WO2012107344A1 - Procédé de préparation de particules polymères hygroscopiques - Google Patents

Procédé de préparation de particules polymères hygroscopiques Download PDF

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WO2012107344A1
WO2012107344A1 PCT/EP2012/051770 EP2012051770W WO2012107344A1 WO 2012107344 A1 WO2012107344 A1 WO 2012107344A1 EP 2012051770 W EP2012051770 W EP 2012051770W WO 2012107344 A1 WO2012107344 A1 WO 2012107344A1
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monomer
water
polymer particles
weight
absorbing polymer
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PCT/EP2012/051770
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German (de)
English (en)
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Norbert Herfert
Thomas Daniel
Klaus Dieter HÖRNER
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate

Definitions

  • the present invention relates to a process for the preparation of water-absorbing polymer particles with improved swelling rate by polymerization of a monomer solution or suspension comprising an ethylenically unsaturated, acid group-carrying monomer, an ethylenically unsaturated monomer, a crosslinker and an initiator.
  • Water-absorbing polymer particles are used in the manufacture of diapers, tampons, sanitary napkins and other sanitary articles, but also as water-retaining agents in agricultural horticulture.
  • the water-absorbing polymer particles are also referred to as superabsorbers.
  • the preparation of water-absorbing polymer particles is described in the monograph "Modern Supersorbent 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 (AULOJpsi) 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 base polymer
  • Crosslinkers suitable for this purpose are compounds which can form covalent bonds with at least two carboxylate groups of the water-absorbing polymer particles.
  • the object of the present invention was to provide an improved process for producing water-absorbing polymer particles, in particular water-absorbing polymer particles with high swelling rate (FSR) and high absorption under a pressure of 49.2 g / cm 2 (AULOJpsi).
  • the object was achieved by a process for producing water-absorbing polymer particles by polymerization of a monomer solution or suspension containing a) an ethylenically unsaturated, acid group-carrying monomer which may be at least partially neutralized,
  • e) optionally one or more water-soluble polymers characterized in that the monomer solution or suspension at least 0.5 weight equivalents of a crosslinker b), wherein one weight equivalent of the weight percent of the crosslinker b), based on the unneutralized monomer a) multiplied by (n -1) and n is the number of ethylenic double bonds in the crosslinker b), and from 7.5 to 50 wt .-% of monomer d), based on the unneutralized monomer a) contains.
  • the water-absorbing polymer particles are usually water-insoluble.
  • the monomer a) is 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 a) 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 (AM PS). 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,
  • the monomer a) usually contains polymerization inhibitors, preferably hydroquinone halide, as a storage stabilizer.
  • the monomer solution preferably contains up to 250 ppm by weight, preferably at most
  • 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.
  • 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, tetraallyloxyethane, methylenebismethacrylate, 15-tuply ethoxylated trimethylolpropane triacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, triallylamine and tetraallylammonium chloride.
  • 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.
  • di- and / or triacrylates of 3- to 10-fold ethoxylated glycerol are particularly advantageous.
  • diacrylates or triacrylates of 1 to 5 times ethoxylated and / or propoxylated glycerol are particularly preferred.
  • 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 0.6 to 2 weight equivalents, particularly preferably 0.65 to 1, 5 weight equivalents, very particularly preferably 0.7 to 1 weight equivalent, in each case based on the unneutralized monomer a). With increasing crosslinker content, the centrifuge retention capacity (CRC) decreases and the absorption under a pressure of 21.0 g / cm 2 passes through a maximum.
  • a weight equivalent corresponds to the weight percent of the crosslinker b), based on the unneutralized monomer a) multiplied by (n-1), wherein and n is the number of ethylenic double bonds in the crosslinker b).
  • n is the number of ethylenic double bonds in the crosslinker b.
  • crosslinker b) having two ethylenic double bonds such as methylenebisacrylamide or polyethylene glycol diacrylate
  • one weight percent also corresponds to one weight equivalent
  • crosslinker b) having three ethylenic double bonds such as 15-times ethoxylated trimethylolpropane triacrylate or triallylamine, one weight percent corresponds to two weight equivalents.
  • initiators c) it is possible to use all compounds which generate free radicals under the polymerization conditions, for example thermal initiators, redox initiators, photoinitiators.
  • Suitable redox initiators are sodium peroxodisulfate / ascorbic acid, hydrogen peroxide / ascorbic acid, sodium peroxodisulfate / sodium bisulfite and hydrogen peroxide / sodium bisulfite.
  • thermal initiators and redox initiators are used, such as sodium peroxodisulfate / hydrogen peroxide / ascorbic acid.
  • the reducing component used is preferably a mixture of the disodium salt of 2-hydroxy-2-sulfinatoacetic acid, the disodium salt of 2-hydroxy-2-sulfonatoacetic acid and sodium bisulfite (available as Brüggolit® FF6 and Brüggolit® FF7 from Brüggemann Chemicals, Heilbronn; DE) or the disodium salt of 2-hydroxy-2-sulfinatoacetic acid in pure form (available as Blancolen® HP from Brüggemann Chemicals, Heilbronn, DE).
  • the ethylenically unsaturated monomers d) copolymerizable with the ethylenically unsaturated acid group-carrying monomer a) are not subject to any restriction. It is possible that the monomers d) themselves are ethylenically unsaturated, acid group-carrying monomers and / or their salts. It is important only that the monomers d) are different from the monomer a).
  • Suitable monomers d) are, for example, ethylenically unsaturated carboxylic acids, such as acrylic acid, methacrylic acid and itaconic acid, and ethylenically unsaturated sulfonic acids, such as styrenesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid (AM PS).
  • Particularly preferred monomers d) are methacrylic acid, itaconic acid and 2-acrylamido-2-methylpropanesulfonic acid. Very particular preference is given to methacrylic acid and 2-acrylamido-2-methylpropanesulfonic acid.
  • Suitable monomers d) are, for example, acrylamide, methacrylamide, tert-butylacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, n-propyl methacrylate, n-propyl acrylate, n-butyl methacrylate, n-butyl acrylate, tert-butyl methacrylate, tert-butyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminopropyl acrylate, diethylamino ethylmethacrylate, diethylaminopropylacrylate, dimethylaminoethylmethacrylamide, di
  • Particularly preferred monomers d) are acrylamide, tert-butylacrylamide, dimethylaminoethyl methacrylate, methyl methacrylate, methyl acrylate, tert-butyl methacrylate, cyclohexyl methacrylate, n-butyl diglycol methacrylate, methoxypolyglycol methacrylate and vinylformamide. Very particular preference is given to methyl acrylate.
  • Further suitable monomers d) are, for example, 2-trimethylammoniumethyl methacrylate chloride, 2-triethylammonium ethyl acrylate chloride, 3-trimethylammonium propyl acrylate chloride,
  • the monomer solution or suspension contains from 7.5 to 50 wt .-%, preferably 9 to 44 wt .-%, particularly preferably from 10 to 30 wt .-%, most preferably from 15 to 25 wt .-%, of Monomers d), each based on the unneutralized monomer 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% by weight, more preferably from 45 to 70% by weight, most preferably from 50 to 65% by weight.
  • monomer suspensions ie monomer solutions with excess monomer a), for example sodium acrylate.
  • the monomer solution may be polymerized prior to polymerization by inerting, i. Flow through with an inert gas, preferably nitrogen or carbon dioxide, are freed of dissolved oxygen.
  • an inert gas preferably nitrogen or carbon dioxide
  • the oxygen content of the monomer solution before polymerization is reduced to less than 1 ppm by weight, more preferably less than 0.5 ppm by weight, most preferably less than 0.1 ppm by weight.
  • Suitable reactors are, for example, kneading reactors or belt reactors.
  • the polymer gel resulting from the polymerization of an aqueous monomer solution or suspension is continuously comminuted 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, for example in an extruder or kneader.
  • the comminuted polymer gel obtained by means of a kneader can 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 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 .-%, wherein the residual moisture content according to the test method No. WSP 230.2-05 "Moisture Content" recommended by EDA-NA. 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. If the residual moisture content is too low, the dried polymer gel is too brittle and in the subsequent comminution steps undesirably large amounts of polymer particles having too small a particle size ("fines") are produced.
  • a fluidized-bed dryer or a paddle dryer can be used for the drying.
  • the dried polymer gel is then ground and classified, for grinding usually single or multi-stage roller mills, preferably two- or three-stage roller mills, pin mills, hammer mills or vibrating mills, can be used.
  • the mean particle size of the polymer particles separated off as 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 average particle size here is the value of the mesh size, which results for a cumulative 50% by weight.
  • the proportion of particles having a particle size of at least 150 ⁇ is preferably at least 90 wt .-%, more preferably at least 95 wt .-%, most preferably at least 98 wt .-%.
  • Polymer particles which are too small are therefore usually separated off and returned to the process. This preferably takes place before, during or immediately after the polymerization, ie before the drying of the polymer gel.
  • the too small polymer particles can be moistened with water and / or aqueous surfactant before or during the recycling. It is also possible to separate small polymer particles in later process steps, for example after surface postcrosslinking or another coating step. In this case, the recycled too small polymer particles are surface postcrosslinked or otherwise coated, for example with fumed silica.
  • the too small polymer particles are preferably added during the last third of the polymerization.
  • the polymer particles which are too small are added very late, for example only in an apparatus downstream of the polymerization reactor, for example an extruder, then the polymer particles which are too small can only be incorporated into the resulting polymer gel with difficulty. Insufficiently incorporated too small polymer particles, however, dissolve again during the grinding of the dried polymer gel, are therefore separated again during classification and increase the amount of recycled too small polymer particles.
  • the proportion of particles having a particle size of at most 850 ⁇ m is preferably at least 90% by weight, particularly preferably at least 95% by weight, very particularly preferably at least 98% by weight.
  • 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.
  • the polymer particles can be surface postcrosslinked to further improve the properties.
  • Suitable surface postcrosslinkers are compounds containing groups that can form covalent bonds with at least two carboxylate groups of the polymer particles. Examples of suitable compounds are polyfunctional amines, polyfunctional amidoamines, polyfunctional epoxides, as described in EP 0 083 022 A2, EP 0 543 303 A1 and US Pat
  • 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 40 20 780 C1 also discloses cyclic carbonates, in DE 198 07 502 A1 2-oxazolidinone and its derivatives, such as 2-hydroxyethyl-2-oxazolidinone, in DE 198 07 992 C1 bis- and poly-2-oxazolidinones , in DE 198 54 573 A1 2-oxotetrahydro-1,3-oxazine and its derivatives, in DE 198 54 574 A1 N-acyl-2-oxazolidinones, in DE 102 04 937 A1 cyclic ureas, in DE 103 34 584 A1 bicyclic Amidoacetals, in EP 1 199 327 A2 oxetanes and cyclic ureas and described in WO 2003/031482 A1 morpholine-2,3-dione and its derivatives as suitable O- ber lakenachvernetzer.
  • 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-hydroxyethyl-2-oxazolidinone, 2-oxazolidinone 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.
  • hydroxide, chloride, bromide, sulfate, hydrogen sulfate, carbonate, bicarbonate, nitrate, phosphate, hydrogen phosphate, dihydrogen phosphate and carboxylate, such as acetate, citrate and lactate are possible.
  • salts with different counterions for example basic aluminum salts, such as aluminum monoacetate or aluminum monolactate.
  • Aluminum sulfate, aluminum monoacetate and aluminum lactate are preferred.
  • polyamines can also be used as polyvalent cations.
  • 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.
  • the surface postcrosslinker coated polymer particles are thermally dried, whereby the surface postcrosslinking reaction can take place 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.
  • Particularly preferred are horizontal mixers, such as paddle mixers, very particularly preferred are vertical mixers.
  • horizontal mixer and vertical mixer via the storage of the mixing shaft ie horizontal mixer have a horizontally mounted mixing shaft and vertical mixer have a vertically mounted mixing shaft.
  • Suitable mixers are, for example, Horizontal Pflugschar® mixers (Gebr. Lödige Maschinenbau GmbH, Paderborn, DE), Vrieco-Nauta Continuous Mixers (Hosokawa Micron BV, Doetinchem, NL), Processall Mixmill Mixers (Processall Incorporated, Cincinnati, US) and Schugi Flexomix® (Hosokawa Micron BV, Doetinchem, NL).
  • the surface postcrosslinkers are typically used as an aqueous solution.
  • the penetration depth of the surface postcrosslinker into the polymer particles can be adjusted by the content of nonaqueous solvent or total solvent amount.
  • solvent for example isopropanol / water, 1,3-propanediol / water and propylene glycol / water, the mixture mass ratio preferably being from 20:80 to 40:60.
  • the thermal drying is preferably carried out in contact dryers, more preferably paddle dryers, very particularly preferably disk dryers.
  • Suitable dryers are, for example, Hosokawa Bepex® Horizontal Paddle Dryer (Hosokawa Micron GmbH, Leingart, DE), Hosokawa Bepex® Disc Dryer (Hosokawa Micron GmbH, Leingart, DE),
  • fluidized bed dryers can also be used. The drying can take place in the mixer itself, by heating the jacket or blowing hot air. Also suitable is a downstream dryer, such as a hopper dryer, a rotary kiln or a heatable screw. Particularly advantageous is mixed and dried in a fluidized bed dryer. Preferred drying temperatures are in the range 100 to 250 ° C, preferably 120 to
  • 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 water-absorbing polymer particles are cooled after the thermal drying.
  • the cooling is preferably carried out in contact coolers, particularly preferably blade coolers, very particularly preferably disk coolers.
  • Suitable coolers include Hosokawa Bepex® Horizontal Paddle Cooler (Hosokawa Micron GmbH, Leingart, DE), Hosokawa Bepex® Disc Cooler (Hosokawa Micron GmbH, Leingart, DE), Holo-Flite® coolers (Metso Minerals Industries Inc .; Danville; US ) and Nara Paddle Cooler (NARA Machinery Europe; Frechen; DE).
  • fluidized bed coolers can also be used.
  • the water-absorbing polymer particles to 20 to 150 ° C, preferably 40 to 120 ° C, more preferably 60 to 100 ° C, most preferably 70 to 90 ° C, cooled off.
  • 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 .-%.
  • the post-humidification is carried out in the cooler after the thermal drying.
  • Suitable coatings for improving the swelling rate and the permeability 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 undesirable tendency of the polymer particles to cake are, for example, pyrogenic silica, such as Aerosil® 200, and surfactants, such as Span® 20.
  • the present invention further provides the water-absorbing polymer particles obtainable by the process according to the invention.
  • the water-absorbing polymer particles according to the invention have a centrifuge retention capacity (CRC) of typically at least 15 g / g, preferably at least 20 g / g, preferably at least 25 g / g, more preferably at least 30 g / g, most preferably at least 35 g / g , on.
  • CRC centrifuge retention capacity
  • the centrifuge retention capacity (CRC) of the water-absorbent polymer particles is usually less than 60 g / g.
  • the water-absorbing polymer particles according to the invention have an absorption under a pressure of 49.2 g / cm 2 (AUL0.7 psi) of typically at least 10 g / g, preferably at least 15 g / g, preferably at least 20 g / g, particularly preferably at least 22 g / g, most preferably at least 23 g / g, on.
  • AUL0.7 psi an absorption under a pressure of 49.2 g / cm 2
  • 49.2 g / cm 2 (AULOJpsi) of the water-absorbing polymer particles is usually less than 30 g / g.
  • the water-absorbing polymer particles according to the invention have a liquid transfer line (SFC) of typically at least 50 ⁇ 10 7 cm 3 s / g, preferably at least 80 ⁇ 10 7 cm 3 s / g, preferably at least 100 ⁇ 10 7 cm 3 s / g preferably at least 120 ⁇ 10 7 cm 3 s / g, very particularly preferably at least 130 ⁇ 10 7 cm 3 s / g.
  • the liquid transfer (SFC) of the water-absorbing polymer particles is usually less than 250 ⁇ 10 7 cm 3 s / g.
  • 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 manufacture of the hygiene articles is described in the monograph "Modern Superabsorbent Polymer Technology", F.L. Buchholz and AT. Graham, Wiley-VCH, 1998, pp. 252-258.
  • 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 weight W1 should be corrected for this moisture content.
  • the centrifuge retention capacity (CRC) of the water-absorbing polymer particles is determined according to the EDANA-recommended test method no. WSP 241.2-05 "Centrifuge Retention Capacity”.
  • the temperature of the heating mantle was adjusted to the reaction temperature in order to complete the reaction as adiabatically as possible.
  • the resulting gel was cooled, discharged and dried for 90 minutes in a convection oven at 175 ° C.
  • the product was then ground and sieved to 150 to 710 ⁇ .
  • the temperature of the heating mantle was adjusted to the reaction temperature in order to complete the reaction as adiabatically as possible.
  • the resulting gel was cooled, discharged and dried for 90 minutes in a convection oven at 175 ° C.
  • the product was then ground and sieved to 150 to 710 ⁇ .
  • the obtained water-absorbent polymer particles were analyzed. The results are summarized in Table 1.
  • Example 5 In a Pflugschar® kneader of the type VT 5R-MK (Gebr. Lödige Maschinenbau GmbH, Paderborn, Germany), 373.3 g of water, 183.6 g of acrylic acid, 1900.8 g of a
  • Example 6 (Comparative Example) A 2 l stainless steel beaker was charged with 326.7 g of 50% strength by weight sodium hydroxide solution and 849.0 g of frozen, deionized 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 to 20 ° C with stirring by means of a cooling bath.
  • Example 6 was repeated, but the monomer solution after the neutralization step was additionally added 78.4 g of a 50 wt .-% aqueous solution of the sodium salt of 2-acrylamido-2-methylpropanesulfonic acid (AM PS).
  • AM PS 2-acrylamido-2-methylpropanesulfonic acid
  • Na-AMPS sodium salt of 2-acrylamido-2-methylpropanesulfonic acid
  • AM PS 2-acrylamido-2-methylpropanesulfonic acid
  • the base polymers of Examples 6 and 7 were used for surface postcrosslinking in a Pflugschar® mixer with heating jacket of the type M5 (Gebr. Lödige Maschinenbau GmbH, Paderborn, Germany) at 23 ° C. and a shaft speed of 250 revolutions per minute by means of a two-component Spray nozzle coated with the following solution (in each case based on the base polymer):
  • the product temperature was increased to 170 ° C. and the reaction mixture was held at this temperature for 45 minutes at a shaft speed of 60 revolutions per minute.
  • the products obtained were allowed to cool again to 23 ° C and sieved to 150 to 600 ⁇ .
  • Na-AMPS sodium salt of 2-acrylamido-2-methylpropanesulfonic acid
  • AM PS 2-acrylamido-2-methylpropanesulfonic acid

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé de préparation de particules polymères hygroscopiques présentant une vitesse de gonflement accrue, par polymérisation d'une solution ou d'une suspension monomère contenant un monomère éthyléniquement insaturé portant des groupes acides, un monomère éthyléniquement insaturé, un agent réticulant et un initiateur.
PCT/EP2012/051770 2011-02-07 2012-02-02 Procédé de préparation de particules polymères hygroscopiques WO2012107344A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112969529A (zh) * 2018-11-14 2021-06-15 巴斯夫欧洲公司 制备超吸收剂的方法

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DE10204937A1 (de) 2002-02-07 2003-08-21 Stockhausen Chem Fab Gmbh Verfahren zur Nachvernetzung im Bereich der Oberfläche von wasserabsorbierenden Polymeren mit Harnstoffderivaten
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112969529A (zh) * 2018-11-14 2021-06-15 巴斯夫欧洲公司 制备超吸收剂的方法
CN112969529B (zh) * 2018-11-14 2023-11-10 巴斯夫欧洲公司 制备超吸收剂的方法

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