EP2580256A2 - Particules polymères hydroabsorbantes présentant une stabilité de couleur améliorée - Google Patents

Particules polymères hydroabsorbantes présentant une stabilité de couleur améliorée

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Publication number
EP2580256A2
EP2580256A2 EP11726118.0A EP11726118A EP2580256A2 EP 2580256 A2 EP2580256 A2 EP 2580256A2 EP 11726118 A EP11726118 A EP 11726118A EP 2580256 A2 EP2580256 A2 EP 2580256A2
Authority
EP
European Patent Office
Prior art keywords
polymer particles
water
alkyl
hydrogen
absorbing polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP11726118.0A
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German (de)
English (en)
Inventor
Norbert Herfert
Thomas Daniel
Mark Elliott
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP11726118.0A priority Critical patent/EP2580256A2/fr
Publication of EP2580256A2 publication Critical patent/EP2580256A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments

Definitions

  • the present invention relates to water-absorbing polymer particles having improved color stability and to processes for their preparation, wherein the water-absorbing polymer particles contain at least one optical brightener.
  • Water-absorbing polymer particles are used for the production of diapers, tampons, feminine pads and other hygiene articles, but also as water-retaining agents in agricultural horticulture.
  • the water-absorbing polymer particles are also often referred to as absorbent resin, superabsorbents, superabsorbent polymers, absorbent polymers, absorbent gelling materials, hydrophilic polymers, hydrogels or superabsorbents.
  • absorbent resin superabsorbents
  • superabsorbent polymers absorbent polymers
  • absorbent gelling materials hydrophilic polymers
  • hydrogels or superabsorbents The preparation of water-absorbing polymer particles is described in the monograph "Modern Superabsorbent Polymer Technology", F.L. Buchholz and AT. Graham, Wiley-VCH, 1998, pages 71-103.
  • the properties of the water-absorbing polymer particles can be adjusted, for example, via the amount of crosslinker used. As the amount of crosslinker increases, the centrifuge retention capacity (CRC) decreases and the absorption under a pressure of 21.0 g / cm 2 (AUL 0.3 psi) goes through a maximum.
  • CRC centrifuge retention capacity
  • water-absorbing polymer particles are generally surface-postcrosslinked.
  • the degree of crosslinking of the particle surface increases, whereby the absorption under a pressure of 49.2 g / cm 2 (AUL0.7 psi) and the centrifuge retention capacity (CRC) can be at least partially decoupled.
  • This surface postcrosslinking can be carried out in aqueous gel phase.
  • dried, ground and sieved polymer particles Preferably, dried, ground and sieved polymer particles
  • Crosslinkers suitable for this purpose are compounds which can form covalent bonds with at least two carboxylate groups of the water-absorbing polymer particles.
  • a common problem with water-absorbing polymer particles is discoloration that occurs when stored under higher temperature or higher humidity. Such conditions often occur when stored in tropical or subtropical countries. Under such conditions, water-absorbing polymer particles tend to yellow, they may even assume brown or almost almost black color. This discoloration of the actually colorless water-absorbing polymer particles is unsightly and undesirable, since it is particularly visible in the desired thin hygiene products and consumers reject unsightly hygiene products.
  • the cause of the discoloration is not fully understood, however, reactive compounds such as residual monomers from the polymerization, the use of some initiators, impurities of the monomer or the neutralizing agent, surface postcrosslinkers or stabilizers of the monomers used to play a role.
  • the color stability of water-absorbing polymer particles can be improved by adding inorganic reducing agents.
  • the inorganic reducing agents may, for example, be added to the polymer gel after the polymerization or after the thermal surface postcrosslinking.
  • WO 2006/058682 A1 teaches that the presence of oxygen in the thermal surface postcrosslinking leads to discoloration.
  • sulfinic acids as polymerization initiators has a favorable effect on the color stability of the resulting water-absorbing polymer particles.
  • WO 2008/092842 A1 and WO 2008/092843 A1 disclose the coating with basic salts for the same purpose. According to WO 2009/060062 A1, the color stability of water-absorbing polymer particles with sulfonic acids and their salts can be increased, the sulfonic acids or their salts preferably being added immediately before the surface post-crosslinking.
  • WO 03/014172 A2 describes a process for the preparation of water-absorbing polymer particles, wherein the acrylic acid used was previously treated with an aldehyde scavenger, since in particular the presence of aldehydes should lead to discoloration.
  • the object of the present invention was to provide a process for producing water-absorbing polymer particles having improved color stability.
  • the object has been achieved by a process for producing water-absorbing polymer particles by polymerization of a monomer solution or suspension comprising a) at least one ethylenically unsaturated, acid group-carrying monomer which may be at least partially neutralized,
  • optionally one or more water-soluble polymers comprising the steps of polymerizing the monomer solution to a polymer gel i), optionally comminution of the resultant polymer gel ii), drying of the polymer gel iii), milling and Classification of the dried polymer gel to polymer particles iv), and optionally thermal surface postcrosslinking of the classified polymer particles v), characterized in that before, during or after one of the steps i) to v) at least one optical brightener is added.
  • the optical brightener is added after step iv) and before, during or after step v). Most preferably, the optical brightener is added after step v).
  • Optical brighteners are chemical compounds that cause lightening by converting ultraviolet radiation invisible to the human eye into longer wavelength light visible to the human eye.
  • the ultraviolet light absorbed from the sunlight is emitted again as a weak bluish fluorescence, ie in the complementary color of the yellowing.
  • the preferred optical brighteners absorb electromagnetic waves in the range of 270 to 400 nm and emit electromagnetic waves in the range of 400 to 450 nm.
  • Suitable optical brighteners are 4,4'-diamino-2,2'-stilbenedisulfonic acids, 4,4'-distyrylbiphenylenes, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole and ethylene-linked benzene Benzimidazolesysteme, as well as by hetero cycles substituted pyrene derivatives.
  • the preferred optical brighteners are compounds of the general formulas (1) to (8):
  • Each R1 is independently a radical of the formula
  • Each R2 is independently hydrogen, a radical of the formula
  • R3 is an unsubstituted or substituted alkyl or aryl group
  • R 4 are each independently M or an unsubstituted or substituted
  • R 5 is hydrogen, an unsubstituted or substituted alkyl or aryl group or
  • R7 and Rs are independently hydrogen or an unsubstituted or substituted alkyl or aryl group, or R 7 and Rs form a heterocyclic ring together with the nitrogen atom, in particular a
  • R6 is hydrogen or an unsubstituted or substituted alkyl or aryl group
  • R9 and R10 are independently hydrogen, -C-C 4 alkyl, phenyl or a radical of
  • R ⁇ is hydrogen, -Cl or
  • Each R 12 is independently -CN, -SO 3 M, -S (C 1 -C 4 alkyl) 2 or
  • R 13 each independently of one another hydrogen, -SO 3 M, -CKC ⁇ C ⁇ alkyl
  • R 14 are each independently hydrogen, -C ⁇ alkyl, -Cl or
  • R 15 and R 16 are independently hydrogen, -C ⁇ C ⁇ alkyl, -SO 3 M, -Cl or
  • Each R 17 is independently hydrogen or -C, -C 4 alkyl
  • M is hydrogen, sodium, potassium, calcium, magnesium, ammonium, mono- di- tri- or tetra-C j -C lkylammonium, mono-, di- or
  • R3, R4, R5, R6, R7 and Rs (unsubstituted or) substituted alkyl group each represents Ci-Ci2Alkyl preferably Ci-C4alkyl.
  • the alkyl groups can be branched or unbranched and can be unsubstituted or substituted by halogen, for example fluorine, chlorine or bromine, with C 1 -C 4 -alkoxy, for example methoxy or ethoxy, with phenyl, with carboxyl, with C 1 -C 4 -alkoxycarbonyl, for example acetyl, with mono - or
  • R3, R4, R5, 6, R7, Rs, R12 and Ris (unsubstituted or) substituted aryl group is preferably a phenyl or naphthyl group.
  • the aryl groups can be unsubstituted or with C 1 -C 4 -alkyl, for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl, with C 1 -C 4 -alkoxy, for example methoxy, ethoxy, propoxy, isopropoxy, butoxy, iso - Butoxy, sec-butoxy or tert-butoxy, with halogen, for example fluorine, chlorine or bromine, with C2-C5Alkanoylamino, for example acetylamino, propionylamino or butyrylamino, be substituted with nitro, with -SO3M or with di-Ci-C4Alkylamino.
  • C 1 -C 4 -alkyl for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec
  • the compounds of general formulas (1) to (8) are preferably in neutralized form, i. preferably M is an alkali metal, more preferably sodium or potassium.
  • Very particularly preferred optical brighteners are the following compounds:
  • the amount of optical brightener based on the water-absorbing polymer particles is preferably from 0.001 to 2% by weight, more preferably from 0.005 to 1% by weight, most preferably from 0.01 to 0.5% by weight.
  • the present invention is based on the finding that the addition of optical brightener can effectively suppress the discoloration of water-absorbing polymer particles, especially in warm, moist storage.
  • At least one color stabilizer is additionally added.
  • the color stabilizer may also be added before, during or after any of steps i) to v), irrespective of the addition of the optical brightener.
  • the at least one color stabilizer is added after step iv) and before, during or after step v). Most preferably, the at least one color stabilizer is added after step v).
  • Suitable color stabilizers are all known antioxidants and reducing agents, as well as reducing agent-releasing compounds.
  • Suitable antioxidants are sterically hindered phenols such as 2,6-bis-tert-butyl-methylphenol or calcium bis [monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate], or organic phosphites such as tris- (2,4-di-tert-butylphenyl) phosphite.
  • Suitable reducing agents are sodium hypophosphite, potassium hypophosphite, sodium phosphite, potassium phosphite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium sulfite, potassium sulfite, sodium dithionite, potassium dithionite, sodium glyoxylate and potassium glyoxylate.
  • Suitable reducing agent-releasing compounds are derivatives of glyoxylic acid, such as disodium 2-hydroxy-2-sulfonatoacetate, dipotassium 2-hydroxy-2-sulfonatoacetate, disodium 2-hydroxy-2-phosphonoacetate, dipotassium 2-hydroxy-2- phosphonoacetate, sodium 2,2-dimethoxyacetate, potassium 2,2-dimethoxyacetate, sodium 2,2-diethoxyacetate and potassium 2,2-diethoxyacetate.
  • color stabilizers are also basic salts of polyvalent metal cations, such as calcium hydroxide, and hydroxyphosphonic acids, such as 1-hydroxy-1, 1'-ethylidenediphosphonic acid, and their partially neutralized and fully neutralized salts.
  • the amount of color stabilizer used, based on the water-absorbing polymer particles, is preferably from 0.001 to 5 wt .-%, particularly preferably from 0.005 to 2 wt .-%, most preferably from 0.01 to 1 wt .-%.
  • the water-absorbing polymer particles are prepared by polymerization of a monomer solution or suspension and are usually water-insoluble.
  • the monomers a) are preferably water-soluble, i. the solubility in water at 23 ° C. is typically at least 1 g / 100 g of water, preferably at least 5 g / 100 g of water, more preferably at least 25 g / 100 g of water, most preferably at least 35 g / 100 g of water.
  • Suitable monomers a) are, for example, ethylenically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, and itaconic acid. Particularly preferred monomers are acrylic acid and methacrylic acid. Very particular preference is given to acrylic acid. Further suitable monomers a) are, for example, ethylenically unsaturated sulfonic acids, such as styrenesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid (AMPS).
  • APMS 2-acrylamido-2-methylpropanesulfonic acid
  • a suitable monomer a) is, for example, an acrylic acid purified according to WO 2004/035514 A1 with 99.8460% by weight of acrylic acid, 0.0950% by weight of acetic acid,
  • the proportion of acrylic acid and / or salts thereof in the total amount of monomers a) is preferably at least 50 mol%, particularly preferably at least 90 mol%, very particularly preferably at least 95 mol%.
  • the monomers a) usually contain polymerization inhibitors, preferably hydroquinone half ethers, as storage stabilizer.
  • the monomer solution preferably contains up to 250 ppm by weight, preferably at most
  • hydroquinone 10 ppm by weight, particularly preferably at least 30 ppm by weight, in particular by 50 ppm by weight, hydroquinone, in each case based on the unneutralized monomer a).
  • an ethylenically unsaturated, acid-group-containing monomer having a corresponding content of hydroquinone half-ether can be used to prepare the monomer solution.
  • Preferred hydroquinone half ethers are hydroquinone monomethyl ether (MEHQ) and / or alpha tocopherol (vitamin E).
  • Suitable crosslinkers b) are compounds having at least two groups suitable for crosslinking. Such groups are, for example, ethylenically unsaturated groups which can be radically copolymerized into the polymer chain, and functional groups which 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 0 530 438 A1, di- and triacrylates, as in
  • Preferred crosslinkers b) are pentaerythritol triallyl ether, tetraalloxyethane, methylenebismethacrylamide, 15-times ethoxylated trimethylolpropane triacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate and triallylamine.
  • Very particularly preferred crosslinkers b) are the polyethyleneglyoxylated and / or propoxylated glycerols esterified with acrylic acid or methacrylic acid to form diioder triacrylates, as described, for example, in WO 2003/104301 A1.
  • Particularly advantageous are di- and / or triacrylates of 3- to 10-fold ethoxylated glycerol.
  • diacrylates or triacrylates of 1 to 5 times ethoxylated and / or propoxylated glycerol.
  • Most preferred are the triacrylates of 3 to 5 times ethoxylated and / or propoxylated glycerol, in particular the triacrylate of 3-times ethoxylated glycerol.
  • the amount of crosslinker b) is preferably from 0.05 to 1, 5 wt .-%, particularly preferably 0.1 to 1 wt .-%, most preferably 0.3 to 0.6 wt .-%, each based on Monomer a).
  • the centrifuge retention capacity (CRC) decreases and the absorbance under a pressure of 21.0 g / cm 2 (AUL 0.3 psi) goes through a maximum.
  • initiators c) it is possible to use all compounds which generate free radicals under the polymerization conditions, for example thermal initiators, redox initiators, photoinitiators.
  • Suitable redox initiators are sodium peroxodisulfate / ascorbic acid, hydrogen peroxide / ascorbic acid, sodium peroxodisulfate / sodium bisulfite and hydrogen peroxide. hydroxide / sodium bisulfite.
  • mixtures of thermal initiators and redox initiators are used, such as sodium peroxodisulfate / hydrogen peroxide / ascorbic acid.
  • the reducing component used is preferably disodium 2-hydroxy-2-sulfonatoacetate or a mixture of disodium 2-hydroxy-2-sulfinatoacetate, disodium 2-hydroxy-2-sulfonatoacetate and sodium bisulfite.
  • Such mixtures are available as Brüggolite® FF6 and Brüggolite® FF7 (Brüggemann Chemicals; Heilbronn; DE).
  • acrylamide, methacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate are ethylenically unsaturated monomers d) which are copolymerizable with the ethylenically unsaturated acid group-carrying monomers a).
  • 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
  • the monomer solution may be polymerized prior to polymerization by inerting, i. By flowing with an inert gas, preferably nitrogen or carbon dioxide, freed of dissolved oxygen.
  • an inert gas preferably nitrogen or carbon dioxide
  • the oxygen content of the monomer solution before polymerization is reduced to less than 1 ppm by weight, more preferably less than 0.5 ppm by weight, most preferably less than 0.1 ppm by weight.
  • the monomer solution or suspension is polymerized.
  • Suitable reactors are, for example, kneading reactors or belt reactors.
  • the polymer gel formed during the polymerization of an aqueous monomer solution or suspension is comminuted continuously by, for example, counter-rotating stirring shafts, as described in WO 2001/038402 A1.
  • the polymerization on the belt is described, for example, in DE 38 25 366 A1 and US Pat. No. 6,241,928.
  • a polymer gel is formed, which must be comminuted in a further process step ii), for example in an extruder or kneader.
  • the comminuted polymer gel obtained by means of a kneader may additionally be extruded.
  • the acid groups of the polymer gels obtained are usually partially neutralized.
  • the neutralization is preferably carried out at the stage of the monomers. This is usually done by mixing the neutralizing agent as an aqueous solution or preferably as a solid.
  • the degree of neutralization is preferably from 25 to 95 mol%, particularly preferably from 30 to 80 mol%, very particularly preferably from 40 to 75 mol%, wherein the customary neutralizing agents can be used, preferably alkali metal hydroxides, alkali metal oxides, alkali metal carbonates or Alkalimetallhydrogenkarbonate and mixtures thereof.
  • alkali metal salts and ammonium salts can be used.
  • Sodium and potassium are particularly preferred as alkali metals, but most preferred are sodium hydroxide, sodium carbonate or sodium bicarbonate and mixtures thereof.
  • 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 polymer gel obtained is dried.
  • the dryers are subject to no restriction.
  • the drying of the polymer gel is preferably carried out 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 .-%, wherein the Residual moisture content according to the EDANA recommended test method No. WSP 230.2-05 "Moisture Content". If the residual moisture content is too high, the dried polymer gel has too low a glass transition temperature T g and is difficult to process further.
  • the dried polymer gel is too brittle and in the subsequent comminution steps undesirably large amounts of polymer particles having too small a particle size ("fines") are produced. , particularly preferably from 35 to 70 wt .-%, completely particularly preferably from 40 to 60% by weight.
  • a fluidized bed dryer or a paddle dryer can be used for drying.
  • the dried polymer gel is 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.
  • the average particle size of the polymer fraction separated as a product fraction is preferably at least 200 ⁇ m, more preferably from 250 to 600 ⁇ m, very particularly from 300 to 500 ⁇ m.
  • the mean particle size of the product fraction can be determined by means of the EDANA recommended test method No. WSP 220.2-05 "Particle Size Distribution", in which the mass fractions of the sieve fractions are cumulatively applied and the average particle size is determined graphically.
  • the mean particle size here is the value of the mesh size, which results for accumulated 50 wt .-%.
  • the proportion of particles having a particle size of at least 150 ⁇ m is preferably at least 90% by weight, more preferably at least 95% by weight, very particularly preferably at least 98% by weight. Particle size particles that are too small in size reduce fluid transfer (SFC). Therefore, the proportion of too small polymer particles ("fines") should be low.
  • Too small polymer particles are therefore usually separated and recycled to the process. This is preferably done before, during or immediately after the polymerization, i. before drying the polymer gel.
  • the too small polymer particles can be moistened with water and / or aqueous surfactant before or during the recycling.
  • the too small polymer particles are preferably added during the last third of the polymerization.
  • the proportion of particles having a particle size of at most 850 pm is preferably at least 90 wt .-%, more preferably at least 95 wt .-%, most preferably at least 98 wt .-%.
  • the proportion of particles having a particle size of at most 600 ⁇ m is preferably at least 90% by weight, particularly preferably at least 95% by weight, very particularly preferably at least 98% by weight.
  • Polymer particles with too large particle size reduce the swelling rate. Therefore, the proportion of polymer particles too large should also be low.
  • Too large polymer particles are therefore usually separated and recycled to the grinding of the dried Polymergeis.
  • the polymer particles can be thermally surface-postcrosslinked to improve the properties in a further process step v).
  • Suitable surface postcrosslinkers are compounds containing groups that can form covalent bonds with at least two carboxylate groups of the polymer particles.
  • Suitable compounds are, for example, polyfunctional amines, polyfunctional amidoamines, polyfunctional epoxides, as described in EP 0 083 022 A2, EP 0 543 303 A1 and EP 0 937 736 A2, di- or polyfunctional alcohols, as described in DE 33 14 019 A1, DE 35 23 617 A1 and EP 0 450 922 A2, or ⁇ -hydroxyalkylamides, as described in DE 102 04 938 A1 and US Pat. No. 6,239,230.
  • Preferred surface postcrosslinkers are ethylene carbonate, ethylene glycol diglycidyl ether, reaction products of polyamides with epichlorohydrin and mixtures of propylene glycol and 1,4-butanediol.
  • Very particularly preferred surface postcrosslinkers are 2-hydroxyethyloxazolidin-2-one, oxazolidin-2-one and 1, 3-propanediol.
  • the amount of surface postcrosslinker is preferably 0.001 to 2 wt .-%, more preferably 0.02 to 1 wt .-%, most preferably 0.05 to 0.2 wt .-%, each based on the polymer particles.
  • polyvalent cations are applied to the particle surface before, during or after the surface postcrosslinking in addition to the surface postcrosslinkers.
  • the polyvalent cations which can be used in the process according to the invention are, for example, divalent cations, such as the cations of zinc, magnesium, calcium, iron and strontium, trivalent cations, such as the cations of aluminum, iron, chromium, rare earths and manganese, tetravalent cations, such as Cations of titanium and zirconium.
  • divalent cations such as the cations of zinc, magnesium, calcium, iron and strontium
  • trivalent cations such as the cations of aluminum, iron, chromium, rare earths and manganese
  • tetravalent cations such as Cations of titanium and zirconium.
  • chloride, bromide, sulfate, hydrogen sulfate, carbonate, bicarbonate, nitrate, phosphate, hydrogen phosphate, dihydrogen phosphate and carboxylate, such as acetate and lactate are possible.
  • Aluminum sulfate and aluminum lactate are preferred
  • the amount of polyvalent cation used is, for example, 0.001 to 1.5% by weight, preferably 0.005 to 1% by weight, particularly preferably 0.02 to 0.8% by weight. in each case based on the polymer particles.
  • the surface postcrosslinking is usually carried out in such a way that a solution of the surface postcrosslinker is sprayed onto the dried polymer particles. Following spraying, the surface postcrosslinker coated polymer particles are thermally dried, with the surface postcrosslinking reaction occurring both before and during drying.
  • the spraying of a solution of the surface postcrosslinker is preferably carried out in mixers with agitated mixing tools, such as screw mixers, disc mixers and paddle mixers.
  • agitated mixing tools such as screw mixers, disc mixers and paddle mixers.
  • horizontal mixers such as paddle mixers
  • vertical mixers very particularly preferred are vertical mixers.
  • horizontal mixer and vertical mixer is made by the storage of the mixing shaft, ie horizontal mixers have a horizontally mounted mixing shaft and vertical mixers have a vertically mounted mixing shaft.
  • Suitable mixers are, for example, Horizontal Pflugschar® mixers (Gebr.
  • solvent for example isopropanol / water, 1,3-propanediol / water and propylene glycol / water, the mixing mass ratio preferably being from 20:80 to 40:60.
  • the thermal surface postcrosslinking is preferably carried out in contact dryers, more preferably paddle dryers, very particularly preferably disk dryers.
  • Suitable dryers include Hosokawa Bepex® Horizontal Paddle Dryer (Hosokawa Micron GmbH, Leingart, DE), Hosokawa Bepex® Disc Dryer (Hosokawa Micron GmbH, Leingart, DE), and Nara Paddle Dryer (NARA Machinery Europe, Frechen, DE). Moreover, fluidized bed dryers can also be used.
  • the thermal surface postcrosslinking can take place in the mixer itself, by heating the jacket or by blowing hot air.
  • a downstream dryer such as a hopper dryer, a rotary kiln or a heatable screw. It is particularly advantageous to mix and dry in a fluidized-bed dryer.
  • Preferred surface postcrosslinking 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 surface-postcrosslinked polymer particles can be classified again, wherein too small and / or too large polymer particles are separated and recycled to the process.
  • the surface-postcrosslinked polymer particles can be coated or post-moistened for further improvement of the properties.
  • the post-wetting is preferably carried out at 30 to 80 ° C, more preferably at 35 to 70 ° C, most preferably at 40 to 60 ° C. If the temperatures are too low, the water-absorbing polymer particles tend to clump together and at higher temperatures water is already noticeably evaporating.
  • the amount of water used for the rewetting is preferably from 1 to 10 wt .-%, particularly preferably from 2 to 8 wt .-%, most preferably from 3 to 5 wt .-%.
  • Suitable coatings for improving the swelling rate and the fluid transfer (SFC) are, for example, inorganic inert substances, such as water-insoluble metal salts, organic polymers, cationic polymers and di- or polyvalent metal cations.
  • Suitable coatings for dust binding are, for example, polyols.
  • Suitable coatings against the unwanted caking tendency of the polymer particles are, for example, fumed silica, such as Aerosil® 200, and surfactants, such as Span® 20.
  • Another object of the present invention are obtainable by the process according to the invention water-absorbing polymer particles.
  • a further subject of the present invention are water-absorbing polymer particles comprising a ') at least one polymerized ethylenically unsaturated, acid group-carrying monomer a), which may be at least partially neutralized,
  • the water-absorbing polymer particles contain at least one optical brightener and the abovementioned optical brighteners can be used in the abovementioned amounts.
  • the polymer particles according to the invention are coated with at least one optical brightener.
  • the optical brightener is mixed, for example, with the polymer gel after step i), preferably with the polymer particles after step iv) and before, during or after step v), whereby a concentration gradient is obtained in the water-absorbing polymer particles.
  • the water-absorbing polymer particles according to the invention may additionally contain a color stabilizer or be coated with a color stabilizer, it being possible to use the abovementioned color stabilizers in the abovementioned amounts.
  • the water-absorbing polymer particles prepared according to the method of the invention have a centrifuge retention capacity (CRC) of typically at least 15 g / g, preferably at least 20 g / g, preferably at least 22 g / g, more preferably at least 24 g / g, most preferably at least 26 g / g, up.
  • the centrifuge retention capacity (CRC) of the water-absorbing polymer particles is usually less than 60 g / g.
  • the Centrifuge Retention Capacity (CRC) is determined according to the EDANA recommended Test Method No. WSP 241.2-05 "Centrifuge Retention Capacity".
  • the water-absorbing polymer particles prepared according to the method of the invention have an absorption under a pressure of 49.2 g / cm 2 (AUL0.7 psi) of typically at least 15 g / g, preferably at least 20 g / g, preferably at least 22 g / g preferably at least 24 g / g, most preferably at least 26 g / g.
  • the absorption under a pressure of 49.2 g / cm 2 (AUL0.7 psi) of the water-absorbent polymer particles is usually less than 35 g / g.
  • the absorption under a pressure of 49.2 g / cm 2 (AUL0.7 psi) is determined analogously to the EDANA recommended test method no. WSP 242.2-05 "Absorption under Pressure", wherein instead of a pressure of 21, 0 g / cm 2 a pressure of 49.2 g / cm 2 is set.
  • a further subject of the present invention are hygiene articles containing water-absorbing polymer particles according to the invention, in particular hygiene articles for feminine hygiene, hygiene articles for light and severe incontinence or small animal litter.
  • the sanitary articles usually contain a water-impermeable back, a water-permeable upper side and in between an absorbent core of the water-absorbing polymer particles according to the invention and fibers, preferably cellulose.
  • the proportion of the water-absorbing polymer particles according to the invention in the absorbent core is preferably from 20 to 100% by weight, preferably from 50 to 100% by weight.
  • the water-absorbing polymer particles are tested by the test methods described below.
  • WSP Standard Test Methods for the Nonwovens Industry
  • Measurements should be taken at an ambient temperature of 23 ⁇ 2 ° C and a relative humidity of 50 ⁇ 10%, unless otherwise specified.
  • the water-absorbing polymer particles are thoroughly mixed before the measurement.
  • the Centrifuge Retention Capacity (CRC) is determined according to the EDANA recommended Test Method No. WSP 241.2-05 "Centrifuge Retention Capacity". Absorption under a pressure of 49.2 g / cm 2 (absorption under pressure)
  • the absorption under a pressure of 49.2 g / cm 2 (AUL0.7 psi) is determined analogously to the EDANA recommended test method no. WSP 242.2-05 "Absorption under Pressure", wherein instead of a pressure of 21, 0 g / cm 2 (AUL0.3psi) a pressure of 49.2 g / cm 2 (AUL0.7psi) is set.
  • Saline Flow Conductivity (SFC) of a swollen gel layer under pressure of 0.3 psi (2070 Pa), as described in EP 0 640 330 A1, is determined as a gel-layer permeability of a swollen gel layer of water-absorbing polymer particles.
  • the punch (39) consists of the same plastic material as the cylinder (37) and now over the entire Support surface evenly distributed 21 holes of equal size. The procedure and evaluation of the measurement remains unchanged compared to EP 0 640 330 A1. The flow is automatically detected.
  • Fluid transfer (SFC) is calculated as follows:
  • the gel bed permeability (GBP) of a swollen gel layer under compressive loading of 0.3 psi (2070 Pa) becomes, as described in US 2005/02567575 (paragraphs [0061] and [0075]), gel-permeability of a swollen gel layer of water-absorbent Polymer particles determined.
  • the formula HC60 L-3b, the HC60 value is calculated.
  • the color measurement corresponds to the tristimulus method according to DIN 5033-6.
  • 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 and the HC60 value are again determined.
  • HySorb® B 7055 (BASF SE, Ludwigshafen, DE) was used in a Pflugschar® mixer M5 (Gebr Lödige Maschinenbau GmbH, Paderborn, DE) at 23 ° C and a shaft speed of 250 revolutions per minute using a two-component spray nozzle with 1, 0 wt .-% of a
  • Tinopal® CBS-X disodium 4,4'-bis (2-sulfostyryl) biphenyl; CAS No. 27344-41 -8; Ciba Specialty Chemicals Inc., Basel; CH
  • stirring was continued for 15 minutes at a shaft speed of 80 revolutions per minute.
  • the product obtained was sieved to a particle size of less than 850 ⁇ m.
  • HySorb® B 7055 (BASF SE, Ludwigshafen, DE) was used in a Pflugschar® mixer M5 (Gebr Lödige Maschinenbau GmbH, Paderborn, DE) at 23 ° C and a shaft speed of 250 revolutions per minute using a two-component spray nozzle with 2.0% by weight of a
  • HySorb® B 7055 (BASF SE, Ludwigshafen, DE) was used in a Pflugschar® mixer M5 (Gebr Lödige Maschinenbau GmbH, Paderborn, DE) at 23 ° C and a shaft speed of 250 revolutions per minute using a two-component spray nozzle with 4.0% by weight of a
  • HySorb® B 7055 (BASF SE, Ludwigshafen, DE) was used in a Pflugschar® mixer M5 (Gebr Lödige Maschinenbau GmbH, Paderborn, DE) at 23 ° C and a shaft speed of 250 revolutions per minute by means of a two-component Spray nozzle with 1, 0 wt .-% of a
  • HySorb® B 7055 (BASF SE, Ludwigshafen, DE) was used in a Pflugschar® mixer M5 (Gebr Lödige Maschinenbau GmbH, Paderborn, DE) at 23 ° C and a shaft speed of 250 revolutions per minute using a two-component spray nozzle with 1, 0 wt .-% of a
  • Tinopal® CBS-X sodium 4,4'-bis (2-sulfostyryl) biphenyl
  • HySorb® B 7055 (BASF SE, Ludwigshafen, DE) was used in a Pflugschar® mixer M5 (Gebr Lödige Maschinenbau GmbH, Paderborn, DE) at 23 ° C and a shaft speed of 250 revolutions per minute using a two-component spray nozzle with 1, 0 wt .-% of a mixture of 89 wt .-% demineralized water and 1 1 wt .-% Tinopal® MSP Liquid (hexaatrium-2,2 '- ⁇ vinylenebis [(3-sulfonato-4.1 - phenylene) imino [6-morpholino-1, 3,5-triazine-4,2-diyl] - imino] ⁇ bis (benzene-1,4-disulfonate); CAS No.
  • HySorb® B 7055 (BASF SE, Ludwigshafen, DE) was used in a Pflugschar® mixer M5 (Gebr Lödige Maschinenbau GmbH, Paderborn, DE) at 23 ° C and a shaft speed of 250 revolutions per minute using a two-component spray nozzle with 1.0% by weight of a 2.0% by weight solution of Tinopal® SFP (hexasodium 2,2 '- ⁇ vinylene bis [(3-sulfonato-4,1-phenylene) imino [6-diethylamino-1] 3, 5-triazine-4,2-diyl] imino] ⁇ bis (benzene-1,4-disulfonate); CAS No.
  • HySorb® B 7055 (BASF SE, Ludwigshafen, DE) was used in a Pflugschar® mixer M5 (Gebr Lödige Maschinenbau GmbH, Paderborn, DE) at 23 ° C and a shaft speed of 250 revolutions per minute by means of a binary Spray nozzle with 1.0% by weight of a mixture of 90% by weight of demineralized water and 10% by weight of Tinopal® NFW Liquid (dinetrium-4,4'-bis (2-sulfostyryl) -biphenyl; CAS no 27344-41 -8; Ciba Specialty Chemicals Inc., Basel; CH). After spraying, stirring was continued for 15 minutes at a shaft speed of 80 revolutions per minute. The product obtained was sieved to a particle size of less than 850 ⁇ m.
  • HySorb® B 7055 are commercially available surface-postcrosslinked water-absorbing polymer particles.
  • Example 9 (Comparative Example) A 2 l stainless steel beaker was charged with 326.7 g of 50% strength by weight sodium hydroxide solution and 675 g of frozen, demineralized water. With stirring, 392.0 g of acrylic acid was added, the rate of addition being adjusted so that the temperature did not exceed 35 ° C. The mixture was then cooled with stirring by means of a cooling bath. When the temperature of the mixture dropped to 20.degree.
  • the resulting polymer gel was extruded three times with the aid of a commercially available meat grinder with a 6 mm perforated disc and dried in a convection oven at 160 ° C. for one hour. The dried polymer gel was then ground and sieved to a particle size of 150 to 850 ⁇ m.
  • This base polymer was used for surface postcrosslinking in a Pflugschar® mixer type M5 with heating jacket (Gebr Lödige Maschinenbau GmbH, Paderborn, DE) at 23 ° C and a shaft speed of 450 revolutions per minute using a two-component spray nozzle with a mixture of 0.10 % By weight of ethylene glycol diglycidyl ether (Denacol® EX-810, Nagase ChemteX Corporation, Osaka; JP), 1, 50% by weight of 1,2-propanediol, 2.8% by weight of demineralized water and 0.4% by weight. % aqueous aluminum sulfate solution (26.8 wt .-%), each based on the base polymer, coated.
  • the product temperature was raised to 150 ° C and the reaction mixture was maintained at that temperature for 60 minutes at a shaft speed of 80 revolutions per minute.
  • the resulting product was allowed to cool back to ambient temperature and sieved.
  • the surface-postcrosslinked water-absorbing polymer particles were screened off to a particle size of 150 ⁇ m to 850 ⁇ m and had the following properties:
  • the obtained water-absorbent polymer particles had a CIE color number of
  • Example 10 100 g of the water-absorbent polymer particles obtained in Example 10 were added to a PE sample bottle (500 ml capacity) with 0.060 g of calcium bis [monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate]. The contents of the bottle were intimately mixed for 15 minutes with the aid of a tumble mixer type T2C (Willy A. Bachofen AG Maschinenfabrik, Basel, CH).
  • Example 10 100 g of the water-absorbing polymer particles obtained in Example 10 were placed in a 500 ml PE sample bottle with 0.090 g of tris (2,4-di-tert-butylphenyl) phosphite added. The contents of the bottle were intimately mixed for 15 minutes with the aid of a tumble mixer type T2C (Willy A. Bachofen AG Maschinenfabrik, Basel, CH).
  • Example 13 (Comparative Example) 14.3 kg of aqueous sodium acrylate solution (37.5% strength by weight), 1.4 kg of acrylic acid and 350 g of demineralized water were mixed with 8.5 g of tri-ethoxylated glycerol triacrylate. This solution was placed in a heated nitrogen sparge drop tower (180 ° C, 12 m high, 2 m diameter, 0.1 m / s gas velocity, 40 mm diameter dropper, 2 mm internal height, and 60 drilled holes in 200 ⁇ diameter) at a metering rate of 32 kg / h. The temperature of the solution was 25 ° C. Shortly before the dropletizer, the monomer solution was mixed via a static mixer with two initiator solutions.
  • initiator 1 was a 3 wt .-% solution of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride in demineralized water and as initiator 2, a 6.1 wt. -% solution of sodium peroxodisulfate used in demineralized water.
  • the metering rate of the initiator solution 1 was 0.932 kg / h and the metering rate of the initiator solution 2 was 0.629 kg / h.
  • the resulting polymer particles were screened to a particle size of 150 to 850 ⁇ to separate any agglomerates formed, and had the following properties:
  • Example 13 The procedure was as in Example 13. To the monomer solution was additionally added 66.1 g of a 2.5% by weight solution of Tinopal® CBS-X (disodium 4,4'-bis (2-sulfostyryl) -biphenyl; CAS No. 27344-41 -8; Ciba Specialty Chemicals Inc., Basel, CH) in demineralized water.
  • Tinopal® CBS-X diisodium 4,4'-bis (2-sulfostyryl) -biphenyl
  • CAS No. 27344-41 -8 Ciba Specialty Chemicals Inc., Basel, CH
  • Example 15 1000 g of the water-absorbing polymer particles of Example 14 were carried in a Pflugschar M5 mixer (Gebr. Lödige Maschinenbau GmbH, Paderborn, DE) at 23 ° C. and a shaft speed of 250 revolutions per minute using a two-component spray nozzle a solution of 0.5 g of 2-hydroxy-2-phosphonatoacetic acid in 40 g of demineralized water. After spraying, stirring was continued for 15 minutes at a shaft speed of 80 revolutions per minute. The product obtained was sieved to a particle size of less than 850 ⁇ m.
  • Example 16 1000 g of the water-absorbing polymer particles of Example 14 were carried in a Pflugschar M5 mixer (Gebr. Lödige Maschinenbau GmbH, Paderborn, DE) at 23 ° C. and a shaft speed of 250 revolutions per minute using a two-component spray nozzle a solution of 1.5 g of sodium glyoxylate in 15 g of demineralized water. After spraying, stirring was continued for 15 minutes at a shaft speed of 80 revolutions per minute. The product obtained was sieved to a particle size of less than 850 ⁇ m.
  • Example 17 The procedure was as in Example 13. To the monomer solution was additionally added 66.1 g of a 2.5% strength by weight solution of Tinopal® CBS-X (disodium 4,4'-bis (2-sulfostyryl) biphenyl CAS No. 27344-41-8, Ciba Specialty Chemicals Inc., Basel, CH) in demineralized water and 2.75 g of 1-hydroxy-1, 1'-ethylidenediphosphonic acid in 50 g of demineralized water.
  • Tinopal® CBS-X disodium 4,4'-bis (2-sulfostyryl) biphenyl CAS No. 27344-41-8, Ciba Specialty Chemicals Inc., Basel, CH
  • aqueous Tinopal® CBS-X sodium 4,4'-bis (2-sulfostyryl) biphenyl; CAS No. 27344-41 -8 (; Ciba Specialty Chemicals Inc .; Basel; CH)
  • the product temperature was raised to 170 ° C and the reaction mixture was held at that temperature for 45 minutes at a shaft speed of 60 revolutions per minute.
  • the resulting product was allowed to cool back to ambient temperature and sieved.
  • the surface-postcrosslinked water-absorbing polymer particles were screened off to a particle size of 150 ⁇ m to 850 ⁇ m and had the following properties:
  • the obtained water-absorbent polymer particles had a CIE color number of

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Abstract

L'invention concerne des particules polymères hydroabsorbantes présentant une stabilité de couleur améliorée et leur procédé de production, lesdites particules polymères hydroabsorbantes contenant au moins un azurant optique.
EP11726118.0A 2010-06-14 2011-06-10 Particules polymères hydroabsorbantes présentant une stabilité de couleur améliorée Withdrawn EP2580256A2 (fr)

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EP10165823 2010-06-14
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PCT/EP2011/059710 WO2011157656A2 (fr) 2010-06-14 2011-06-10 Particules polymères hydroabsorbantes présentant une stabilité de couleur améliorée

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WO2011157656A2 (fr) 2011-12-22
KR20130096218A (ko) 2013-08-29
BR112012031895A2 (pt) 2016-11-08
WO2011157656A3 (fr) 2012-07-26
JP2013530281A (ja) 2013-07-25
CN103068861B (zh) 2015-11-25
JP5766283B2 (ja) 2015-08-19
CN103068861A (zh) 2013-04-24

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