before the mixer by adding superoxide absorber with surface postcrosslinker ,
  • vapors of cosolvents removed from the dryer can be condensed outside the dryer again and, if necessary, recycled.
  • polyvalent cations are applied to the particle surface in addition to the postcrosslinkers before, during or after the postcrosslinking. This is in principle a further surface postcrosslinking by ionic, noncovalent bonds, but is sometimes also referred to as "complexing" with the metal ions in question or simply as “coating” with the relevant substances (the "complexing agent").
  • Polyvalent cations are applied by spraying solutions of divalent or polyvalent cations, usually divalent, trivalent or tetravalent metal cations, but also polyvalent cations, such as formally wholly or partly of vinylamine monomers, such as partially or completely hydrolyzed polyvinylamide
  • divalent metal cations which may be used are, in particular, the divalent cations of metals of groups 2 (in particular Mg, Ca, Sr, Ba), 7 (in particular Mn), 8 (in particular Fe), 9 (in particular Co), 10 (in particular Ni), 11 (in particular Cu) and 12 (in particular Zn) of the Periodic Table of the Elements
  • Examples of trivalent metal cations which may be used are in particular the trivalent cations of Group 3 metals, including lanthanides (in particular Sc, Y, La, Ce), 8 (in particular Fe), 1 1 (in particular Au) and 13 (in particular Al) of the Periodic Table of the Elements.
  • tetravalent cations are, in particular, the tetravalent cations of metals of the lanthanides (in particular Ce) and of group 4 (in particular Ti, Zr, Hf) of the Periodic Table of the Elements.
  • the metal cations can be used alone or mixed with each other. Particularly preferred is the use of trivalent metal cations. Very particularly preferred is the use of aluminum cations. Of the cited metal cations, all metal salts which have sufficient solubility in the solvent to be used are suitable.
  • metal salts with weakly complexing anions such as chloride, nitrate and sulfate, hydrogen sulfate, carbonate, bicarbonate, nitrate, phosphate, hydrogen phosphate, or dihydrogen phosphate.
  • Preferred are salts of mono- and dicarboxylic acids, hydroxy acids, keto acids and amino acids or basic salts. Examples of acetates, propionates, tartrates, maleates, citrates, lactates, malates and succinates are also preferred is the use of hydroxides.
  • Particularly preferred is the use of 2-hydroxycarboxylic acid salts such as citrates and lactates.
  • particularly preferred metal salts are alkali metal and alkaline earth metal aluminates and their hydrates, for example sodium aluminate and its hydrates, aluminum acetate, aluminum propionate, aluminum citrate and aluminum lactate.
  • the cations and salts mentioned can be used in pure form or as a mixture of different cations or salts.
  • the salts of the two and / or trivalent metal cation used may contain further secondary constituents such as unneutralized carboxylic acid and / or alkali metal salts of the neutralized carboxylic acid.
  • Preferred alkali metal salts are those of sodium, potassium and ammonium. They are typically used as an aqueous solution which is obtained by dissolving the solid salt in water, or is preferably produced directly as such, whereby optionally drying and purification steps are avoided.
  • the hydrates of said salts can be used, which often dissolve faster in water than the anhydrous salts.
  • the amount of metal salt used is generally at least 0.001 wt .-%, preferably at least 0.01 wt .-% and in a particularly preferred form at least 0.1 wt .-%, for example at least 0.4 wt .-% and generally at most 5 wt .-%, preferably at most 2.5 wt .-% and in a particularly preferred form at most 1 wt .-%, for example at most 0.7 wt .-% in each case based on the mass of the base polymer.
  • the salt of the trivalent metal cation can be used as a solution or suspension.
  • solvents for the metal salts water, alcohols, DMF, DMSO and mixtures of these components can be used. Particularly preferred are 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 divalent or polyvalent cation is carried out in the same way as with surface postcrosslinkers, including the 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 on the superabsorbent particles can be both before and after the surface postcrosslinking.
  • the spraying of the metal salt solution in the same step is carried out 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 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 ° C.
  • the surface postcrosslinked superabsorbent is optionally ground and / or sieved in the usual way. Milling is typically not required here, but most often, the setting of the desired particle size distribution of the product, the screening of formed agglomerates or fine grain is appropriate. Agglomerates and fines are either discarded or preferably recycled to the process in a known manner and at the appropriate place; Agglomerates after comminution.
  • the particle sizes desired for surface postcrosslinked superabsorbents are the same as for base polymers.
  • the superabsorbers according to the invention are provided with further additives which stabilize against discoloration.
  • Such stabilizers against discoloration are, for example, derivatives of sulfinic acid.
  • Particularly suitable derivatives of sulfinic acid are, for example, compounds of the following formula (V):
  • M represents a hydrogen atom, an ammonium ion, a monovalent metal ion or one equivalent of a divalent metal ion of Groups 1, 2, 8, 9, 10, 12 or 14 of the Periodic Table of the Elements;
  • R 27 is OH or NR 30 R 31 , wherein R 30 and R 31 independently of one another are H or C 1 -C 6 -alkyl;
  • R 28 is H or an alkyl, alkenyl, cycloalkyl or aryl group, this group optionally having 1, 2 or 3 substituents which are independently selected from C 1 -C 6 -alkyl, OH, O-C 1 -C 6 -alkyl, Alkyl, halogen and CF3; and
  • R 29 is COOM, SO 3M, COR 30 , CONR 30 R 31 or COOR 30 , wherein M, R 30 and R 31 have the meanings given above or, when R 28 is aryl, which is optionally substituted as indicated above, also stands for H,
  • alkyl represents straight-chain or branched alkyl groups which preferably have 1-6, in particular 1-4, carbon atoms.
  • alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl, etc.
  • Alkenyl represents straight-chain or branched alkenyl groups which preferably have 3-8 carbon atoms, in particular 3-6 carbon atoms.
  • a preferred alkenyl group is the allyl group.
  • Cycloalkyl is in particular C 1 -C 6 -cycloalkyl, with cyclopentyl and cyclohexyl being particularly preferred.
  • Aryl also in aralkyl is preferably phenyl or naphthyl. When the aryl group is a phenyl group and is substituted, it preferably has two substituents. These are available in particular in the 2- and / or 4- position.
  • Halogen is F, Cl, Br and I, preferably Cl and Br.
  • M is preferably an ammonium, alkali metal or one equivalent of an alkaline earth metal or zinc ion. Suitable alkali metal ions are in particular sodium and potassium ions, and suitable alkaline earth metal ions are, above all, magnesium, strontium and calcium ions.
  • R 27 is preferably a hydroxy or amino group.
  • R 28 is preferably a hydrogen atom or an alkyl or aryl group which may be substituted as above. It preferably has one or two hydroxyl and / or alkoxy substituents.
  • R 29 is preferably either COOM or COOR 30 (M and R 30 have the meanings given above) or, when R 27 is aryl, which may be substituted as indicated above, also for a hydrogen atom.
  • the superabsorbent contains compounds of the above formula wherein M is an alkali metal ion or one equivalent of an alkaline earth metal or zinc ion; R 27 is a hydroxy or amino group; R 28 is H or alkyl and R 29 is COOM or COOR 30 , wherein when R 29 is COOM, M in this COOM moiety is H, an alkali metal ion or an equivalent of an alkaline earth metal ion, and when R 29 is COOR 30 , R 30 is Ci-C 6 alkyl.
  • the superabsorbent contains compounds of the above formula wherein M is an alkali metal ion or one equivalent of an alkaline earth metal or zinc ion; R 27 is a hydroxy or amino group; R 28 is aryl which is optionally substituted as indicated above, in particular hydroxyphenyl or C 1 -C 4 alkoxyphenyl; and R 29 is a hydrogen atom.
  • Groups 1 H, Li, Na, K, Rb, Cs, Fr), 2 (Be, Mg, Ca, Sr, Ba, Ra), 8 (Fe, Ru, Os), 9 (Co, Rh, Ir ), 10 (Ni, Pd, Pt), 12 (Zn, Cd, Hg), and 14 (C, Si, Ge, Sn, Pb) of the periodic table of elements in the current IUPAC numbering (International Union of Pure and Applied Chemistry, 104 TW Alexander Drive, Building 19, Research Tri- angle Park, NC 27709, USA, www.iupac.org), the international nomenclature organization responsible for chemistry, corresponds to Groups Ia, IIa, IIb, IVa and VIIIb in the numbering used by CAS (Chemical Abstracts Service, 2540 Olentangy River Road, Columbus, OH 43202, USA, www.cas.org).
  • the sulfinic acid derivatives of the above formula can be used in pure form, but optionally also in the usual manner resulting from the preparation of such compounds with the sulfite of the corresponding metal ion and the corresponding sulfonic acid.
  • the preparation of such sulfinic acid derivatives of the above formula is known and described for example in WO 99/18 067 A1. They are also common commodities and, for example, in the form of mixtures from the sodium salt of 2-hydroxy-2-sulfinatoacetic acid, the disodium salt of 2-hydroxy-2-sulfonatoacetic acid and sodium bisulfite by L.
  • the superabsorber according to the invention is also mixed with at least one inorganic water-insoluble particulate solid.
  • any inorganic water-insoluble powder is suitable for this purpose.
  • examples are in general solid, chemically inert (that is, superabsorbent non-interfering) substances such as oxides, oxide hydroxides, hydroxides, sulfates, carbonates zeolites, inorganic pigments, minerals or clays.
  • sulfates such as magnesium sulfate or barium sulfate
  • carbonates such as calcium carbonate, magnesium carbonate or dolomite
  • silicates such as calcium silicate or magnesium silicate
  • carbides such as perlite or silicon carbide, diatomaceous earth or fly ash.
  • Suitable oxides are the metal oxides of Groups 2 to 14 of the Periodic Table of the Elements, including the lanthanides and actinides.
  • particularly suitable oxides are magnesium oxide, calcium oxide, strontium oxide, barium oxide, titanium dioxide, zirconium dioxide, vanadium oxide, chromium oxide, molybdenum oxide, tungsten oxide, manganese dioxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, boron oxide, aluminum oxide, silicon dioxide, tin oxide, lead oxide, lanthanum oxide or ceria.
  • the use of a trivial name for metal oxides should not be a statement about the valence of the metal and the stoichiometry of the oxide.
  • one element forms multiple oxides, generally all are suitable.
  • the oxide is selected according to considerations specific to the individual case, for example by price, toxicity, stability or color.
  • particularly suitable oxides are titanium dioxide, in particular in the anatase or rutile modifications, precipitated or pyrolysis-produced silicon dioxide.
  • Clays are silicates or aluminosilicates which are usually obtained by mining of natural sediments and occasionally also their further processing. However, some clays are made synthetically. It is also possible to use mixtures of these substances.
  • the inorganic water-insoluble solid is particulate, it is in powder form.
  • the average particle size is typically in the range of at least 0.001 ⁇ , preferably at least 0.002 ⁇ , more preferably at least 0.005, and most preferably at least 0.01 ⁇ , and generally at most 500 ⁇ , preferably at most 200 ⁇ , more preferably Form at most 100 ⁇ and in a very particularly preferred form of at most 50 ⁇ .
  • the particles themselves may be aggregates or agglomerates of smaller primary particles.
  • the particle size can be determined by means of sieve analysis, but it is simpler and therefore preferred to determine the particle size by means of laser diffraction technology. These methods are well known and routinely performed on suitable and commercially available equipment.
  • the aforementioned optional further anti-discoloration stabilizers and the inorganic water-insoluble particulate solid, when added, are generally present in amounts of at least 0.0001% by weight, preferably at least 0.001% by weight, and more preferably at least
  • a lower amount of known stabilizers against discoloration is necessary with the alkaline earth salt-containing superabsorber according to the invention than without alkaline earth salt.
  • the mixture of superabsorbents with the stabilizers according to the invention to be used against discoloration, optional further stabilizers and the inorganic water-insoluble particulate solid can be carried out by any known mixing method.
  • the anti-discoloration stabilizers to be used according to the invention, if in solid form, and the inorganic water-insoluble particulate solid are mixed in bulk or as a suspension in a solvent or suspending agent, the anti-discoloration stabilizers to be used according to the invention, if in dissolved or liquid form and optional others Stabilizers can optionally be mixed in solution or in liquid form.
  • the stabilizers are blended into the superabsorber as a powder or suspension because of the easier homogeneous distribution.
  • the additives may well enter into a firmer connection with the superabsorber, for example as a comparatively firmly adhering surface layer or as particles firmly adhering to the surface of the superabsorber particles.
  • the interference of the additives in the known superabsorber can certainly also be understood and referred to as a "coating".
  • a solvent or suspending agent is used as the solvent or suspending agent, which is chemically compatible with both the superabsorbent and the additive, that is to say that no undesired chemical reactions occur therewith.
  • water or an organic solvent is used, for example an alcohol or polyol, or mixtures thereof.
  • suitable solvents or suspending agents are water, isopropanol / water, 1,3-propanediol / water and propylene glycol. col / water, wherein the mixture mass ratio is preferably from 20:80 to 40:60.
  • a suspension agent is used for the stabilizers to be used according to the invention or the inorganic particulate solid, water is preferred.
  • a surfactant may be added to the solution or suspension.
  • Stabilizers and other additives are generally mixed with the superabsorbent in exactly the same way as the surface postcrosslinker-containing solution or suspension applied to the superabsorbent, such as described below.
  • the additive can be applied to a (not) postcrosslinked superabsorber (a "base polymer” or “base polymer”) as part of the solution applied to the surface postcrosslinking or one of its components, ie added to the solution of the surface postcrosslinker or one of its components.
  • the superabsorber coated with surface postcrosslinking agents and additives then passes through the further process steps required for surface postcrosslinking, for example a thermally induced reaction of the surface postcrosslinking agent with the superabsorber. This process is comparatively simple and economical.
  • stabilizers and additives are preferably applied after the surface postcrosslinking in a separate process step. If stabilizers and additives are applied as a solution or suspension, the application is carried out on the already surface-postcrosslinked superabsorber in the same way as the application of the surface postcrosslinker to the base polymer. Most, but not necessarily, is then heated as well as in the surface postcrosslinking to rewet the superabsorber. However, the temperature set in this drying is then generally at most 1 10 ° C, preferably at most 100 ° C, and most preferably at most 90 ° C to avoid undesirable reactions of the additive.
  • the temperature is adjusted so that, in view of the residence time in the drying unit, the desired water content of the superabsorber is achieved. It is also possible and convenient to add the additive individually or together with other customary auxiliaries, for example dust binders, anti-caking agents or water for rewetting the superabsorber, as described below for these aids, for example in a cooler connected downstream of the surface postcrosslinking.
  • auxiliaries for example dust binders, anti-caking agents or water for rewetting the superabsorber, as described below for these aids, for example in a cooler connected downstream of the surface postcrosslinking.
  • the temperature of the polymer particles in this case is between 0 ° C and 190 ° C, preferably less than 160 ° C, more preferably less than 130 ° C, even more preferably less than 100 ° C, and most preferably less than 70 ° C ,
  • the polymer particles are optionally rapidly cooled to temperatures below a possible decomposition temperature of the additive after coating.
  • any known coatings such as film-forming polymers, thermoplastic polymers, dendrimers, polycationic polymers (such as polyvinylamine, polyethylenimine or polyallylamine), or all of them, may be applied to the surface of the superabsorber particles, whether postcrosslinked or postcrosslinked, in the manufacturing process in any process step as required the water-soluble mono- or polyvalent metal salts known to the person skilled in the art, such as, for example, aluminum sulfate, sodium, potassium, zirconium or iron salts, are additionally applied.
  • useful alkali metal salts are sodium and potassium sulfate, sodium and potassium lactates, citrates, sorbates.
  • additives are used and sprayed on in the form of dispersions, they are preferably used as aqueous dispersions, and it is preferable to additionally apply a dedusting agent for fixing the additive to the surface of the SAP.
  • 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 simultaneous spraying of postcrosslinking agent, dedusting agent and powdery inorganic additive in the postcrosslinking is added separately in the cooler, for example by spraying from above, below or from the side.
  • Particularly suitable dedusting agents which can also serve to fix powdery inorganic additives on the surface of the water-absorbing polymer 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, glycerol, sorbitol and neopentyl glycol.
  • Particularly suitable are 7 to 20 times ethoxylated glycerol or trimethylolpropane, such as, for example, polyol TP 70® (Perstorp, SE).
  • 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 water-absorbing polymer particles.
  • the superabsorbents according to the invention generally have a centrifuge retention capacity (CRC, measuring method see below) 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. Usually it is not above 40 g / g.
  • the superabsorbers according to the invention typically have an absorption under pressure (AUL0.7 psi, measuring method see below) of at least 18 g / g, preferably at least 20 g / g, preferably at least 22 g / g and usually not more than 30 g / g.
  • AUL0.7 psi absorption under pressure
  • the superabsorbent according to the invention further typically have 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 40x10 "7 cm 3 s / g and übli - not over 1000x10 "7 cm 3 s / g.
  • SFC measurement method s saline flow conductivity
  • the L value of the superabsorber (CIE color number) in the non-stored state is typically at least 75, preferably at least 80, particularly preferably at least 85 and at most 100.
  • the a-value of the superabsorbent (CIE color number) in the non-stored state is typically from -2.5 to +2.5, preferably from -2.0 to +2.0, more preferably from -1.5 to +1 ; 5.
  • the b-value of the superabsorbent (CIE color number) in the non-stored state is typically from 0 to 12, preferably from 2 to 1.
  • the superabsorber according to the invention After the relatively stressful aging test described below, the superabsorber according to the invention, after measurement for the L and a values, has only slightly worse results compared to the non-stored state, in particular b values of preferably not more than 13, particularly preferably not more than 12, up.
  • b values preferably not more than 13, particularly preferably not more than 12, up.
  • a b-value above 12 is critical in feminine hygiene articles and ultrathin diapers; a b-value of more than 15 is already critical in conventional diapers because this discoloration can be perceived by the consumer in use.
  • a further subject of the present invention are hygiene articles containing superabsorbents according to the invention, preferably ultrathin diapers, containing an absorbent layer consisting of 50 to 100 wt .-%, preferably 60 to 100 wt .-%, preferably 70 to 100 wt .-%, especially preferably from 80 to 100% by weight, very particularly preferably from 90 to 100% by weight, of superabsorbents according to the invention, wherein the coating of the absorbent layer is of course not taken into account.
  • the superabsorbents according to the invention are also very particularly advantageous for the production of laminates and composite structures, as described, for example, in US 2003/0181115 and US 2004/0019342.
  • the superabsorbents of the invention are also suitable for the preparation of completely analogous Structures using UV-crosslinkable hotmelt adhesives which are sold, for example, as AC-Resin® (BASF SE, Germany).
  • UV-crosslinkable hot-melt adhesives which are sold, for example, as AC-Resin® (BASF SE, Germany).
  • AC-Resin® BASF SE, Germany.
  • UV-crosslinkable hot-melt adhesives have the advantage of being processable at as low as 120 to 140 ° C, so they are better compatible with many thermoplastic substrates.
  • Another significant advantage is that UV-crosslinkable hot melt adhesives are toxicologically very harmless and also cause no exhalations in the toiletries.
  • the combination of the superabsorbents according to the invention with UV-crosslinkable hotmelt adhesives is therefore particularly advantageous.
  • Suitable UV-crosslinkable hot-melt adhesives are described, for example, in EP 0 377 199 A2, EP 0 445 641 A1, US Pat. No. 5,026,806, EP 0 655 465 A1 and EP 0 377 191 A2.
  • the superabsorbent according to the invention can also be used in other 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 plaster, water-absorbing material for burn dressings or for other weeping wounds), cosmetics (carrier material for pharmaceutical chemicals and medicaments, rheumatism plaster, 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 a
  • liquid absorption articles according to the invention differ from those known in that they contain the superabsorber according to the invention.
  • a process has also been found for the preparation of articles for the absorption of liquid, in particular hygiene articles, which is characterized in that at least one superabsorber according to the invention is used in the production of the article in question.
  • methods for producing such articles using superabsorbents are known.
  • the superabsorbent is tested using the test methods described below.
  • CRC 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 with 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.
  • Moisture content of the hydrogel residual moisture, water content
  • the water content of the water-absorbing polymer particles is determined according to the standard test method no. WSP 230.2-05 "Moisture content”.
  • the mean particle size of the product fraction is determined according to the standard test method no. WSP 220.2-05 "Particle size distribution”.
  • the color measurement is carried out according to the CIELAB method (Hunterlab, Volume 8, Volume 1996, No. 7, pages 1 to 4) with a colorimeter, model "LabScan XE S / N LX17309" (HunterLab, Reston, USA)
  • the values for a and b indicate the position of the color on the red / green color axes or yellow / blue, where + a stands for red, -a for green, + b for yellow and -b for blue
  • Measurement 1 (initial color): A 9 cm inner diameter plastic dish is filled with superabsorbent particles and then smoothed over the edge with a knife and the CIE color numbers and HC60 value are determined.
  • Measurement 2 (after aging): A 9 cm inner diameter plastic dish is filled with superabsorbent particles and then smoothed over the edge with a knife. The dish is then placed open in a controlled at 60 ° C cabinet with a constant relative humidity of 86%. The peel is taken out after 21 days. After cooling to room temperature, the CIE color numbers are determined.
  • the superabsorbent is in a Pflugschar ® mixer (manufacturer: Gebr Lödige Maschinenbau GmbH, Elsener Straße 7 - 9, 33102 Paderborn, Germany, type M5) at room temperature and a shaft speed of 250 revolutions per minute using a two-component spray nozzle with respectively coated amount of the respective solution. After spraying, mixing is continued for 15 minutes at a shaft speed of 80 revolutions per minute, the product is dried in a vacuum drying oven at 80 ° C. and 250 mbar pressure for 60 minutes and freed from lumps by means of an 850 ⁇ m sieve.
  • HySorb ® B 7055 100 g HySorb ® B 7055 was mixed with 0.050 g of 2,6-di-tert-butyl-4-methyl-phenol according to general procedure I.
  • Example 2 100 g HySorb ® B 7055 was mixed with 0.050 g of 2,6-di-tert-butyl-4-methyl-phenol according to general procedure I.
  • HySorb ® B 7055 were [monoethyl (3,5-di-hydroxibenzyl tert-butyl-4) phosphonate] mixed with 0.060 g of calcium bis according to general procedure I.
  • Example 3
  • HySorb ® B 7055 100 g HySorb ® B 7055 was mixed with 0.075 g of 3,5-di-tert-butyl-4-hydroxiphenylpropion- acid according to general procedure I mixed.
  • Example 4 100 g HySorb ® B 7055 was mixed with 0.075 g of 3,5-di-tert-butyl-4-hydroxiphenylpropion- acid according to general procedure I mixed.
  • HySorb ® B 7055 100 g HySorb ® B 7055 was mixed with 0.100 g of 4,4-thio-bis (6-tert-butyl-meta-cresol) according to general procedure I.
  • Example 5 100 g HySorb ® B 7055 were mixed with 0,040 g of pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) according to general procedure I mixed.
  • HySorb ® B 7055 were propionate with 0.130 g octadecyl-3- (3,5-di-tert-butyl-4-hydroxybenzophenone phenyl)) according to the general procedure I mixed.
  • HySorb ® B 7055 100 g HySorb ® B 7055 were 4,6-bis mixed with 0.050 g (dodecylthiomethyl) -ortho-cresol according to the general procedure I.
  • HySorb ® B 7055 100 g HySorb ® B 7055 was mixed with 0.070 g of 3,3 ', 3', 5,5 ', 5'-hexa-tert-butyl-a, a', a'- (mesitylene-2,4,6-triyl ) tri-para-cresol according to general procedure I.
  • HySorb ® B 7055 100 g HySorb ® B 7055 were, 3-diylbis ((3,5-di-tert-butyl-4-hydroxiphenylpropionamid) 3-) mixed with 0.050 g N, N-hexane-1 according to the general procedure I.
  • HySorb ® B 7055 100 g HySorb ® B 7055 was mixed with 0.050 g of tris (2,4-di-tert-butylphenyl) phosphite according to general procedure I mixed.
  • HySorb ® B 7055 100 g HySorb ® B 7055 were 3,9-bis (octa-decyloxi) -2,4,8,10-tetraoxa-3,9-diphosphaspiro undecane mixed with 0.060 g [5.5] according to general procedure I.
  • HySorb ® B 7055 100 g HySorb ® B 7055 was mixed with 0.040 g of bis (2,4-di-tert-butylphenol) pentaerythritol diphosphite according to the general procedure I mixed.
  • HySorb ® 7055 B was prepared according to general procedure II with 1, 5 wt .-%, based on the amount of the superabsorbent, of a 4.0 wt .-% solution of calcium bis [monoethyl (3,5-di-tert .-Butyl-4-hydroxibenzyl) phosphonate] in methanol.
  • Example 14
  • HySorb ® 7055 B was prepared according to general procedure II with 2.0 wt .-%, based on the amount of the superabsorbent, of a 2.5 wt .-% solution of tris (2, 4-d i-tert- butylphenyl) phosphite in iso-propanol.
  • HySorb ® B 7055 was obtained with 0.5 wt .-%, according to the general procedure II bis-3- (5-tert on the amount of the superabsorbent, of a 40 wt .-% aqueous dispersion of ethylene lenbis (oxyethylene) .-Butyl-4-hydroxy-m-tolyl) -propionate). Notwithstanding the general rule II, the product was not dried, but sieved directly after mixing.
  • the coated superabsorbers thus prepared were subjected to the aging test.
  • the results are summarized in Table 1.
  • the examples show that the superabsorbers according to the invention are much lighter and less discolored after aging.
  • the mixture was freed by passing nitrogen through a glass frit of oxygen.
  • 0.51 g of sodium persulfate (dissolved in 5 ml of water) and 0.06 g of hydrogen peroxide (dissolved in 6 ml of water) were added and the monomer solution was transferred to a glass dish.
  • the glass dish was dimensioned such that a layer thickness of the monomer solution of 5 cm was established.
  • 0.047 g of mixture were acid from the sodium salt of 2-hydroxy-2-sulfinatoessig-, the disodium salt of 2-hydroxy-2-sulfonatoacetic acid and sodium bisulfite (Brüggolit ® FF6, L.
  • the gel obtained was wound three times with the aid of a commercially available meat grinder with a 6 mm perforated disc and in the laboratory drying cupboard at 160 ° C.
  • This base polymer was for surface postcrosslinking in a ploughshare ® - mixer with heating jacket (manufacturer: Gebr Lödige Maschinenbau GmbH, Elsener- 7 - 9, 33102 Paderborn, Germany; Type M5.) At room temperature and a shaft speed of 450 revolutions per minute by means of a two-substance -Sprühdüse with a mixture of 0.10 wt .-% ethylene glycol diglycidyl ether (Denacol EX-810 ® from Nagase ChemteX Corporation, Osaka, Japan) by weight, 1 50 .-% 1, 2-propanediol, 2.8 wt .-% Water and 0.4 wt .-% aqueous aluminum sulfate solution (26.8 wt .-%), each based on the base polymer, coated.
  • a ploughshare ® - mixer with heating jacket manufactured by means of a two-substance -Sprühd
  • Example V16 150 g of the superabsorber of Example V16 were according to general procedure I, 0.15 g of a hydrophobic precipitated silica (Sipernat ® D-17, Evonik Degussa GmbH, Frankfurt am Main, Germany) and the amounts of calcium bis [shown in the following Table 2 monoethyl (3,5-di-tert-butyl-4-hydroxypentyl) phosphonate].
  • a hydrophobic precipitated silica Sipernat ® D-17, Evonik Degussa GmbH, Frankfurt am Main, Germany
  • the coated superabsorbers produced in this way were subjected to the aging test.
  • the results are summarized in Table 2.
  • the examples show that even small amounts of the stabilizer stabilize the superabsorber according to the invention against discoloration on aging.
  • Example V16 150 g of the superabsorber of Example V16 were according to general procedure I, 0.15 g of a hydrophobic precipitated silica (Sipernat ® D-17, Evonik Degussa GmbH, Frankfurt am Main, Germany) and the amounts indicated in Table 3 below tris (2,4-di-tert-butylphenyl) phosphite.
  • a hydrophobic precipitated silica Sipernat ® D-17, Evonik Degussa GmbH, Frankfurt am Main, Germany
  • Example V16 was repeated except that the monomer solution was additionally added with 0.59 g of calcium bis [monoethyl (3,5-di-tert-butyl-4-hydroxibenzyl) phosphonate] prior to further cooling to 15 ° C.
  • Example V16 was repeated except that 0.59 g of calcium bis [monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate] was added to the gel in the wake.
  • the monomer solution was mixed via a static mixer with two initiator solutions.
  • initiator 1 a 3 wt .-% solution of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride in deionized water
  • initiator 2 a 6.1 wt. % solution of sodium peroxodisulfate in deionized water.
  • the metering rate of the initiator solution 1 was 1.462 kg / h
  • the metering rate of the solution 2 was 0.629 kg / h.
  • the resulting polymer particles were screened to separate any agglomerates formed.
  • the sieve fraction of 150 to 850 ⁇ was recovered as a product.
  • Example V28 100 g of the superabsorbent of Example V28 were mixed with 0.10 g of pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) according to general procedure I.
  • Example V28 100 g of the superabsorbent of Example V28 were mixed with 0.10 g of tris (2,4-di-tert-butylphenyl) phosphite according to general procedure I.
  • Example V28 100 g of the superabsorbent of Example V28 were mixed with 0.05 g of pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) and 0.05 g of tris (2,4-di tert-butylphenyl) phosphite according to general procedure I.
  • a 3 wt .-% solution of ascorbic acid in deionized water was used.
  • the metering rate of the initiator solution 1 was 0.548 kg / h
  • the metering rate of the solution 2 was 0.449 kg / h
  • the metering rate of the solution 3 was 0.183 kg / h.
  • the resulting polymer particles were screened to separate any agglomerates formed.
  • the sieve fraction of 150 to 850 ⁇ was recovered as a product.
  • the monomer solution was mixed via a static mixer with three initiator solutions.
  • initiator 1 a 3 wt .-% solution of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride in deionized water
  • initiator 2 a 6.1 wt. -% solution of sodium peroxodisulfate in deionized water
  • initiator 3 was a 3 wt .-% solution of a mixture of the sodium salt of 2-hydroxy-2-sulfinatoacetic acid, the disodium salt of 2-hydroxy-2-sulfonatoessig- acid and sodium bisulfite (Brüggolit ® FF7, L.
  • the obtained polymer particles were sieved to separate any formed agglomerates. The sieve fraction of 150 to 850 ⁇ was recovered as a product.
  • Example 32 100 g of the superabsorber of Example V31 were mixed with 0.10 g of calcium bis [monoethyl (3,5-di-tert-butyl-4-hydroxypentyl) phosphonate] according to general procedure I.
  • Example 32 100 g of the superabsorber of Example V31 were mixed with 0.10 g of calcium bis [monoethyl (3,5-di-tert-butyl-4-hydroxypentyl) phosphonate] according to general procedure I.
  • Example 32 100 g of the superabsorber of Example V31 were mixed with 0.10 g of calcium bis [monoethyl (3,5-di-tert-butyl-4-hydroxypentyl) phosphonate] according to general procedure I.
  • Example V32 100 g of the superabsorber of Example V32 were mixed with 0.10 g of diethyl (3,5-di-tert-butyl-4-hydroxibenzyl) phosphonate according to general procedure I.
  • the superabsorbents prepared in this way were subjected to the aging test.
  • the results are summarized in Table 6. The examples show that the superabsorbers according to the invention are much lighter and less discolored after aging.
  • the shaft of the reactor was rotated continuously at 96 revolutions per minute.
  • the reaction mixture was cooled from the outside so that the subsequent addition of initiator took place at about 20 ° C.
  • 0.046 g of ascorbic acid dissolved in 9.12 g of water
  • 0.127 g of 30 wt .-% aqueous hydrogen peroxide solution diluted with 1 , 15 g of water
  • This base polymer was for surface postcrosslinking in a ploughshare ® - mixer with heating jacket (manufacturer: Gebr Lödige Maschinenbau GmbH, Elsener- 7 - 9, 33102 Paderborn, Germany; Type M5.) At room temperature and a shaft speed of 450 revolutions per minute by means of a two-substance Spray nozzle with a mixture of 0.125 wt .-% N- (2-hydroxyethyl) -2-oxazolidinone, 1, 5 wt .-% water, 1, 5 wt.% 1, 3-propanediol, 0.003 wt .-% sorbitan monococoate (" Span® 20") and 2.8% by weight of a 25% by weight aqueous aluminum lactate solution, based in each case on the base polymer After spraying, the product temperature was raised to 175 ° C. and the reaction mixture 80 The resulting product was allowed to cool back to room temperature and sieved The surface-postcrosslinked superabsorber was
  • Example 34 100 g of the superabsorbent of Example V26 were mixed with 0.050 g of 2,2'-ethylidenebis [4,6-bis (1,1-dimethylethyl) phenol] according to general procedure I.
  • Example 34 100 g of the superabsorbent of Example V26 were mixed with 0.050 g of 2,2'-ethylidenebis [4,6-bis (1,1-dimethylethyl) phenol] according to general procedure I.
  • Example 34 100 g of the superabsorbent of Example V26 were mixed with 0.050 g of 2,2'-ethylidenebis [4,6-bis (1,1-dimethylethyl) phenol] according to general procedure I.
  • Example 34 100 g of the superabsorbent of Example V26 were mixed with 0.050 g of 2,2'-ethylidenebis [4,6-bis (1,1-dimethylethyl) phenol] according to general procedure I.
  • Example V33 was repeated, but in the case of surface postcrosslinking, the base polymer was additionally coated with 0.2% by weight of tris- (2,4-di-tert-butylphenyl) phosphite, based on the base polymer.
  • Example V33 (comparison) was repeated, but in the polymerization after reaching an internal temperature of 60 ° C of the reaction mixture in Pflugschar ® paddle dryer still 1, 2 g pentaerythritol tetrakis (3- (3,5-di-tert. -butyl-4-hydroxyphenyl) propionate).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un superabsorbant qui contient au moins un stabilisant contre un changement de couleur, lequel est choisi parmi les phénols, l'acide phosphonique (HP(O)(OH)2), l'acide phosphoreux (H3PO3) et les sels et esters de ces acides. Le superabsorbant présente une stabilité améliorée aux changements de couleur lors d'un stockage à haute température ou en présence d'une forte humidité.
PCT/EP2010/063199 2009-09-16 2010-09-09 Superabsorbant à stabilité de couleur WO2011032876A1 (fr)

Priority Applications (3)

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BR112012005901A BR112012005901A2 (pt) 2009-09-16 2010-09-09 superabsorvente, processo para produzir um superabsorvente, artigo para absorver fluidos, e, processo para produzir artigos para absorver fluidos
JP2012529215A JP2013504674A (ja) 2009-09-16 2010-09-09 色安定性の超吸収剤
CN2010800414261A CN102597082A (zh) 2009-09-16 2010-09-09 颜色稳定的超吸收剂

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EP09011809 2009-09-16
EP09011809.2 2009-09-16

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CN (1) CN102597082A (fr)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8497337B2 (en) 2009-11-23 2013-07-30 Basf Se Process for producing water-absorbing polymer particles with improved color stability

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* Cited by examiner, † Cited by third party
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CN104365491A (zh) * 2014-11-18 2015-02-25 芜湖悠派卫生用品有限公司 一种有机环保猫砂及其制备方法
CN104351062A (zh) * 2014-11-25 2015-02-18 芜湖悠派卫生用品有限公司 一种椰壳活性炭猫砂及其制备方法
WO2018029045A1 (fr) * 2016-08-10 2018-02-15 Basf Se Procédé de fabrication de superabsorbants
CN112295386B (zh) * 2019-08-02 2022-06-14 中国石油化工股份有限公司 用于苯乙烯废气处理中产生的二氧化锰的活化剂及其应用
CN111792980A (zh) * 2020-06-18 2020-10-20 湖南国发精细化工科技有限公司 一种含有防变色剂的邻仲丁基酚

Citations (72)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4020256A (en) 1975-07-03 1977-04-26 The Dow Chemical Company Method for preparing polymers from water soluble vinyl monomers
DE3519013A1 (de) 1985-05-25 1986-11-27 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von pulverfoermigen wasserloeslichen polymerisaten und deren verwendung
GB2184733A (en) * 1985-12-18 1987-07-01 Basf Corp Stabilizer package for the preparation of thermoplastic polyurethane having improved high temperature color stability
DE3825366A1 (de) 1987-07-28 1989-02-09 Dai Ichi Kogyo Seiyaku Co Ltd Verfahren zur kontinuierlichen herstellung eines acrylpolymergels
EP0348180A2 (fr) 1988-06-22 1989-12-27 Mitsubishi Petrochemical Company Limited Procédé de préparation d'une résine absorbant de l'eau
EP0377191A2 (fr) 1988-12-31 1990-07-11 BASF Aktiengesellschaft Composés sensibles aux radiations à insaturation éthylénique copolymérisables et leur procédé de préparation
EP0377199A2 (fr) 1988-12-31 1990-07-11 BASF Aktiengesellschaft Compositions réticulables par UV à base de polymères d'esters (méth)-acryliques
EP0386897A2 (fr) 1989-02-28 1990-09-12 Nippon Shokubai Co., Ltd. Procédé pour préparer des polymères absorbant l'eau de qualité améliorée et les produits obtenus
WO1990015830A1 (fr) 1989-06-12 1990-12-27 Weyerhaeuser Company Polymere hydrocolloidal
US5026806A (en) 1988-10-31 1991-06-25 Basf Aktiengesellschaft UV-crosslinkable materials based on isoamyl (meth)acrylate copolymers
EP0441975A1 (fr) 1989-09-04 1991-08-21 Nippon Shokubai Co., Ltd. Procede pour la preparation de resine pouvant absorber de l'eau
EP0445619A2 (fr) 1990-03-08 1991-09-11 BASF Aktiengesellschaft Procédé de préparation de polymères à dimensions fines solubles dans l'eau
EP0445641A1 (fr) 1990-03-08 1991-09-11 BASF Aktiengesellschaft Composés non saturés éthyléniques
EP0457660A1 (fr) 1990-05-14 1991-11-21 Societe Francaise Hoechst Nouveaux polymères absorbants, leur procédé de fabrication et leur application
EP0505163A1 (fr) 1991-03-18 1992-09-23 Nalco Chemical Company Réduction de monomères résiduels en polymères superabsorbants
EP0530438A1 (fr) 1991-09-03 1993-03-10 Hoechst Celanese Corporation Polymère superabsorbant à propriétés de pouvoir absorbant perfectionné
EP0534228A1 (fr) 1991-09-18 1993-03-31 Hoechst Aktiengesellschaft Procédé de modification de polymérisats hydrophiles
JPH0586251A (ja) 1991-09-26 1993-04-06 Uni Charm Corp 高吸水性ポリマー組成物
EP0547847A1 (fr) 1991-12-18 1993-06-23 Nippon Shokubai Co., Ltd. Procédé de préparation d'une résine absorbant l'eau
JPH05230291A (ja) * 1992-02-18 1993-09-07 Showa Denko Kk 低温長期保存下での耐変色性に優れた樹脂組成物
EP0559476A1 (fr) 1992-03-05 1993-09-08 Nippon Shokubai Co., Ltd. Méthode de préparation d'une résine absorbante
WO1993021237A1 (fr) 1992-04-16 1993-10-28 The Dow Chemical Company Resines hydrophiles reticulees et procede de preparation
EP0605215A1 (fr) 1992-12-25 1994-07-06 Nippon Shokubai Co., Ltd. Absorbant et procédé de préparation d'une résine absorbante
EP0632068A1 (fr) 1993-06-18 1995-01-04 Nippon Shokubai Co., Ltd. Procédé de préparation d'une résine absorbante
EP0640330A1 (fr) 1993-06-30 1995-03-01 The Procter & Gamble Company Produits absorbants hygiéniques
EP0655465A1 (fr) 1993-11-25 1995-05-31 BASF Aktiengesellschaft Procédé pour éliminer des résidus volatiles de polyacrylates fondues
EP0668080A2 (fr) 1994-02-17 1995-08-23 Nippon Shokubai Co., Ltd. Agent d'absorption d'eau, sa méthode de production et composition absorbant l'eau
WO1996040427A1 (fr) 1995-06-07 1996-12-19 Freeman Clarence S Procede et appareil de polymerisation et polymere
DE19646484A1 (de) 1995-11-21 1997-05-22 Stockhausen Chem Fab Gmbh Flüssigkeitsabsorbierende Polymere, Verfahren zu deren Herstellung und deren Verwendung
DE19543368A1 (de) 1995-11-21 1997-05-22 Stockhausen Chem Fab Gmbh Wasserabsorbierende Polymere mit verbesserten Eigenschaften, Verfahren zu deren Herstellung und deren Verwendung
EP0816383A1 (fr) 1996-06-24 1998-01-07 Clariant GmbH Procédé de préparation d'hydrogels hydrophiles à forte capacité de gonflement
WO1999018067A1 (fr) 1997-10-02 1999-04-15 L. Brüggemann KG Derives d'acide sulfinique, leur production et leur utilisation
EP0955086A2 (fr) 1998-04-28 1999-11-10 Nippon Shokubai Co., Ltd. Procédé et production d'une resin adsorbante constituée d'hydrogel moulé
DE19846413A1 (de) 1998-10-08 2000-04-13 Basf Ag Verfahren zur Herstellung von hydrophilen wasserquellbaren Polymeren sowie deren Verwendung
WO2000055245A1 (fr) 1999-03-12 2000-09-21 Basf Aktiengesellschaft Composition polymerique superabsorbente de couleur stable
JP2000327926A (ja) * 1999-05-25 2000-11-28 Sanyo Chem Ind Ltd 吸収剤組成物および吸収性物品
WO2001038402A1 (fr) 1999-11-20 2001-05-31 Basf Aktiengesellschaft Procede de preparation continue de polymerisats geliformes reticules a fines particules
US6241928B1 (en) 1998-04-28 2001-06-05 Nippon Shokubai Co., Ltd. Method for production of shaped hydrogel of absorbent resin
EP1191051A2 (fr) 2000-09-20 2002-03-27 Nippon Shokubai Co., Ltd. Préparation de particules polymériques absorbant l'eau
WO2002032962A2 (fr) 2000-10-20 2002-04-25 Millennium Pharmaceuticals, Inc. Procedes et compositions des proteines humaines 80090, 52874, 52880, 63497, et 33425 et leurs utilisations
WO2002055469A1 (fr) 2001-01-12 2002-07-18 Degussa Ag Procede continu pour la production et la purification d'acide (meth)acrylique
WO2002094329A1 (fr) 2001-05-23 2002-11-28 Basf Aktiengesellschaft Articles absorbants contenant un agent desodorisant
WO2002094328A2 (fr) 2001-05-23 2002-11-28 Basf Aktiengesellschaft Article absorbant
US20020193546A1 (en) 1990-06-06 2002-12-19 Waterguard Telecommunications Technologies, Inc. A Texas Corporation Polymerization process, apparatus mid polymer
WO2003014172A2 (fr) 2001-08-03 2003-02-20 Basf Aktiengesellschaft Procédé pour fabriquer des résines hydrophiles
WO2003059962A1 (fr) 2002-01-16 2003-07-24 Sumitomo Seika Chemicals Co., Ltd. Procede de production d'une resine absorbant l'eau
WO2003078378A1 (fr) 2002-03-15 2003-09-25 Stockhausen Gmbh Cristal d'acide (meth)acrylique et procede pour produire et purifier de l'acide (meth)acrylique aqueux
US20030181115A1 (en) 2002-02-04 2003-09-25 Kinya Nagasuna Absorbent structure, its production process, and absorbent article comprising said absorbent structure
WO2003104299A1 (fr) 2002-06-11 2003-12-18 Basf Aktiengesellschaft Procede de production d'esters de polyalcools
WO2003104301A1 (fr) 2002-06-11 2003-12-18 Basf Aktiengesellschaft (meth)acrylesters de glycerine polyalcoxy
WO2003104300A1 (fr) 2002-06-01 2003-12-18 Basf Aktiengesellschaft Esters (meth)acryliques de trimethylolpropane polyalcoxyle
US20040019342A1 (en) 2001-09-19 2004-01-29 Kinya Nagasuna Absorbent structure, absorbent article, water-absorbent resin, and its production process and evaluation method
WO2004035514A1 (fr) 2002-10-10 2004-04-29 Basf Aktiengesellschaft Procede de production d'acide acrylique
DE10331450A1 (de) 2003-07-10 2005-01-27 Basf Ag (Meth)acrylsäureester monoalkoxilierter Polyole und deren Herstellung
WO2005011860A2 (fr) 2003-07-25 2005-02-10 Stockhausen Gmbh Polymeres pulverulents hydrophiles, a fines particules liees par des adhesifs thermoplastiques
DE10331456A1 (de) 2003-07-10 2005-02-24 Basf Ag (Meth)acrylsäureester alkoxilierter ungesättigter Polyolether und deren Herstellung
WO2005054356A1 (fr) 2003-12-03 2005-06-16 Basf Aktiengesellschaft Superabsorants contenant au moins un phénol monovalent et / ou polyvalent à encombrement stérique
DE10355401A1 (de) 2003-11-25 2005-06-30 Basf Ag (Meth)acrylsäureester ungesättigter Aminoalkohole und deren Herstellung
WO2005073260A1 (fr) 2004-01-28 2005-08-11 Basf Aktiengesellschaft Procede pour preparer des polymeres
EP1577349A1 (fr) 2002-12-27 2005-09-21 Sumitomo Seika Chemicals Co., Ltd. Composition de resine absorbant l'eau
US20050256757A1 (en) 2004-04-30 2005-11-17 Sierra Alisa K Method of manufacturing and method of marketing gender-specific absorbent articles having liquid-handling properties tailored to each gender
EP1645596A1 (fr) 2003-07-11 2006-04-12 Sumitomo Seika Chemicals Co., Ltd. Composition de resine absorbant l'eau
WO2006058682A1 (fr) 2004-11-30 2006-06-08 Basf Aktiengesellschaft Procede de postreticulation de particules polymeres absorbant l'eau
DE102005044035A1 (de) 2005-09-14 2007-03-15 Basf Ag Verfahren zum Vertropfen von Flüssigkeiten
WO2007093531A1 (fr) 2006-02-17 2007-08-23 Basf Se Procédé de production de particules polymères absorbant l'eau par polymérisation de gouttes d'une solution de monomère
WO2008055856A1 (fr) 2006-11-09 2008-05-15 Basf Se Procédé de fabrication de superabsorbants
WO2008086976A1 (fr) 2007-01-16 2008-07-24 Basf Se Procédé de fabrication de particules polymères par polymérisation de gouttes de liquide dans une phase gazeuse
WO2008092843A1 (fr) 2007-01-29 2008-08-07 Basf Se Procédé de fabrication de particules polymères blanches, résistantes à la décoloration, absorbant l'eau, présentant une grande capacité d'absorption et une grande conductivité de liquides
WO2008092842A1 (fr) 2007-01-29 2008-08-07 Basf Se Procédé de fabrication de particules polymères blanches, résistantes à la décoloration, absorbant l'eau, présentant une grande capacité d'absorption et une grande conductivité de liquides
WO2009005114A1 (fr) * 2007-07-04 2009-01-08 Nippon Shokubai Co., Ltd. Agent particulaire hydro-absorbant et son procédé de production
WO2009027356A1 (fr) 2007-08-30 2009-03-05 Basf Se Procédé de fabrication de particules polymères absorbant l'eau, par polymérisation de gouttes d'une solution monomère
WO2009060062A1 (fr) 2007-11-08 2009-05-14 Evonik Stockhausen Gmbh Structures polymères absorbant l'eau qui présentent une meilleure stabilité de couleur

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19807504A1 (de) * 1998-02-21 1999-08-26 Basf Ag Vernetzte quellfähige Polymere
US6444744B1 (en) * 1998-03-11 2002-09-03 Nippon Shokubai Co., Ltd. Hydrophilic resin, absorbent article, and acrylic acid for polymerization
JP2000230129A (ja) * 1998-12-11 2000-08-22 Nippon Shokubai Co Ltd 吸水剤組成物
DE10161864A1 (de) * 2001-12-14 2003-07-03 Basf Ag Stabilisatorzusammensetzung III
CN1831019B (zh) * 2001-12-19 2010-05-12 株式会社日本触媒 吸水性树脂及其制备方法
JP2005186016A (ja) * 2003-12-26 2005-07-14 San-Dia Polymer Ltd 吸収剤
CN101151285B (zh) * 2005-04-07 2011-05-11 株式会社日本触媒 聚丙烯酸（盐）吸水树脂，及其生产方法，以及在生产吸水树脂的聚合中使用的丙烯酸

Patent Citations (74)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4020256A (en) 1975-07-03 1977-04-26 The Dow Chemical Company Method for preparing polymers from water soluble vinyl monomers
DE3519013A1 (de) 1985-05-25 1986-11-27 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von pulverfoermigen wasserloeslichen polymerisaten und deren verwendung
GB2184733A (en) * 1985-12-18 1987-07-01 Basf Corp Stabilizer package for the preparation of thermoplastic polyurethane having improved high temperature color stability
DE3825366A1 (de) 1987-07-28 1989-02-09 Dai Ichi Kogyo Seiyaku Co Ltd Verfahren zur kontinuierlichen herstellung eines acrylpolymergels
EP0348180A2 (fr) 1988-06-22 1989-12-27 Mitsubishi Petrochemical Company Limited Procédé de préparation d'une résine absorbant de l'eau
US5026806A (en) 1988-10-31 1991-06-25 Basf Aktiengesellschaft UV-crosslinkable materials based on isoamyl (meth)acrylate copolymers
EP0377191A2 (fr) 1988-12-31 1990-07-11 BASF Aktiengesellschaft Composés sensibles aux radiations à insaturation éthylénique copolymérisables et leur procédé de préparation
EP0377199A2 (fr) 1988-12-31 1990-07-11 BASF Aktiengesellschaft Compositions réticulables par UV à base de polymères d'esters (méth)-acryliques
EP0386897A2 (fr) 1989-02-28 1990-09-12 Nippon Shokubai Co., Ltd. Procédé pour préparer des polymères absorbant l'eau de qualité améliorée et les produits obtenus
WO1990015830A1 (fr) 1989-06-12 1990-12-27 Weyerhaeuser Company Polymere hydrocolloidal
EP0441975A1 (fr) 1989-09-04 1991-08-21 Nippon Shokubai Co., Ltd. Procede pour la preparation de resine pouvant absorber de l'eau
EP0445619A2 (fr) 1990-03-08 1991-09-11 BASF Aktiengesellschaft Procédé de préparation de polymères à dimensions fines solubles dans l'eau
EP0445641A1 (fr) 1990-03-08 1991-09-11 BASF Aktiengesellschaft Composés non saturés éthyléniques
EP0457660A1 (fr) 1990-05-14 1991-11-21 Societe Francaise Hoechst Nouveaux polymères absorbants, leur procédé de fabrication et leur application
US20020193546A1 (en) 1990-06-06 2002-12-19 Waterguard Telecommunications Technologies, Inc. A Texas Corporation Polymerization process, apparatus mid polymer
EP0505163A1 (fr) 1991-03-18 1992-09-23 Nalco Chemical Company Réduction de monomères résiduels en polymères superabsorbants
EP0530438A1 (fr) 1991-09-03 1993-03-10 Hoechst Celanese Corporation Polymère superabsorbant à propriétés de pouvoir absorbant perfectionné
EP0534228A1 (fr) 1991-09-18 1993-03-31 Hoechst Aktiengesellschaft Procédé de modification de polymérisats hydrophiles
JPH0586251A (ja) 1991-09-26 1993-04-06 Uni Charm Corp 高吸水性ポリマー組成物
EP0547847A1 (fr) 1991-12-18 1993-06-23 Nippon Shokubai Co., Ltd. Procédé de préparation d'une résine absorbant l'eau
JPH05230291A (ja) * 1992-02-18 1993-09-07 Showa Denko Kk 低温長期保存下での耐変色性に優れた樹脂組成物
EP0559476A1 (fr) 1992-03-05 1993-09-08 Nippon Shokubai Co., Ltd. Méthode de préparation d'une résine absorbante
WO1993021237A1 (fr) 1992-04-16 1993-10-28 The Dow Chemical Company Resines hydrophiles reticulees et procede de preparation
EP0605215A1 (fr) 1992-12-25 1994-07-06 Nippon Shokubai Co., Ltd. Absorbant et procédé de préparation d'une résine absorbante
EP0632068A1 (fr) 1993-06-18 1995-01-04 Nippon Shokubai Co., Ltd. Procédé de préparation d'une résine absorbante
EP0640330A1 (fr) 1993-06-30 1995-03-01 The Procter & Gamble Company Produits absorbants hygiéniques
EP0655465A1 (fr) 1993-11-25 1995-05-31 BASF Aktiengesellschaft Procédé pour éliminer des résidus volatiles de polyacrylates fondues
EP0668080A2 (fr) 1994-02-17 1995-08-23 Nippon Shokubai Co., Ltd. Agent d'absorption d'eau, sa méthode de production et composition absorbant l'eau
EP1570869A1 (fr) 1994-02-17 2005-09-07 Nippon Shokubai Co., Ltd. Agent d'absorption d'eau, sa méthode de production et composition absorbant de l'eau
WO1996040427A1 (fr) 1995-06-07 1996-12-19 Freeman Clarence S Procede et appareil de polymerisation et polymere
DE19646484A1 (de) 1995-11-21 1997-05-22 Stockhausen Chem Fab Gmbh Flüssigkeitsabsorbierende Polymere, Verfahren zu deren Herstellung und deren Verwendung
DE19543368A1 (de) 1995-11-21 1997-05-22 Stockhausen Chem Fab Gmbh Wasserabsorbierende Polymere mit verbesserten Eigenschaften, Verfahren zu deren Herstellung und deren Verwendung
EP0816383A1 (fr) 1996-06-24 1998-01-07 Clariant GmbH Procédé de préparation d'hydrogels hydrophiles à forte capacité de gonflement
WO1999018067A1 (fr) 1997-10-02 1999-04-15 L. Brüggemann KG Derives d'acide sulfinique, leur production et leur utilisation
EP0955086A2 (fr) 1998-04-28 1999-11-10 Nippon Shokubai Co., Ltd. Procédé et production d'une resin adsorbante constituée d'hydrogel moulé
US6241928B1 (en) 1998-04-28 2001-06-05 Nippon Shokubai Co., Ltd. Method for production of shaped hydrogel of absorbent resin
DE19846413A1 (de) 1998-10-08 2000-04-13 Basf Ag Verfahren zur Herstellung von hydrophilen wasserquellbaren Polymeren sowie deren Verwendung
WO2000055245A1 (fr) 1999-03-12 2000-09-21 Basf Aktiengesellschaft Composition polymerique superabsorbente de couleur stable
JP2000327926A (ja) * 1999-05-25 2000-11-28 Sanyo Chem Ind Ltd 吸収剤組成物および吸収性物品
WO2001038402A1 (fr) 1999-11-20 2001-05-31 Basf Aktiengesellschaft Procede de preparation continue de polymerisats geliformes reticules a fines particules
EP1191051A2 (fr) 2000-09-20 2002-03-27 Nippon Shokubai Co., Ltd. Préparation de particules polymériques absorbant l'eau
WO2002032962A2 (fr) 2000-10-20 2002-04-25 Millennium Pharmaceuticals, Inc. Procedes et compositions des proteines humaines 80090, 52874, 52880, 63497, et 33425 et leurs utilisations
WO2002055469A1 (fr) 2001-01-12 2002-07-18 Degussa Ag Procede continu pour la production et la purification d'acide (meth)acrylique
WO2002094329A1 (fr) 2001-05-23 2002-11-28 Basf Aktiengesellschaft Articles absorbants contenant un agent desodorisant
WO2002094328A2 (fr) 2001-05-23 2002-11-28 Basf Aktiengesellschaft Article absorbant
WO2003014172A2 (fr) 2001-08-03 2003-02-20 Basf Aktiengesellschaft Procédé pour fabriquer des résines hydrophiles
US20040019342A1 (en) 2001-09-19 2004-01-29 Kinya Nagasuna Absorbent structure, absorbent article, water-absorbent resin, and its production process and evaluation method
US20050085604A1 (en) 2002-01-16 2005-04-21 Masayoshi Handa Process for producing water-absorbing resin
WO2003059962A1 (fr) 2002-01-16 2003-07-24 Sumitomo Seika Chemicals Co., Ltd. Procede de production d'une resine absorbant l'eau
US20030181115A1 (en) 2002-02-04 2003-09-25 Kinya Nagasuna Absorbent structure, its production process, and absorbent article comprising said absorbent structure
WO2003078378A1 (fr) 2002-03-15 2003-09-25 Stockhausen Gmbh Cristal d'acide (meth)acrylique et procede pour produire et purifier de l'acide (meth)acrylique aqueux
WO2003104300A1 (fr) 2002-06-01 2003-12-18 Basf Aktiengesellschaft Esters (meth)acryliques de trimethylolpropane polyalcoxyle
WO2003104299A1 (fr) 2002-06-11 2003-12-18 Basf Aktiengesellschaft Procede de production d'esters de polyalcools
WO2003104301A1 (fr) 2002-06-11 2003-12-18 Basf Aktiengesellschaft (meth)acrylesters de glycerine polyalcoxy
WO2004035514A1 (fr) 2002-10-10 2004-04-29 Basf Aktiengesellschaft Procede de production d'acide acrylique
EP1577349A1 (fr) 2002-12-27 2005-09-21 Sumitomo Seika Chemicals Co., Ltd. Composition de resine absorbant l'eau
DE10331456A1 (de) 2003-07-10 2005-02-24 Basf Ag (Meth)acrylsäureester alkoxilierter ungesättigter Polyolether und deren Herstellung
DE10331450A1 (de) 2003-07-10 2005-01-27 Basf Ag (Meth)acrylsäureester monoalkoxilierter Polyole und deren Herstellung
EP1645596A1 (fr) 2003-07-11 2006-04-12 Sumitomo Seika Chemicals Co., Ltd. Composition de resine absorbant l'eau
WO2005011860A2 (fr) 2003-07-25 2005-02-10 Stockhausen Gmbh Polymeres pulverulents hydrophiles, a fines particules liees par des adhesifs thermoplastiques
DE10355401A1 (de) 2003-11-25 2005-06-30 Basf Ag (Meth)acrylsäureester ungesättigter Aminoalkohole und deren Herstellung
WO2005054356A1 (fr) 2003-12-03 2005-06-16 Basf Aktiengesellschaft Superabsorants contenant au moins un phénol monovalent et / ou polyvalent à encombrement stérique
WO2005073260A1 (fr) 2004-01-28 2005-08-11 Basf Aktiengesellschaft Procede pour preparer des polymeres
US20050256757A1 (en) 2004-04-30 2005-11-17 Sierra Alisa K Method of manufacturing and method of marketing gender-specific absorbent articles having liquid-handling properties tailored to each gender
WO2006058682A1 (fr) 2004-11-30 2006-06-08 Basf Aktiengesellschaft Procede de postreticulation de particules polymeres absorbant l'eau
DE102005044035A1 (de) 2005-09-14 2007-03-15 Basf Ag Verfahren zum Vertropfen von Flüssigkeiten
WO2007093531A1 (fr) 2006-02-17 2007-08-23 Basf Se Procédé de production de particules polymères absorbant l'eau par polymérisation de gouttes d'une solution de monomère
WO2008055856A1 (fr) 2006-11-09 2008-05-15 Basf Se Procédé de fabrication de superabsorbants
WO2008086976A1 (fr) 2007-01-16 2008-07-24 Basf Se Procédé de fabrication de particules polymères par polymérisation de gouttes de liquide dans une phase gazeuse
WO2008092843A1 (fr) 2007-01-29 2008-08-07 Basf Se Procédé de fabrication de particules polymères blanches, résistantes à la décoloration, absorbant l'eau, présentant une grande capacité d'absorption et une grande conductivité de liquides
WO2008092842A1 (fr) 2007-01-29 2008-08-07 Basf Se Procédé de fabrication de particules polymères blanches, résistantes à la décoloration, absorbant l'eau, présentant une grande capacité d'absorption et une grande conductivité de liquides
WO2009005114A1 (fr) * 2007-07-04 2009-01-08 Nippon Shokubai Co., Ltd. Agent particulaire hydro-absorbant et son procédé de production
WO2009027356A1 (fr) 2007-08-30 2009-03-05 Basf Se Procédé de fabrication de particules polymères absorbant l'eau, par polymérisation de gouttes d'une solution monomère
WO2009060062A1 (fr) 2007-11-08 2009-05-14 Evonik Stockhausen Gmbh Structures polymères absorbant l'eau qui présentent une meilleure stabilité de couleur

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
"Hunterlab", vol. 8, 1996, pages: 1 - 4
"Modern Superabsorbent Polymer Technology", 1997, J. WILEY & SONS
DATABASE WPI Week 199340, Derwent World Patents Index; AN 1993-317644, XP002605560 *
DATABASE WPI Week 200130, Derwent World Patents Index; AN 2001-284977, XP002615991 *
DATABASE WPI Week 200915, Derwent World Patents Index; AN 2009-B36405, XP002615992 *
REIHE KONTAKT; STUDIUM, THOMAS RICHTER: "Literaturstellen beschrieben: Zerstäuben von Flüssigkeiten", vol. 660, 2004, EXPERT-VERLAG
VDI-REIHE; GÜNTER WOZNIAK: "Zerstäubungstechnik", 2002, SPRINGER-VERLAG

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8497337B2 (en) 2009-11-23 2013-07-30 Basf Se Process for producing water-absorbing polymer particles with improved color stability

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