Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/12—Polymerisation in non-solvents
  • C08F2/16—Aqueous medium
  • C08F2/18—Suspension polymerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/04—Polymerisation in solution
  • C08F2/10—Aqueous solvent

Definitions

• a process for the continuous production of water-absorbing polymer particles is known in which polymerized water-soluble monomers in the presence of a crosslinking agent and initiators in a reactor which is equipped with a plurality of mutually parallel rotating stirrer shafts, with stirrer blades are provided.
• the polymerization is carried out continuously in a kneading reactor with at least two axially parallel waves.
• a strong back-mixing takes place, so that the monomer solution is added to the finely divided water-containing polymer gel and the polymerization of the monomer takes place on the surface of the polymer gel.
• the thus obtainable water-absorbing polymer particles have a relatively high residual monomer content.
• EP 0 223 063 A2 teaches a process for the continuous production of water-absorbing polymer particles in a single-shaft kneading reactor whose mixing segments effect a transport of the substances in the axial direction from the beginning to the end of the kneading reactor.
• WO 2001/038402 A1 and WO 2003/022896 A1 disclose a process for the continuous preparation of water-absorbing polymer particles in a kneading reactor with at least two axially parallel waves, the reaction mixture being transported in the axial direction through the kneading reactor.
• Water-absorbent polymers are used in the manufacture of diapers, tampons, sanitary napkins and other sanitary articles, but also as water-retaining agents in agricultural horticulture.
• the object of the present invention was to provide an improved process for preparing water-absorbent polymer particles with low centrifuge retention capacity (CRC).
• the object was achieved by a process for producing water-absorbing polymer particles by polymerization of a monomer solution or suspension containing
• the inert gas volume flow is at most 10 m 3 / h per m 3 reactor volume and the homogeneously crosslinked water-absorbing polymer particles (base polymer) obtained by the polymerization have a centrifuge retention capacity (CRC) of at most 38 g / g.
• CRC centrifuge retention capacity
• non-postcrosslinked water-absorbing polymer particles are referred to.
• the homogeneously crosslinked water-absorbing polymer particles (base polymer) obtainable by the process according to the invention have a centrifuge retention capacity (CRC) of preferably at most 37 g / g, preferably at most 36.5 g / g, particularly preferably at most 36 g / g, very particularly preferably at most 35.5 g / g, on.
• the centrifuge retention capacity (CRC) of the water-absorbent polymer particles is usually at least 20 g / g.
• the centrifuge retention capacity is determined according to the test method no.
• WSP 241.2-05 "Centrifuge Retention Capacity” recommended by the EDANA (European Disposables and Nonwovens Association), whereby the water-absorbing polymer particles are determined to a water content of less than 5% by weight before determination. % dried and comminuted to a particle size in the range of 150 to 850 microns.
• the centrifuge retention capacity (CRC) can be adjusted to the desired value by adjusting the amount of crosslinker b). However, the centrifuge retention capacity (CRC) is also influenced by the degree of neutralization of the monomer a) and the recirculation of undersize, ie a lower degree of neutralization or the recirculation of more undersize decrease the centrifuge retention capacity (CRC).
• the inert gas volume flow is preferably from 0.001 to 5 m 3 / h per m 3 reactor volume, preferably from 0.01 to 2.5 m 3 / h per m 3 reactor volume, particularly preferably from 0.1 to 2 m 3 / h per m 3 reactor volume, most preferably 0.2 to 1 m 3 / h per m 3 reactor volume
• Nitrogen especially of industrial quality, is preferably used as the inert gas.
• Technical nitrogen usually contains at least 99.8% by volume of nitrogen and less than 0.0005% by volume of oxygen.
• steam as inert gas is also possible.
• the present invention is based on the finding that for the inerting of the kneading reactor, a significantly lower inert gas volume flow than hitherto customary can be used.
• the inventive method therefore allows considerable savings in the inert gas.
• an excessively low inert gas volume flow in the preparation of water-absorbent polymer particles having a high centrifuge retention capacity (CRC) leads to a turbulent reaction course and to an increased power consumption of the kneader shafts.
• the inert gas volume flow can also be wholly or partly conveyed together with the monomer solution or suspension via a common feed line into the kneading reactor.
• redox initiators are used, wherein the reducing agent is preferably metered into the kneading reactor separately from the monomer solution or suspension.
• 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
• 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 monomers a) usually contain polymerization inhibitors, preferably hydroquinone half ethers, as a storage stabilizer.
• the monomer solution preferably contains up to 250 ppm by weight, preferably at most 130 ppm by weight, more preferably at most 70 ppm by weight, preferably at least 10 ppm by weight, more preferably at least 30 ppm by weight, in particular by 50% by weight .-ppm, hydroquinone, in each case based on the unneutralized monomer a).
• an ethylenically unsaturated, acid group-carrying monomer having a corresponding content of hydroquinone half-ether can be used to prepare the monomer solution.
• hydroquinone half ethers are hydroquinone monomethyl ether (MEHQ) and / or alpha-tocopherol (vitamin E).
• Suitable crosslinkers b) are compounds having at least two groups suitable for crosslinking. Such groups are, for example, ethylenically unsaturated groups which can be incorporated in the polymer chain by free-radical polymerization, and functional groups which can form covalent bonds with the acid groups of the monomer a). Furthermore, polyvalent metal salts 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.
• overall suitable crosslinkers b) are, for example, ethylene glycol dimethacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, allyl methacrylate, trimethylolpropane triacrylate, triallylamine, tetraallylammonium chloride, tetraallyloxyethane, as described in EP 0 530 438 A1, di- and triacrylates, as in EP 0 547 847 A1, EP 0 559 476 A1, EP 0 632 068 A1, WO 93/21237 A1, WO 2003/104299 A1, WO 2003/104300 A1, WO
• Preferred crosslinkers b) are pentaerythritol triallyl ether, tetraalloxyethane, methylenebis methacrylamide, 15-times ethoxylated trimethylolpropane triacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate and triallylamine.
• Very particularly preferred crosslinkers b) are the polyethoxylated and / or propoxylated glycerols esterified with acrylic acid or methacrylic acid to form di- or triacrylates, as described, for example, in WO 2003/104301 A1.
• Particularly advantageous are di- and / or triacrylates of 3- to 10-fold ethoxylated glycerol.
• diacrylates or triacrylates of 1 to 5 times ethoxylated and / or propoxylated glycerol.
• Most preferred are the triacrylates of 3 to 5 times ethoxylated and / or propoxylated glycerol, in particular the triacylate of 3-times ethoxylated glycerol.
• the amount of crosslinker b) is preferably 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).
• CRC centrifuge retention capacity
• initiators c) it is possible to use all compounds which generate free radicals under the polymerization conditions, for example thermal initiators, redox initiators, photoinitiators.
• Suitable redox initiators are sodium peroxodisulfate / ascorbic acid, hydrogen peroxide / ascorbic acid, sodium peroxodisulfate / sodium bisulfite and hydrogen peroxide / sodium bisulfite.
• Preference is given to using mixtures of thermal initiators and redox initiators, such as sodium peroxodisulfate / hydrogen peroxide / ascorbic acid.
• the reducing component used is preferably a mixture of the sodium salt of 2-hydroxy-2-sulfinatoacetic acid, the disodium salt of 2-hydroxy-2-sulfonatoacetic acid and sodium bisulfite.
• Such mixtures are available as Brüggolite® FF6 and Brüggolite® FF7 (Brüggemann Chemicals; Heilbronn; DE).
• Examples of 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.
• 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 dissipated insufficiently.
• 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.
• the oxygen content of the monomer solution before the polymerization is preferably reduced to less than 1 ppm by weight, more preferably less than 0.5 ppm by weight, most preferably from 0.1 to 0.3 ppm by weight ,
• Kneader reactors which can be used in the process according to the invention are obtainable, for example, from List AG, Arisdorf, CH and in CH 0 664 704 A5, EP 0 517 068 A1, WO 97/12666 A1, DE 21 23 956 A1, EP 0 603 525 A1, DE 195 36 944 A1 and DE 41 18 884 A1.
• Such kneading reactors with two shafts achieve a high degree of self-cleaning due to the arrangement of the kneading and transport elements, which is an important requirement for continuous polymerisation.
• the two waves rotate in opposite directions to each other.
• mixing bars suitable for the wall as well as L-shaped or U-shaped shaped attachments are suitable.
• the reaction can also be carried out under reduced pressure at 100 to 800 mbar, in particular 200 to 600 mbar.
• the kneading reactor can be heated or cooled as needed.
• the monomer solution or suspension is polymerized therein at a temperature in the range of preferably 0 to 140 ° C, more preferably 30 to 120 ° C, most preferably 50 to 100 ° C.
• the inventive method is carried out so that the proportion of heat removal by evaporation of water from the reaction mixture, based on the heat of reaction, at least 5%, more preferably at least 15%, most preferably at least 20%.
• process variants are preferred in which the proportion of heat removal by the product discharge, based on the heat of reaction, preferably at least 25%, preferably at least 45%, most preferably at least 55%.
• the reactor inner wall and at least one, preferably all, shafts of the kneading reactor are cooled.
• the polymer gel obtained in the polymerization usually has a residual monomer content of 3,000 to 6,000 ppm by weight.
• the production process is characterized by low residence times in the reactor and thus a good space / time yield.
• a good space / time yield Even at residence times of less than 30 minutes at a reactor volume of at least 500 l, water-absorbing polymer particles having a high monomer conversion are found.
• Particular preference is given to process variants with a high mass throughput which allows residence times of less than 20 minutes and even less than 15 minutes.
• the time until the peak temperature is reached (peak temperature) in the process according to the invention is preferably 5 minutes and less preferably in the range of 2 to 4 minutes. In this range, the optimum in terms of throughput in the reactor and product quality (low agglomerates, good residual monomer values, etc.).
• the polymer gel leaving the kneading reactor can subsequently be stored in a residence time vessel at temperatures of preferably 50 to 120 ° C., more preferably 80 to 100 ° C.
• the residence time is preferably 3 minutes to 3 hours, more preferably 5 to 30 minutes.
• the container may be an upwardly open container, but it is also possible a sealed container, to which a slight vacuum is applied.
• 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%, the usual 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 their mixtures.
• the polymer gel is also possible to carry out the neutralization after the polymerization at the stage of the polymer gel formed during the polymerization. Furthermore, it is possible to neutralize up to 40 mol%, preferably 10 to 30 mol%, particularly preferably 15 to 25 mol%, of the acid groups before the polymerization by adding a part of the neutralizing agent already to the monomer solution and the desired final degree of neutralization is adjusted only after the polymerization at the level of the polymer gel. If 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
• the solids content of the gel before drying is preferably from 25 to 90% by weight, more preferably from 35 to 70% by weight, most preferably from 40 to 60% by weight. - Alternatively, a fluidized bed dryer or a heated ploughshare mixer can be used for drying.
• 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.
• the proportion of particles having a particle size of at least 150 .mu.m 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 850 microns is preferably at least 90 wt .-%, more preferably at least 95 wt .-%, most preferably at least 98 wt .-%.
• Polymer particles with too large particle size reduce the swelling rate. Therefore, the proportion of polymer particles too large should also be low.
• Preferred 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 postcrosslinkers are 2-hydroxyethyloxazolidin-2-one, oxazolidin-2-one and 1,3-propanediol.
• the amount of 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 in addition to the postcrosslinkers before, during or after the postcrosslinking.
• 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, hydrogensulfate, carbonate, hydrogencarbonate, nitrate, phosphate, hydrogenphosphate, dihydrogenphosphate 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 postcrosslinking is usually carried out by spraying a solution of the postcrosslinker onto the dried 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 spraying of a solution of the postcrosslinker is preferably carried out in mixers with moving mixing tools, such as screw mixers, disk mixers, plowshare mixers and paddle mixers.
• moving mixing tools such as screw mixers, disk mixers, plowshare mixers and paddle mixers.
• horizontal mixers such as plowshare mixers and paddle mixers, very particular preference is given to vertical mixers.
• suitable mixers are Lödige mixers, Beex mixers, Nauta mixers, Processall mixers and Schugi mixers.
• the postcrosslinkers are typically used as an aqueous solution. About the content of non-aqueous solvent or total solvent amount, the penetration depth of the postcrosslinker can be adjusted in the polymer particles.
• 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 drying is preferably carried out in contact dryers, more preferably paddle dryers, very particularly preferably disk dryers.
• Suitable dryers include Bepex-T rockner and Nara-T rockner.
• fluidized bed dryers can also be used.
• the drying can take place in the mixer itself, by heating the jacket or blowing hot air.
• 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 0 C, preferably 120 to 220 0 C, particularly preferably 130 to 210 ° C most preferably 150 to 200 0 C. by weight, the preferred residence time at this temperature in the reaction mixer or dryer is preferably at least 10 minutes , more preferably at least 20 minutes, most preferably at least 30 minutes, and usually at most 60 minutes. Subsequently, the postcrosslinked polymer particles can be classified again.
• the postcrosslinked polymer particles can be coated or rehydrated to further improve the properties.
• Suitable coatings for improving the swelling rate and the permeability (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.
• the water-absorbing polymer particles produced by the process according to the invention have a moisture content of preferably 0 to 15% by weight, more preferably 0.2 to 10% by weight, very particularly preferably 0.5 to 8% by weight, the water content being determined according to the test method No. WSP 230.2-05 "Moisture Content" recommended by the EDANA (European Disposables and Nonwovens Association).
• the postcrosslinked water-absorbing polymer particles obtainable by the process according to the invention have a centrifuge retention capacity (CRC) of typically at least 20 g / g, preferably at least 22 g / g, preferably at least 24 g / g, more preferably at least 26 g / g, most preferably 30 to 32 g / g, on.
• CRC centrifuge retention capacity
• the polyethylenically unsaturated crosslinker used is 3-times ethoxylated glycerol triacrylate.
• the amount used was 1.1 kg per ton of monomer solution.
• the throughput of the monomer solution was 18 t / h.
• the individual components are metered continuously into a reactor List Contikneter with capacity 6.3 m 3 (Messrs. List, Arisdorf, Switzerland).
• the reaction solution had the influent of a temperature of 30 0 C.
• the reactor was operated at a rotational speed of the shafts of 38 rpm.
• the residence time of the reaction mixture in the reactor was 15 minutes.
• the monomer solution was made inert with 2.4 m 3 nitrogen / h, wherein the nitrogen was metered into the kneading reactor together with the monomer solution.
• a further 96 m 3 of nitrogen / h were metered directly into the kneading reactor. This corresponded to a total inert gas volume flow of 15.6 m 3 / h per m 3 of reactor volume.
• the power consumption of the kneader shafts was 72% of the maximum power consumption.
• the dried hydrogel was ground and screened to a particle size of 150 to 850 microns.
• the dried polymer particles had a centrifuge retention capacity of 39 g / g.
• Example 3 (comparative example)
• Example 2 The procedure was as in Example 1. The amount of 3-ethoxylated Glycerintriacrylat was to 1, 5 kg per ton of monomer solution and the recycled amount of undersize was increased to 1,000 kg / h. The power consumption of the kneader shafts was 72% of the maximum power consumption.
• the dried polymer particles had a centrifuge retention capacity of 34.5 g / g.
• Example 3 The procedure was as in Example 3. Only the amount of nitrogen used to inert the monomer solution was used. The inert gas volume flow was therefore only 0.38 m 3 / h per m 3 reactor volume. The power consumption of the kneader shafts was still 72% of the maximum power consumption.
• Example 3 The comparison of Example 3 with Example 4 demonstrates that the inert gas volume flow when making water-absorbent polymer particles with low centrifuge retention capacity (CRC) has no effect on the power consumption of the kneader shafts.
• CRC centrifuge retention capacity

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• 2009
  • 2009-03-16 CN CN2009801090356A patent/CN101970505A/zh active Pending
  • 2009-03-16 WO PCT/EP2009/053030 patent/WO2009115472A1/de active Application Filing
  • 2009-03-16 EP EP09721312A patent/EP2257574A1/de not_active Withdrawn
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