Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B7/00—Mixing; Kneading
• • 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
• • 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
  • C08F6/00—Post-polymerisation treatments
  • C08F6/008—Treatment of solid polymer wetted by water or organic solvents, e.g. coagulum, filter cakes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/12—Powdering or granulating
  • C08J3/128—Polymer particles coated by inorganic and non-macromolecular organic compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
  • C08J3/245—Differential crosslinking of one polymer with one crosslinking type, e.g. surface crosslinking
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2300/00—Characterised by the use of unspecified polymers
  • C08J2300/14—Water soluble or water swellable polymers, e.g. aqueous gels

Definitions

• the invention relates to a process for the preparation of post-treated surface- crosslinked water-absorbent polymer particles; to a post-treated surface-crosslinked water- absorbent polymer particle obtainable by such a process; to a plurality of post-treated sur- face-crosslinked water-absorbent polymer particles; to a composite material comprising such a post-treated surface-crosslinked water-absorbent polymer particle or such a plurality of post-treated surface-crosslinked water-absorbent polymer particles; to a process for the production of a composite material; to a composite material obtainable by such a process; to a use of the post-treated surface-crosslinked water-absorbent polymer particle or the plural- ity of post-treated surface-crosslinked water-absorbent polymer particles; to a device for the preparation of post-treated surface-crosslinked water-absorbent polymer particles; and to a process for the preparation of post-treated surface-crosslinked water-absorbent polymer particles using such
• Superabsorbers also called super absorbing polymers (SAP) are water-insoluble, crosslinked polymers which are able to absorb large amounts of aqueous fluids, especially body fluids, more especially urine or blood, with swelling and the formation of hydrogels, and to retain such fluids under a certain pressure.
• SAP super absorbing polymers
• the preparation of superabsorbers is generally carried out by free-radical polymerization of acid-group-carrying monomers in the presence of crosslinkers, it being possible for polymers having different absorber properties to be prepared by the choice of the mo- nomer composition, the crosslinkers and the polymerization conditions and of the processing conditions for the hydrogel obtained after the polymerization (for details see, for example, Modern Superabsorbent Polymer Technology, FL Buchholz, GT Graham, Wiley- VCH, 1998).
• the acid-group-carrying monomers can be polymerized in the presence of the crosslinkers in a batch process or in a continuous process. Both in continuous and in batchwise polymerization, partially neutralized acrylic acid is typically used as the monomer. Suitable neutralization processes are described, for example, in EP 0 372 706 A2, EP 0 574 260 Al , WO 2003/051415 Al , EP 1 470 905 Al , WO 2007/028751 Al, WO 2007/028746 A 1 and WO 2007/028747 Al .
• the polymer gel, also called hydrogel, obtained after the polymerization is usually comminuted, dried and classified in order to obtain a particulate superabsorber with a well defined particles size distribution.
• these superabsorbent particles are often surface crosslinked.
• the particles are mixed with an aqueous solution containing a surface crosslinking agent and optionally further additives and the thus obtained mixture is heat treated in order to promote the crosslinking reaction. Thereby, an absorption behavior of the superabsorbent particles is improved. This improves the performance of the superabsorbent particles being used in sanitary articles.
• the superabsorbent particles are typically meant to absorb urine.
• the superabsorbent particles having absorbed urine radiate a malodor typical for urine and urine degradation.
• a further object is to provide a process for the production of surface-crosslinked water-absorbent polymers, being characterized by producing less fine particles. It is a further object of the invention to provide a process for the production of surface-crosslinked water- absorbent polymers, wherein surface-crosslinked polymer particles show a better odor control, for example after absorbing urine. It is a further object of the invention to provide a process for the production of surface-crosslinked water-absorbent polymers, being characterized by a more gentle treatment of polymer particles.
• a further object is to provide superabsorbent polymer particles which have been produced by a less expensive process.
• It is a further object of the present invention to provide a superabsorbent polymer particles produced by a process having at least one, preferably a balanced combination of at least two, of the above advantages, wherein the superabsorbent polymer particles show no reduction of quality.
• Water-absorbent polymer particles which have an improved odor control characteristics are provided.
• Figure 1 a flow chart diagram depicting the steps of a process according to the invention
• Figure 2 a flow chart diagram depicting the steps of another process according to the invention.
• Figure 3 a flow chart diagram depicting the steps of another process according to the invention.
• Figure 4 a scheme of a particle mixing device according to the invention
• Figure 5 a flow chart diagram depicting the process steps (xi) to (xiii) of a process according to the invention
• Figure 6 a flow chart diagram depicting the process steps (xi) to (xiii) of another process according to the invention.
• Figure 7 a block diagram of a device for the preparation of post-treated surface- crosslinked water-absorbent polymer particles according to the invention
• Figure 8a a scheme of a longitudinal cross section of a further mixing device according to the invention.
• Figure 8b a scheme of a transversal cross section of the further mixing device in figure 8a).
• PAgz further gas pressure
• a contribution to the solution of at least one of these objects is made by a process for the preparation of post-treated surface-crosslinked water-absorbent polymer particles, comprising the process steps of
• the process according to the present invention is preferably a continuous process in which the aqueous monomer solution is continuously provided and is continuously fed into the polymerization reactor.
• the polymerization reactor is a polymerization belt reactor.
• the aqueous monomer solution is continuously provided and is continuously fed onto the belt of the polymerization belt reactor. Details of the features of a preferred belt reactor are described below.
• the polymer gel obtained is continuously discharged out of the polymerization reactor and is continuously optionally comminuted, dried, ground and sized in the subsequent process steps.
• This continuous process may, however, be interrupted in order to, for example, substitute certain parts of the process equipment, like the belt material of the conveyor belt if a conveyor belt is used as the polymerization reactor,
• Surface-crosslinked water-absorbent polymer particles which are preferred according to the invention are particles that have an average particle size in accordance with WSP 220.2 (test method of " Word Strategic Partners” ED ANA and INDA) in the range of from 10 to 3,000 ⁇ , preferably 20 to 2,000 ⁇ and particularly preferably 150 to 850 ⁇ .
• WSP 220.2 test method of " Word Strategic Partners" ED ANA and INDA
• an aqueous monomer solution containing at least one partially neutralized, monoethylenically unsaturated monomer bearing carboxylic acid groups (al) and at least one crosslinker (a3) is prepared.
• Preferred monoethylenically unsaturated monomers bearing carboxylic acid groups (al) are those cited in DE 102 23 060 Al as preferred monomers ( l), whereby acrylic acid is particularly preferred.
• Preferred monoethylenically unsaturated monomers bearing carboxylic acid groups (al) are acrylic acid, methacrylic acid, ethacrylic acid, a-chloro-acrylic acid, a-cyano-acrylic acid, ⁇ -methylacrylic acid (Crotonic acid), a-phenyl-acrylic acid, ⁇ - acryloxypropionic acid, sorbic acid, a-chlorosorbic acid, 2'-methylisocrotonic acid, cinamic acid, p-chloro cinamic acid, ⁇ -stearylic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fumaric acid, tri-carboxy-ethylen- and maleic
• the water-absorbent polymer produced by the process according to the invention comprises monomers bearing carboxylic acid groups to at least 50 wt.-%, preferably to at least 70 wt.-% and further preferably to at least 90 wt.-%, based on the dry weight. It is particularly preferred according to the invention, that the water-absorbent polymer produced by the process according to the invention is formed from at least 50 wt.-%, preferably at least 70 wt.-% of acrylic acid, which is preferably neutralized to at least 20 mol-%, particularly preferably to at least 50 mol-%.
• the concentration of the at least one partially neutralized, monoethylenically unsaturated monomer bearing carboxylic acid groups (al) in the aqueous monomer solution that is provided in process step (i) is preferably in the range between 10 to 60 wt.-%, preferably 30 to 55 wt.-% and most preferably between 40 to 50 wt.-%, based on the total weight of the aqueous monomer solution.
• preparing the aqueous monomer solution comprising at least one partially neu- tralized, monoethylenically unsaturated monomer bearing carboxylic acid groups (al), comprises a neutralization of a monomer, comprising at least one monoethylenically unsaturated monomer bearing carboxylic acid groups.
• preparing the aqueous monomer solution further comprises (il) providing of a first portion of acrylic acid comprising mono methyl ether hydro- quinone (MEHQ) or hydroquinone (HQ) or both; and
• the neutralization of the monomers bearing carboxylic acid groups is preferably established by addition of sodium hydroxide to at least a part of the aqueous monomer solution at the beginning of step (i).
• a part of the aqueous monomer solution comprises acrylic acid as the monomer bearing carboxylic acid groups, called the first portion of acrylic acid.
• the first portion of acrylic acid preferably comprises mono methyl ether hydroquinone (MEHQ) or hydroquinone (HQ).
• MEHQ mono methyl ether hydroquinone
• HQ hydroquinone
• the first portion of acrylic acid is preferably contacted with sodium hydroxide (NaOH), wherein a pH of 10 or more is obtained resulting in a first aqueous Na-acrylate comprising phase.
• the first portion of acrylic acid preferably comprises the sodium hydroxide in a ratio to the acrylic acid from 0.1 : 1 to 1.5: 1 , or preferably in a ratio from 0.2: 1 to 1.3: 1 , or preferably in a ratio from 0.3 : 1 to 1 : 1.
• the preferred addition of sodium hydroxide to the acrylic acid results in a conversion of at least part of the acrylic acid to sodium acrylate.
• the first portion of acrylic acid preferably comprises the mono methyl ether hydroquinone (MEHQ) or hydroquinone (HQ) in an amount from 0.1 to 10 wt.-%, or preferably in an amount from 0.3 to 7 wt.-%, or preferably in an amount from 0.5 to 5 wt- %, based on the total weight of the first portion of acrylic acid.
• the first portion of acrylic acid comprises mono methyl ether hydroquinone (MEHQ).
• step (i) the preparation of the aqueous monomer solution preferably comprises several further steps: a. providing the first portion acrylic acid comprising sodium acrylate and MEHQ or HQ and;
• steps ⁇ and ⁇ can be performed in any order and in any combination with step a. In one preferred embodiment only step a is performed. In a further preferred embodiment steps a and ⁇ are performed. In yet a further preferred embodiment steps a and ⁇ are performed. Also the order can be varied in step (i). In a preferred embodiment the crosslinker (a3) is provided first and then step a and optionally one of steps ⁇ and/or ⁇ can be performed. In a further preferred embodiment step a alone or in a combination with one of steps ⁇ or ⁇ is firstly performed and afterwards the crosslinker (oc3) is added.
• the acrylate and acrylic acid content of the aqueous monomer solution is less than 55 wt.-%, preferably less than 50 wt.-%, or preferably less than 45 wt.-%, related to the total weight of the aqueous monomer solution. It is furthermore preferred that the acrylate and acrylic acid content of the aqueous monomer solution is not below 30 wt.-%.
• the aqueous monomer solution may also comprise monoethylenically unsaturated monomers (a2) which are copolymerizable with (al).
• Preferred monomers (a2) are those monomers which are cited in DE 102 23 060 Al as preferred monomers (a2), whereby acrylamide is particularly preferred.
• a crosslinking of the polymer is achieved by radical polymerization of the ethylenically unsaturated groups of the crosslinker molecules with the monoethylenically unsaturated monomers (al) or (a2), while with the compounds of crosslinker class II and the polyvalent metal cations of crosslinker class IV a crosslinking of the polymer is achieved respectively via condensation reaction of the functional groups (crosslinker class II) or via electrostatic interaction of the polyvalent metal cation (crosslinker class IV) with the functional groups of the monomer (al) or (a2).
• cross-linker class III a cross-linking of the polymers is achieved correspondingly by radical polymerizatio'n of the ethylenically unsaturated groups as well as by condensation reaction between the functional groups of the cross-linkers and the functional groups of the monomers (al) or (a2).
• Preferred crosslinkers (a3) are all those compounds which are cited in DE 102 23 060 Al as crosslinkers (a3) of the crosslinker classes I, II, III and IV, whereby as compounds of crosslinker class I, N, 1ST -methylene bisacrylamide, polyethylene- glycol di(meth)acrylates, triallylmethylammonium chloride, tetraallylammonium chloride and allylnonaethyleneglycol acrylate produced with 9 mol ethylene oxide per mol acrylic acid are particularly preferred, wherein N, 1ST -methylene bisacrylamide is even more preferred, and as compounds of crosslinker class IV, Al 2 (S0 4 ) 3 and its hydrates are particularly pre- ferred.
• Preferred water-absorbent polymers produced by the process according to the invention are polymers which are crosslinked by crosslinkers of the following crosslinker classes or by crosslinkers of the following combinations of crosslinker classes respectively: I, II, III, IV, I II, I III, I IV, I II III, I II IV, I III IV, II III IV, II IV or III IV.
• water-absorbent polymers produced by the process according to the invention are polymers which are crosslinked by any of the crosslinkers disclosed in DE 102 23 060 Al as crosslinkers of crosslinker classes I, whereby ⁇ , ⁇ ' -methylene bisacrylamide, polyethyleneglycol di(meth)acrylates, triallyl-methylammonium chloride, tetraallylammonium chloride and allylnonaethylene-glycol acrylate produced from 9 mol ethylene oxide per mol acrylic acid are particularly preferred as crosslinkers of crosslinker class I, wherein N, N' -methylene bisacrylamide is even more preferred.
• the aqueous monomer solution may further comprise water-soluble polymers (a4).
• Preferred water-soluble polymers (a4) include partly or completely saponified polyvinyl alcohol, polyvinylpyrrolidone, starch or starch derivatives, polyglycols or polyacrylic acid. The molecular weight of these polymers is not critical, as long as they are water-soluble.
• Preferred water-soluble polymers (a4) are starch or starch derivatives or polyvinyl alcohol.
• the water-soluble polymers (a4), preferably synthetic, such as polyvinyl alcohol, can not only serve as a graft base for the monomers to be polymerized.
• auxiliary substances these auxiliary substances including, in particular, complexing agents, such as, for example, EDTA.
• the relative amount of monomers ( l) and (a2) and of crosslinking agents (a3) and water-soluble polymers (a4) and auxiliary substances (a5) in the aqueous monomer solution is preferably chosen such that the water-absorbent polymer structure obtained after drying the optionally comminuted polymer gel is based - to the extent of from 20 to 99.999 wt.-%, preferably to the extent of 55 to 98.99 wt- % and particularly preferably to the extent of 70 to 98.79 wt.-% on monomers (al), to the extent of from 0 to 80 wt.-%, preferably to the extent of 0 to 44.99 wt.-% and particularly preferably to the extent of 0.1 to 44.89 wt.-% on the monomers (a2), to the extent of from 0 to 5 wt.-%, preferably to the extent of 0.001 to 3 wt.-% and particularly preferably to the extent of 0.01 to 2.5 wt.-%
• Optimum values for the concentration in particular of the monomers, crosslinking agents and water-soluble polymers in the monomer solution can be determined by simple preliminary experiments or from the prior art, in particular from the publications US 4,286,082, DE 27 06 135 Al, US 4,076,663, DE 35 03 458 Al, DE 40 20 780 CI, DE 42 44 548 A1, DE 43 33 056 Al and DE 44 18 818 Al .
• fine particles of a water-absorbent polymer may optionally be added to the aqueous monomer solution.
• fine water- absorbent polymer particles may be added to the aqueous monomer solution at one selected from the group consisting of after step (iii), after step (iv), and before step (v), or a combination of at least two thereof.
• surface-crosslinked fine particles or non- surface-crosslinked fine particles or both may optionally be added to the aqueous monomer solution.
• fine particles refers to surface-crosslinked fine particles and non-surface- crosslinked fine particles.
• Fine particles are preferably water-absorbent polymer particles the composition of which corresponds to the composition of the above described water-absorbent polymer particles, wherein it is preferred that at least 90 wt.-% of the water-absorbent fine particles, preferably at least 95 wt.-% of the water-absorbent fine particles and most preferred at least 99 wt.-% of the water-absorbent fine particles based on the total weight of the water- absorbent fine particles have a particle size of less than 200 ⁇ , preferably less than 150 ⁇ and particular preferably less than 100 ⁇ .
• the water- absorbent fine particles which may optionally be added to the aqueous monomer solution in process step (ii) are fine particles which are obtained in process step (x) or (xii) or both of the process according to the present invention and which are thus recycled.
• the fine particles can be added to the aqueous monomer solution by means of any mixing device the person skilled of the art would consider as appropriate for this purpose.
• the fine particles are added to the aqueous monomer solution in a mixing device in which a first stream of the fine particles and a second stream of the aqueous monomer solution are directed continuously, but from different directions, onto a rotating mixing device.
• a mixing device in which a first stream of the fine particles and a second stream of the aqueous monomer solution are directed continuously, but from different directions, onto a rotating mixing device.
• a so called "Rotor Stator Mixer” which comprises in its mixing area a preferably cylindrically shaped, non-rotating stator, in the centre of which a likewise preferably cylindrically shaped rotor is rotating.
• the walls of the rotor as well as the walls of the stator are usually provided with notches, for example notches in the form of slots, through which the mixture of fine particles and aqueous monomer solution can be sucked through and thus can be subjected to high shear forces.
• the first stream of the fine particles and the second stream of the aqueous monomer solution form an angle ⁇ in the range from 60 to 120°, preferably in the range from 75 to 105°, or preferably in the range from 85 to 95°, or preferably form an angle of about 90°.
• the stream of the mixture of fine particles and aqueous monomer solution that leaves the mixer and the first stream of fine particles that enters the mixer form an angle ⁇ in the range from 60 to 120°, preferably in the range from 75 to 105°, or preferably in the range from 85 to 95°, or preferably form an angle of about 90°.
• Such a kind of mixing set up can, for example, be realized by means of mixing devices which are disclosed in DE-A-25 20 788 and DE-A-26 17 612.
• Specific examples of mixing devices which can be used to add the fine particles to the aqueous monomer solution in process step (ii) of the present invention are the mixing devices which can be obtained by the IKA® Werke GmbH & Co. KG, Staufen, Germany, under designations MHD 2000/4, MHD 2000/05, MHD 2000/10, MDH 2000/20, MHD 2000/30 und MHD 2000/50, wherein the mixing device MHD 2000/20 is particularly preferred.
• the amount of fine particles that may be added to the aqueous monomer solution in process step (ii) is preferably in the range from 0.1 to 15 wt.-%, even more preferred in the range from 0.5 to 10 wt.-% and most preferred in the range from 3 to 8 wt.-%, based on the weight of the aqueous monomer solution.
• a polymerization initiator or at least one component of a polymerization initiator system that comprises two or more components is added to the aqueous monomer solution.
• polymerization initiators for initiation of the polymerisation all initiators forming radicals under the polymerization conditions can be used, which are commonly used in the production of superabsorbers. Among these belong thermal catalysts, redox catalysts and photo-initiators, whose activation occurs by energetic irradiation.
• the polymerization initiators may be dissolved or dispersed in the aqueous monomer solution. The use of water- soluble catalysts is preferred.
• thermal initiators may be used all compounds known to the person skilled in the art that decompose under the effect of an increased temperature to form radicals. Particularly preferred are thermal polymerisation initiators with a half life of less than 10 seconds, more preferably less than 5 seconds at less than 180°C, more preferably at less than 140°C. Peroxides, hydroperoxides, hydrogen peroxide, persulfates and azo compounds are particularly preferred thermal polymerization initiators. In some cases it is advantageous to use mixtures of various thermal polymerization initiators. Among such mixtures, those consisting of hydrogen peroxide and sodium or potassium peroxodisulfate are preferred, which may be used in any desired quantitative ratio.
• Suitable organic peroxides are preferably ace- tylacetone peroxide, methyl ethyl ketone peroxide, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, capryl peroxide, isopropyl peroxidicarbonate, 2-ethylhexyle peroxidicarbonate, tert.-butyl hydroperoxide, cumene hydroperoxide, and peroxides of tert.-amyl perpivalate, tert.-butyl perpivalate, tert.-butyl perneohexonate, tert.-butyl isobutyrate, tert.-butyl per-2- ethylhexenoate, tert.-butyl perisononanoate, tert.-butyl permaleate, tert.-butyl perbenzoate, tert.-butyl-3,5,5-trimethyl
• thermal polymerisation initiators are preferred: azo compounds such as azo-bis- isobutyronitril, azo-bis-dimethylvaleronitril, azo-bis-ami-dinopropane dihydrochloride, 2,2'- azobis-(N,N-dimethylene)isobutyramidine di-hydrochloride, 2- (carbamoylazo)isobutyronitrile and 4,4'-azobis-(4-cyano-valeric acid).
• azo compounds such as azo-bis- isobutyronitril, azo-bis-dimethylvaleronitril, azo-bis-ami-dinopropane dihydrochloride, 2,2'- azobis-(N,N-dimethylene)isobutyramidine di-hydrochloride, 2- (carbamoylazo)isobutyronitrile and 4,4'-azobis-(4-cyano-valeric acid).
• the aforementioned compounds are used in conventional
• Redox catalysts comprise two or more components, usually one or more of the peroxo compounds listed above, and at least one reducing component, preferably ascorbic acid, glucose, sorbose, mannose, ammonium or alkali metal hydrogen sulfite, sulfate, thiosulfate, hyposulfite or sulfide, metal salts such as iron II ions or silver ions or sodium hydroxy- methyl sulfoxylate.
• reducing component preferably ascorbic acid, glucose, sorbose, mannose, ammonium or alkali metal hydrogen sulfite, sulfate, thiosulfate, hyposulfite or sulfide, metal salts such as iron II ions or silver ions or sodium hydroxy- methyl sulfoxylate.
• ascorbic acid or sodium pyrosulfite is used as reducing com- ponent of the redox catalyst.
• 1 ⁇ 10 "5 to 1 mol-% of the reducing component of the redox catalyst and 1 ⁇ 10 "5 to 5 mol-% of the oxidizing component of the redox catalyst are used, in each case referred to the amount of monomers used in the polymerization.
• the oxidising component of the redox catalyst or as a complement thereto, one or more, preferably water-soluble azo compounds may be used.
• the polymerization is preferably initiated by action of energetic radiation, so-called photo-initiators are generally used as initiator. These can comprise for example so-called a- splitters, H-abstracting systems or also azides. Examples of such initiators are benzophe- none derivatives such as Michlers ketone, phenanthrene derivatives, fluorine derivatives, anthraquinone derivatives, thioxanthone derivatives, cumarin derivatives, benzoinether and derivatives thereof, azo compounds such as the above-mentioned radical formers, substituted hexaarylbisimidazoles or acylphosphine oxides.
• photo-initiators are generally used as initiator. These can comprise for example so-called a- splitters, H-abstracting systems or also azides. Examples of such initiators are benzophe- none derivatives such as Michlers ketone, phenanthrene derivatives, fluorine derivatives, anthraquinone derivatives,
• azides are: 2-(N,N- dimethylamino)ethyl-4-azidocinnamate, 2-(N,N-dimethylamino)ethyl-4- azidonaphthylketone, 2-(N,N-di-methylamino)ethyl-4-azidobenzoate, 5-azido-l-naphthyl- 2'-(N,N-dimethylami-no)ethylsulfone, N-(4-sulfonylazidophenyl)maleinimide, N-acetyl-4- sulfonyl-azidoaniline, 4-sulfonylazidoaniline, 4-azidoaniline, 4-azidophenacyl bromide, p- azidobenzoic acid, 2,6-bis(p-azidobenzylidene)cyclohexanone and 2,6-bis(p- azidobenz
• a further group of photo-initiators are di- alkoxy ketales such as 2,2-dimethoxy-l ,2-diphenylethan-l-one.
• the photo-initiators when used, are generally employed in quantities from 0.0001 to 5 wt.-% based on the monomers to be polymerized.
• the initiator comprises the following components
• iiib an organic initiator molecule comprising at least three oxygen atoms or at least three nitrogen atoms;
• the initiator comprises the peroxodisulfate and the organic initiator molecule in a molar ratio in the range of from 20: 1 to 50: 1.
• concentration of the initiator component iiia. is in the range from 0.05 to 2 wt.-%, based on the amount of monomers to be polymerized.
• organic initiator molecule is selected from the group consisting of 2,2-dimethoxy-l ,2-diphenylethan-l -one, 2,2-azobis-(2- amidinopropane)dihydrochloride, 2,2-azobis-(cyano valeric acid) or a combination of at least two thereof.
• the peroxodisulfate is of the general formula M2S208, with M being selected from the group consisting of NH4, Li, Na, Ka or at least two thereof.
• M being selected from the group consisting of NH4, Li, Na, Ka or at least two thereof.
• the above described components are in particular suitable for UV initiation of the polymerization in step (vi) of the process of the present invention.
• Employing this composition further yields low residual monomer and reduced yellowing in the water-absorbent polymer particle, obtainable by the process according to the present invention.
• step (iii), adding the polymerization initiator may be realized before step (iv), simultaneously to step (iv), or overlapping in time with step (iv), i.e. when the oxygen content of the aqueous monomer solution is decreased.
• a polymerization initiator system is used that comprises two or more components, one or more of the components of such a polymerization initiator system may, for example, be added before process step (iv), whereas the remaining component or the remaining components which are necessary to complete the activity of the polymerisation initiator system, are added after process step (iv), perhaps even after process step (v).
• decreasing the oxygen content of the aqueous monomer solution may also be performed before process step (iii) according to the invention.
• the oxygen content of the aqueous monomer solution is optionally decreased.
• decreasing the oxygen content of the aqueous monomer solution may also be performed before, during or after process step (ii) according to the invention.
• the oxygen content of the aqueous monomer solution is decreased after the fine particles have been added in process step (ii).
• oxygen content of the aqueous monomer solution is decreased, this may be realized by bringing the aqueous monomer solution into contact with an inert gas, such as nitrogen.
• the phase of the inert gas being in contact with the aqueous monomer solution is free of oxygen and is thus characterized by a very low oxygen partial pressure.
• oxygen converts from the aqueous monomer solution into the phase of the inert gas until the oxygen partial pressures in the phase of the inert gas and the aqueous monomer solution are equal.
• Bringing the aqueous monomer phase into contact with a phase of an inert gas can be accomplished, for example, by introducing bubbles of the inert gas into the monomer solution in co-current, countercurrent or intermediate angles of entry. Good mixing can be achieved, for example, with nozzles, static or dynamic mixers or bubble columns.
• the oxygen content of the monomer solution before the polymerization is preferably lowered to less than 1 ppm by weight, more preferably to less than 0.5 ppm by weight, based on the monomer solution.
• the aqueous monomer solution is charged into a polymerization reactor, preferably onto a conveyor belt, especially preferred at an upstream position of the conveyor belt and in process step (vi) the monomers in the aqueous monomer solution are polymerized in the polymerization reactor, thereby obtaining a polymer gel.
• a polymer gel sheet is obtained in a downstream portion of the conveyor belt, which, before drying, is preferably comminuted in order to obtain polymer gel particles.
• a polymer gel strand is obtained in a downstream portion of the conveyor belt, which, before drying, is preferably comminuted in order to obtain gel particles.
• Every reactor can be used which the person skilled in the art would regard as appropriate for the continuous or batchwise polymerization of monomers like acrylic acid in aqueous solutions.
• An example of a suitable polymerization reactor is a kneading reactor. In a kneader the polymer gel formed in the polymerization of the aqueous monomer solution is comminuted continuously by, for example, contrarotatory stirrer shafts, as described in WO 2001/38402.
• the polymerization reactor is identical to a first comminuting device according to the invention.
• the rotating component according to the invention may be a rotating stirrer shaft.
• a preferred polymerization reactor is a conveyor belt.
• a conveyor belt that is useful for the process according to the present invention any conveyor belt can be used which the person skilled in the art considers to be useful as a support material onto which the above described aqueous monomer solution can be charged and subsequently polymerized to form a hydrogel.
• the conveyor belt usually comprises an endless moving conveyor belt passing over supporting elements and at least two guide rollers, of which at least one is driven and one is configured so as to be adjustable.
• a winding and feed system for a release sheet that may be used in sections on the upper surface of the conveyor belt is provided.
• the system includes a supply and metering system for the reaction components, and optional irradiating means arranged in the direction of movement of the conveyor belt after the supply and metering system, together with cooling and heating devices, and a removal system for the polymer gel strand that is arranged in the vicinity of the guide roller for the return run of the conveyor belt.
• the conveyor belt is supported in the vicinity of the supply system for the reaction components by a plurality of trough-shaped supporting and bearing elements that form a deep trough-like or dish-like configuration for the reaction components that are introduced.
• each supporting element is preferably formed by a cylindrical or spherical roller that is rotatable about its longitudinal axis.
• a conveyor belt that is flexible in both the longitu- dinal and the transverse directions is preferred.
• the belt can be made of various materials, although these preferably have to meet the requirements of good tensile strength and flexibility, good fatigue strength under repeating bending stresses, good deformability and chemical resistance to the individual reaction components under the conditions of the polymerization. These demands are usually not met by a single material.
• a multi-layer material is commonly used as belt of the present invention.
• the mechanical requirements can be satisfied by a carcass of, for example, fabric inserts of natural and/or synthetic fibers or glass fibers or steel cords.
• the chemical resistance can be achieved by a cover of, for example, polyethylene, polypropylene, poly- isobutylene, halogenated polyolefmes such as polyvinyl chloride or polytetrafluorethylene, polyamides, natural or synthetic rubbers, polyester resins or epoxy resins.
• the preferred cover material is silicone rubber.
• the polymer gel obtained in the polymerization reactor is optionally comminuted, thereby obtaining polymer gel particles.
• Preferred polymer gel particles are one selected from the group consisting of polymer gel strands, polymer gel flakes, and polymer gel nuggets, or a combination of at least two thereof.
• the optional comminuting according to the invention comprises preferably at least two comminuting steps. Therein, a first comminuting step is performed in a first comminuting device and a further comminuting step in a further comminuting device.
• the first comminuting device may be the polymerization reactor or a part of the polymerization reactor, or a separate device, or both. Hence, the first comminuting step may be performed before, during, or after discharging the polymer gel out of the polymerization reactor.
• a preferred polymerization reactor which is the first comminuting device is a kneading reactor. If the first comminuting step is performed in the polymerization reactor, the polymer gel particles obtained are preferably further comminuted in the further comminuting step after discharging out of the polymerization reactor.
• the first comminuting step is preferably performed after discharging the polymer gel as a polymer gel sheet from the conveyor belt in a first comminuting device, wherein the first comminuting device is a separate device.
• the polymer gel sheet is discharged from the conveyor belt as a continuous sheet that is of a soft semi-solid consistency and is then passed on for further processing such as comminuting.
• Comminution of the polymer gel is preferably performed in at least two, more pref- erably at least three steps: in the first comminuting step, a cutting unit, preferably a knife, for example a knife as disclosed in WO-A-96/36464, is used for cutting the polymer gel into flat gel strips, preferably with a length within the range of from 5 to 500 mm, preferably from 10 to 300 mm and particularly preferably, from 100 to 200 mm, a height within the range of from 1 to 30 mm, preferably from 5 to 25 mm and particularly preferably from 10 to 20 mm as well as a width within the range of from 1 to 500 mm, preferably from 5 to 250 mm and particularly preferably from 10 to 200 mm; - in a second step, a shredding unit, preferably a breaker, is used for shredding the gel strips into gel pieces, preferably with a length within the range of 3 to 100 mm, preferably from 5 to 50 mm, a height within the range from 1
• a polymer gel which has been comminuted in this way is particularly suited to belt drying.
• the three-step comminution offers a better "airability" because of the air channels located between the granulate kernels.
• Another preferred comminution of the polymer gel is performed in at least two steps: in a first comminuting step the polymer gel is crushed by a plurality of rotating discs of the first comminuting device, preferably rotating toothed wheels. Thereby a plu- rality of polymer gel strands is produced.
• a "wolf (grinding) unit preferably a mincer, preferably having a screw and a hole plate, whereby the screw conveys against the hole plate is used in order to grind and crush the polymer gel strands into polymer gel particles which are preferably smaller than the polymer gel strands.
• step (viii) of the process according to the present invention the polymer gel is dried.
• water is preferably removed from the polymer gel by a rate in the range of from 120 to 240 kg/minute, preferably from 130 to 230 kg/minute, more preferably from 140 to 220 kg/ minute, more preferably from 150 to 210 kg/minute, most preferably from 160 to 200 kg/minute, based on a portion of the polymer gel in the range of from 0.5 to 5 t, preferably from 0.8 to 4.5 t, most preferably from 1 to 4 t.
• decreasing a water content of the polymer gel from a range of from 40 to 60 wt.-%, based on the total weight of the polymer gel, to a range of from 3 to 7 wt.-%, based on the total weight of the dried polymer gel, is achieved in a time period in the range of from 1 to 60 minutes, preferably from 2 to 50 minutes, more preferably from 3 to 40 minutes.
• the drying of the polymer gel can be effected in any dryer or oven the person skilled in the art considers as appropriate for drying the above described polymer gel and/or polymer gel particles.
• Rotary tube furnaces, fluidized bed dryers, plate dryers, paddle dryers and infrared dryers may be mentioned by way of example.
• a belt dryer is a convective system of drying, for the particularly gentle treatment of through-airable products.
• the product to be dried is placed onto an endless conveyor belt which lets gas through, and is subjected to the flow of a heated gas stream, preferably air.
• the drying gas is preferably recirculated in order that it may become very highly saturated in the course of repeated passage through the product layer.
• a certain fraction of the drying gas preferably not less than 10 %, more preferably not less than 15 % and most preferably not less than 20 % and preferably up to 50 %, more preferably up to 40 % and most preferably up to 30 % of the gas quantity per pass, leaves the dryer as a highly saturated vapor and carries off the water quantity evaporated from the product.
• the temperature of the heated gas stream is preferably not less than 50°C, more preferably not less than 100°C and most preferably not less than 150°C and preferably up to 250°C, more preferably up to 220°C and most preferably up to 200°C.
• a belt dryer can be embodied as a single-belt, multi- belt, multi-stage or multistory system.
• the present invention is preferably practiced using a belt dryer having at least one belt.
• One-belt dryers are very particularly preferred.
• the drying properties of the water- absorbent polymers are individually determined as a function of the processing parameters chosen.
• the hole size and mesh size of the belt is conformed to the product.
• certain surface enhancements such as electropolishing or Teflonizing, are possible.
• the polymer gel and/or polymer gel particles to be dried are preferably applied to the belt of the belt dryer by means of a swivel belt.
• the feed height i.e., the vertical distance between the swivel belt and the belt of the belt dryer, is preferably not less than 10 cm, more preferably not less than 20 cm and most preferably not less than 30 cm and preferably up to 200 cm, more preferably up to 120 cm and most preferably up to 40 cm.
• the thickness on the belt dryer of the polymer gel and/or polymer gel particles to be dried is preferably not less than 2 cm, more preferably not less than 5 cm and most preferably not less than 8 cm and preferably not more than 20 cm, more preferably not more than 15 cm and most preferably not more than 12 cm.
• the belt speed of the belt dryer is preferably not less than 0.005 m/s, more preferably not less than 0.01 m/s and most preferably not less than 0.015 m/s and preferably up to 0.05 m/s, more preferably up to 0.03 m/s and most preferably up to 0.025 m/s.
• the belt dryer comprises a moving belt moving in a direc- tion of a length of a longitudinal housing.
• the moving belt is at least partly comprised in a longitudinal housing.
• a longitudinal extension of the moving belt is in the range from 2 to 100 times, preferably in the range from 3 to 80 times, most preferably in the range from 5 to 50 times, the width of the moving belt.
• the width of the moving belt is preferably in the range of from 10 to 500 cm, more preferably from 50 to 300 cm, more preferably from 80 to 250 cm.
• the length of the belt is preferably in the range of from 20 cm to 100 m, more preferably from 50 cm to 50 m, most preferably from 1 to 40 m.
• the moving belt comprises a surface with a plurality of orifices.
• the orifices of a moving belt of a belt dryer can have any size and/or shape that the person skilled in the art deems appropriate.
• the orifices have a shape selected from the group consisting of round, oval, triangular, quadrangular, polygonal or a combination of at least two of these.
• the orifices preferably each have a size in the range of from 0.01 to 50 cm , more preferably from 0.1 to 20 cm 2 , more preferably from 0.3 to 15 cm 2 , most preferably from 0.5 to 10 cm 2 .
• the orifices are oriented in a regular manner to each other.
• a number of orifices in the moving belt is in the range of from 1 to 100 orifices per m , more
• the longitudinal housing comprises the moving belt to at least 50 %, or preferably to at least 70 %, or preferably to at least 90 % of a longitudinal extension of the moving belt.
• the moving belt is surrounded by the longitudinal housing at least over its total length and width with preferably one inlet and one outlet.
• the longitudinal extension is a length over which the moving belt extends in the longitudinal directions of the belt.
• the longitudinal extension is a length of an upper run of the conveyor belt.
• the belt dryer satisfies at least one, preferably all of the following conditions:
• the speed of the moving belt is in the range from 0.2 to 2 m/minute, or preferably in the range from 0.3 to 1.5 m/minute;
• the ratio of the longitudinal extension to the width of the moving belt is in the range from 5: 1 to 20.T , or preferably in the range from 7: 1 to 18: 1, or preferably in the range from 10: 1 to 15: 1 ;
• the moving belt is capable of moving the polymer gel in the range from 0.1 to 10 1 per hour, or preferably in the range from 0.5 to 9 t per hour, or preferably in the range from 1 to 8 t per hour.
• the dried polymer gel is ground thereby obtaining particulate water-absorbent polymer particles.
• the water-absorbent polymer particles in process step (ix) are characterized by a temperature in the range of from 15 to 50 °C, preferably from 20 to 45°C, more preferably from 25 to 40°C.
• any device can be used the person skilled in the art considers as appropriate for grinding the above described dried polymer gel and/or polymer gel particles.
• a suitable grinding device a single- or multistage roll mill, preferably a two- or three-stage roll mill, a pin mill, a hammer mill or a vibratory mill may be mentioned.
• the ground water- absorbent polymer particles are sized, preferably using appropriate sieves.
• the content of polymer particles having a particle size of less than 150 ⁇ is less than 10 wt.-%, preferably less than 8 wt.-% and particularly preferably less than 6 wt.-% and that the content of polymer particles having a particle size of more than 850 ⁇ is also less than 10 wt.-%, preferably less than 8 wt.-% and particularly preferably less than 6 wt.-%.
• water-absorbent polymer particles at least 30 wt.-%, more preferred at least 40 wt.-% and most preferred at least 50 wt.-% of the water-absorbent- polymer particles have a particle size in a range of from 300 to 600 ⁇ .
• a Si- oxide is added to the sized water-absorbent polymer particles.
• a preferred Si-oxide is Si0 2 .
• the Si-oxide is added to reduce a caking of the water-absorbent polymer particles.
• the water-absorbent polymer particles in process step during the adding of the Si-oxide have a temperature in the range of from 70 to 120°C, preferably from 75 to 1 15°C, more preferably from 80 to 1 10°C, more preferably from 80 to 105°C, most preferably from 80 to 100°C.
• the Si-oxide is mixed with the water-absorbent polymer particles in a Si mixing device.
• the Si mixing device is a disc mixer.
• a preferred disc mixer comprises at least 5, preferably at least 6, more preferably at least 7, more preferably at least 8, more preferably at least 9, more preferably at least 10, more preferably at least 15, most preferably at least 20, rotating discs.
• the Si-oxide is added to the sized water-absorbent polymer particles in an amount in the range of from 0.1 to 1 wt.-%, preferably from 0.2 to 0.8 wt.-%, more preferably from 0.3 to 0.5 wt.-%, based on the weight of the sized water-absorbent polymer particles.
• the Si-oxide added to the sized water-absorbent polymer particles is comprised by a plurality of particles, wherein the particles are characterized by
• the ground and sized water-absorbent polymer particles are contacted, preferably mixed, with a further crosslinker, thereby obtaining surface-crosslinked water-absorbent polymer particle.
• the further crosslinker is comprised by a crosslinking composition which comprises further components.
• the ground and sized water-absorbent polymer particles are heated after or simultaneously to or both the contacting, preferably for promoting a surface-crosslinking reaction.
• a preferred further crosslinker is a surface crosslinker.
• Preferred further crosslinkers are disclosed in US 201 1/0204288 Al and incorporated herein by reference and in the following.
• Preferred further crosslinkers are compounds which comprise groups which can form covalent bonds with at least two carboxylate groups of the polymer particles.
• Suitable compounds are, for example, polyfunctional amines, polyfunctional amido amines, poly- functional epoxides, as described in EP 0 083 022 A2, EP 0 543 303 Al and EP 0 937 736 A2, di- or polyfunctional alcohols, as described in DE 33 14 019 Al , DE 35 23 617 Al and EP 0 450 922A2, or ⁇ -hydroxyalkylamides, as described in DE 102 04 938 Al and U.S. Pat. No. 6,239,230.
• Suitable further crosslinkers are cyclic carbonates in DE 40 20 780 CI , 2-oxazolidinone and derivatives thereof, such as 2-hydroxyethyl-2- oxazolidinone, in DE 198 07 502 Al , bis- and poly-2-oxazolidinones in DE 198 07 992 CI , 2-oxotetrahydro-l,3-oxazine and derivatives thereof in DE 198 54 573 Al , N -acyl-2- oxazolidinones in DE 198 54 574 Al, cyclic ureas in DE 102 04 93 7 Al , bicyclic amido acetals in DE 103 34 584 Al , oxetanes and cyclic ureas in EP 1 199 327 A2 and mor- pholine-2,3-dione and derivatives thereof in WO 2003/031482 Al.
• 2-oxazolidinone and derivatives thereof such as 2-hydroxyethyl-2-
• Preferred further crosslinkers 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 further crosslinkers are 2-hydroxyethyl-2-oxazolidinone, 2- oxazolidinone and 1 ,3 -propanediol.
• further crosslinkers which comprise additional polymerizable ethylenically unsaturated groups, as described in DE 3713 601 Al .
• the amount of further crosslinker added is preferably in the range of from 0.001 to 2 wt.-%, more preferably from 0.02 to 1 wt.-% and most preferably from 0.05 to 0.2 wt.-%, based in each case on the sized water-absorbent polymer particles.
• polyvalent cations are applied to the surfaces of the sized water-absorbent polymer particles in addition to the further crosslinker before, during or after the contacting with the further crosslinker.
• the polyvalent cations usable 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 the cations of titanium and zirconium.
• Possible counterions are chloride, bromide, sulfate, hydrogensulfate, carbonate, hydrogencarbonate, nitrate, phosphate, hydrogenphos- phate, dihydrogenphosphate and carboxylate, such as acetate, citrate and lactate. Aluminium sulfate and aluminum lactate are preferred.
• polyamines are polyvalent cations.
• the amount of polyvalent cation used is, for example, 0.001 to 1.5 wt.-%, preferably 0.005 to 1 wt.-%, more preferably 0.02 to 0.8 wt.-%, based in each case on the sized water- absorbent polymer particles.
• the contacting with the further crosslinker is typically performed in such a way that the crosslinking composition, comprising the further crosslinker, is sprayed as a solution onto the sized water-absorbent polymer particles.
• a preferred further mixing device comprises moving mixing tools, such as a screw mixer, a disc mixer, and a paddle mixer.
• a preferred further mixing device is a horizontal mixer or a vertical mixer or both. Particularly preferred is a horizontal mixer.
• a mixer is horizontal if a mixing tool of the mixer rotates around a horizontal axis.
• a mixer is vertical if a mixing tool of the mixer rotates around a vertical axis.
• Suitable mixers are, for example, horizontal Ploughshare® Mixers (Gebriider Lodige Maschinenbau GmbH, Pader- born, Germany), Vrieco-Nauta continuous mixers (Hosokawa Micron BY, Doetinchem, the Netherlands), Processall Mixmill mixers (Processall Incorporated, Cincilmati, US), Schugi Flexomix® (Hosokawa Micron BY, Doetinchem, the Netherlands), and particularly preferred are ringlayer mixers CoriMix® by Gebriider Lodige Maschinenbau GmbH, Pader- born, Germany.
• the crosslinking composition is typically used in the form of an aqueous solution.
• the penetration depth of the crosslinking composition into the polymer particles can be adjusted via the content of non-aqueous solvent and total amount of solvent. If exclusively water is used as the solvent, a surfactant is preferably added. This improves the wetting behavior and reduces the tendency to form lumps. However, preference is given to using solvent mixtures, for example isopropanol/water, 1 ,3- propanediol/water and propylene glycol/water, where the mixing ratio in terms of mass is preferably from 20:80 to 40:60.
• a residence time of the polymer particles in the mixer is preferably from 10 to 120 minutes, more preferably from 10 to 90 minutes, most preferably from 30 to 60 minutes.
• the fill level of the mixer is preferably from 30 to 80 %, more preferably from 40 to 75 %, most preferably from 50 to 70 %.
• the fill level of the mixer can be adjusted via a height of an overflow weir.
• the crosslinking reaction which may have started prior to the drying, is finalized during the drying.
• the contacting with the crosslinking composition or the further crosslinker or both and preferably also the heating of the sized water- absorbent polymer particles are performed in a further mixing device.
• a particularly pre- ferred further mixing device is a High-performance Ringlayer CoriMix® CM 350 by Ge- brtider Lodige Mascheninenbau GmbH, Paderborn, Germany.
• contacting is a mixing by a plurality of contacts of at least a part of the sized water-absorbent polymer particles to a rotating component, wherein the mixing is per- formed for a duration in the range of from 0.1 to 60 seconds, preferably from 0.1 to 55 seconds, more preferably from 0.1 to 40 seconds, more preferably from 0.1 to 30 seconds, more preferably from 0.1 to 20 seconds, most preferably from 0.1 to 10 seconds.
• the contact of the sized water-absorbent polymer particles to the rotating component is preferably made a plurality of times during the duration of the mixing.
• a mixing shaft of the Si mixing device rotates during mixing at a first maximum speed and a mixing shaft of the further mixing device rotates during mixing at a second maximum speed, wherein the second maximum speed is more, preferably at least 10 rpm, more preferably at least 20 rpm, more preferably at least 30 rpm, more preferably at least 40 rpm, more preferably at least 50 rpm, more preferably at least 100 rpm, more preferably at least 120 rpm, more preferably at least 140 rpm, more preferably at least 160 rpm, more preferably at least 180 rpm, more preferably at least 200 rpm, more preferably at least 220 rpm, more preferably at least 240 rpm, more preferably at least 260 rpm, more preferably at least 280 rpm, more preferably at least 300 rpm, more prefera- bly at least 320 rpm, more preferably at least 340 rpm, more preferably at least 360 rpm, more
• the further mixing device comprises a rotating shaft and a plurality of mixing tools, wherein the mixing tools are connected to the rotating shaft, wherein during mixing the rotating shaft rotates at a speed in the range of from 500 to 1200 rpm, preferably from 550 to 1200 rpm, more preferably from 600 to 1200 rpm, more preferably from 650 to 1200 rpm, more preferably from 700 to 1200 rpm, more preferably from 750 to 1 150 rpm, more preferably from 800 to 1 100 rpm, more preferably from 850 to 1050 rpm, most preferably from 900 to 1000 rpm.
• the further mixing device comprises a plurality of mixing tools, wherein the mixing tools are rods or paddles or both.
• a preferred plurality of mixing tools comprises rods and paddles.
• the further mixing device comprises an annular layer of at least a part of the sized water-absorbent polymer particles.
• a preferred annular layer is shaped by a centrifugal force or a wall of a mixing chamber or preferably both.
• the preferred drying of the sized water-absorbent polymer particles is performed in a drying device, wherein the drying device comprises at least two rotating shafts.
• a preferred rotating shaft is horizontal.
• the least two rotating shafts are horizontal.
• the drying of the sized water-absorbent polymer particles is performed in a drying device, wherein the drying de- vice is a paddle mixer or a paddle dryer or both.
• a particularly preferred paddle dryer and paddle mixer is an Andritz Gouda Paddle Dryer, preferably of type GPWD12W120, by An- dritz AG, Graz, Austria.
• the crosslinking composition further comprises a reducing agent or a poly alkylene glycol or both.
• a preferred poly alkylene glycol is a poly ethylene glycol.
• a preferred poly ethylene glycol has a molecular weight in the range of from 50 to 1000, preferably from 150 to 750, more preferably from 200 to 500, most preferably from 350 to 450.
• the surface-crosslinked polymer particles are cooled prior to process step (xii) of the process according to the present invention.
• the cooling may be performed in any cooling device the person skilled in the art deems appropriate for cooling the surface- crosslinked water-absorbent polymer particles.
• the cooling device is chosen to effectively cool the surface-crosslinked water-absorbent polymer particles and to minimize a deterioration of a surface-crosslinked surface by for example abrasion.
• a chelating agent is added to the surface- crosslinked water-absorbent polymer particles, preferably in a fluidized bed.
• a preferred chelating agent is EDTA.
• the chelating agent is added as part of an aqueous solution.
• the chelating agent is added during cooling of the surface-crosslinked water-absorbent polymer particles.
• the chelating agent is added in an amount in the range of from 500 to 3,000 ppm by weight, preferably from 1 ,000 to 2,000 ppm by weight, based on the weight of the surface-crosslinked water-absorbent polymer particles.
• a molecule of the chelating agent comprises at least two, preferably at least four, active sides.
• the chelating agent is a salt.
• a preferred salt is an alkali metal salt.
• the cooling of the surface-crosslinked water-absorbent polymer particles is performed in a cooling device; wherein the cooling device comprises a fluidized bed of the surface-crosslinked water-absorbent polymer particles.
• the cooling device comprises a fluidized bed of the surface-crosslinked water-absorbent polymer particles.
• an in- gas-stream enters the cooling device and an out-gas-stream exits the cooling device, wherein the in-gas-stream comprises less Si-oxide than the out-gas-stream.
• a preferred out- gas-stream is directed upwards.
• the out-gas-stream is an air-stream.
• the out-gas-stream comprises the Si-oxide in an amount in the range of from 10 to 30 wt.-%, preferably from 15 to 25 wt.-%, based on the weight of a Si-oxide content of the surface-crosslinked water-absorbent polymer particles prior to the cooling.
• the Si-oxide comprised by the out-gas-stream is comprised by particles, wherein at least 50 wt.-%, preferably at least 60 wt.-%, more preferably at least 70 wt.-%, of the particles have a particle size of less than 1 ⁇ , preferably less than 0.9 ⁇ , more preferably less than 0.8 ⁇ , most preferably less than 0.7 ⁇ .
• the surface- crosslinked water-absorbent polymer particles are contacted with water during cooling.
• a preferred contacting is a spraying water onto or into or both the fluidized bed.
• the surface-crosslinked water-absorbent polymer particles are contacted with the water for remoisturizing.
• the contacting for remoisturizing is preferably performed at 30 to 80°C, more preferably at 35 to 70°C, most preferably at 40 to 60°C.
• the amount of water used for remoisturizing is preferably from 1 to 10 wt.-%, more preferably from 2 to 8 wt.-% and most preferably from 3 to 5 wt.-%, based on the weight of the surface-crosslinked water-absorbent polymer particles.
• the remoisturizing preferably increases the mechanical stability of the polymer particles and reduces their tendency to static charging.
• the surface-crosslinked water-absorbent polymer parti- cles can be coated.
• Suitable coatings for improving the swell 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 for counteracting the undesired caking tendency of the polymer particles are, for example, fumed silica, such as Aerosil® 200, and surfactants, such as Span® 20.
• the surface-crosslinked water-absorbing polymer particles produced by the process according to the invention have a moisture content of preferably 0 to 15 wt.-%, more preferably 0.2 to 10 wt.-% and most preferably 0.5 to 8 wt- %.
• the surface-crosslinked water-absorbent polymer particles are sized , preferably using appropriate sieves such as for example one selected from the group consisting of a tumbler sieve, a vibrating sieve, and a tilted sieve, or a combination of at least two thereof.
• the sized surface-crosslinked water-absorbent polymer particles are contacted, preferably mixed, with Ag-zeolite particles in an amount in the range from 100 to 5000 wt.-ppm, based on the total weight of the sized surface cross-linked water-absorbent polymer particles, thereby obtaining post- treated surface-crosslinked water-absorbent polymer particles.
• the Ag-zeolite particles can be any zeolite particles comprising Ag the person skilled in the art would select for odor control in applications of the surface-crosslinked water- absorbent polymer particles of the invention, such as applications in female care, baby care or adult care products. Preferably, further zeolites are added. According to a definition of the International Meneralogical Association (D. S.
• a zeolite is a crystalline substance selected from the group of aluminium silicates with the general structure: M x /n[A10 2 ) x (Si0 2 ) y ] * H 2 0 wherein x, y and n can be any natural number from 1 to 1000.
• M x can be any metal.
• M x is selected from the group consisting of Na, K, Li, ST, Mg, Cu, Zn, Fe, Ag, Au, Pt, Pd or a combination of at least two thereof.
• the metal M is Ag, Zn, Na or a combination of at least two thereof.
• the ratio of Si/Al is in the range from 1 to 300, or preferably in the range from 1 to 250, or preferably in the ration from 1 to 100.
• Preferred zeolite particles are selected from the group consisting of mordenite, anal- cime, brewsterite, chabazite, clinoptilolite, darciadite, erionite, faujastite, ferrierite, gmelin- ite, heulandite, levyne, natrolite, paulingite, phillipsite and stilbite or a combination of at least two thereof, in accordance with the list of zeolite species of the International Minera- logical Association (D. S. Coombs et al., Canadian Mineralogist, 35, 1979, 1571-1606).
• a preferred Ag-zeolite provides the structure (Ag, Zn, Na)i 2 [A10 2 )(Si0 2 )] 12 * H 2 0.
• the particle size of the Ag-zeolite preferably lies in the range from 1.5 to 4 ⁇ , or preferably in the range from 1.8 to 3.8 ⁇ , or preferably in the range from 2 to 3.5 ⁇ .
• the zeolite, especially the Ag-zeolite preferably provides a bulk density in the range from 0.35
• process step (xiii) the contacting is performed utilizing a particle mixing device
• the particle mixing device comprises
• PSAP first gas pressure
• the further volume is fluid-conductively connected to the first volume
• first gas pressure PSAP
• further gas pressure PAPgz
• a preferred first volume is a transmission line.
• a preferred further volume is a transmission line.
• a preferred transmission line is pipeline or a tube or both.
• the first stream at least partly surrounds the further stream.
• the further stream is directed into to first stream.
• the sized surface-crosslinked water-absorbent poly- mer particles of the first stream and the Ag-zeolite particles are mixed in the particle mixing device.
• the particle mixing device comprises no mixing tool, preferably no rotating mixing tool.
• the further stream is driven by a difference between the first gas pressure and the further gas pressure.
• the first gas pressure is less than the fur- ther gas pressure due to the Bernoulli Effect.
• the particle mixing device utilizes the Bernoulli Effect for mixing the at least portion of the sized surface-crosslinked water- asbirbent polymer particles of the first stream and the Ag-zeolite particles of the further stream.
• the post-treated surface-crosslinked water- absorbent polymer particles comprise the Ag-zeolite particles in an amount in the range from 0.01 to 0.5 wt.-%, preferably in the range from 0.05 to 0.45 wt.-%, more preferably in the range from 0.1 to 0.4 wt.-%, based on the post-treated surface-crosslinked water- absorbent polymer particles
• the Ag-zeolite particles have an Ag content in the range from 0.1 to 5 wt.-%, preferably in the range from 0.15 to 4.5 wt.-%, more preferably in the range from 0.2 to 4 wt.-%, based on the total weight of the Ag-zeolite particles
• the Ag-zeolite particles fulfil at least one, preferably two, more preferably all, of the following criteria:
• a preferred average particle size is a weight-average particle size.
• Preferred combinations of the above criteria fulfilled by the Ag-zeolite particles are a)b), a)c), b)c), and a)b)c).
• the Ag-zeolite particles further comprise Zn or Na or both.
• the Zn is comprises by the Ag-zeolite particles in an amount in the range from 0.05 to 3 wt.-%, preferably in the range from 0.1 to 2.8 wt.-%, more preferably in the range from 0.15 to 2.7 wt.-%, based on the total weight of the Ag-zeolite particles.
• the Na is comprises by the Ag-zeolite particles in an amount in the range from 0.05 to 10 wt.-%, preferably in the range from 0.1 to 8 wt.-%, more preferably in the range from 0.2 to 7 wt.-%, based on the total weight of the Ag-zeolite particles.
• process step (xi) further comprises heating the ground and sized water-absorbent polymer particles to a temperature in the range from 100 to 200 °C, preferably from 105 to 190°C, more preferably from 110 to 180°C, more preferably from 120 to 170°C, most preferably from 130 to 160°C.
• process step (xiii) the contacting further comprises:
• a weight of the first portion of the sized surface-crosslinked water-absorbent polymer particles is less than a weight of the further portion of the sized surface-crosslinked water-absorbent polymer particles.
• the first portion of the sized surface-crosslinked water-absorbent polymer particles comprising the Ag-zeolite particles is generated in the particle mixing device.
• the further portion of the sized surface- crosslinked water-absorbent polymer particles comprises Ag-zeolite particles in an amount which is less than 0.5 wt.-%, preferably less than 0.1 wt.-%, more preferably less than 0.005 wt.-%, based on the total weight of the further portion of the sized surface-crosslinked water-absorbent polymer particles.
• the mixing of the first portion of the sized surface-crosslinked water-absorbent polymer particles and the further portion of the sized surface-crosslinked water-absorbent polymer particles is performed in the particle mixing device.
• the polymerization in step (vi) is performed in presence of a blowing agent.
• the blowing agent may be added to the aqueous monomer solution in one selected from the group consisting of step (i), step (ii), step (iii), step (iv), step (v), and step (vi), or in a combination of at least two thereof.
• the blowing agent is added to the monomer solution in step (i).
• the blowing agent should be added prior or immediately after the polymerization in step (vi) is initiated.
• the blowing agent is added to the monomer solution immediately after or simultaneously to adding the initiator or a component of an initiator system to the monomer solution.
• the blowing agent is added to the monomer solution in an amount in the range of from 500 to 4000 ppm by weight, preferably from 1000 to 3500 ppm by weight, more preferably from 1500 to 3200 ppm by weight, most preferably from 2000 to 3000 ppm by weight, based on the total weight of the monomer solution.
• a blowing agent is a substance which is capable of producing a cellular structure or pores or both via a foaming process during polymerization of the monomers.
• the foaming process is preferably endothermic.
• a preferred endothermic foaming process is started by heat from an exothermic polymerisation or crosslinking or both reaction.
• a preferred blowing agent is a physical blowing agent or a chemical blowing agent or both.
• a preferred physical blowing agent is one selected from the group consisting of a CFC, a HCFC, a hy- drocarbon, and C0 2 , or a combination of at least two thereof.
• a preferred C0 2 is liquid C0 2 .
• a preferred hydrocarbon is one selected from the group consisting of pentane, isopentane, and cyclopentane, or a combination of at least two thereof.
• a preferred chemical blowing agent is one selected from the group consisting of a carbonate blowing agent, a nitrite, a peroxide, calcined soda, an oxalic acid derivative, an aromatic azo compound, a hydrazine, an azide, a ⁇ , ⁇ '- Dinitrosoamide, and an organic blowing agent, or a combination of at least two thereof.
• a very particularly preferred blowing agent is a carbonate blowing agent.
• Carbonate blowing agents which may be used according to the invention are disclosed in US 5, 118, 719 A, and are incorporated herein by reference.
• a preferred carbonate blowing agent is a carbonate containing salt, or a bicarbonate containing salt, or both.
• Another preferred carbonate blowing agent comprises one selected from the group consisting of C0 2 as a gas, C0 2 as a solid, ethylene carbonate, sodium carbonate, potassium carbonate, ammonium carbonate, magnesium carbonate, or magnesium hydroxic carbonate, calcium carbonate, barium carbonate, a bicarbonate, a hydrate of these, other cations, and naturally occurring carbonates, or a combination of at least two thereof.
• a preferred naturally occurring carbonate is dolomite.
• the above mentioned carbonate blowing agents release C0 2 when being heated while dissolved or dispersed in the monomer solution.
• a particularly preferred carbonate blowing agent is MgC0 3 , which may also be represented by the formula (MgC0 3 ) 4 -Mg(OH) 2 -5-H 2 0.
• Another preferred carbonate blowing agent is agent is (NH 4 ) 2 C0 3 .
• the MgC0 3 and (NH ) 2 C0 3 may also be used in mixtures.
• Preferred carbonate blowing agents are carbonate salts of multivalent cations, such as Mg, Ca, Zn, and the like.
• Examples of such carbonate blowing agents are Na 2 C0 3 , K 2 C0 3 , (NH 4 ) 2 C0 3 , MgC0 3 , CaC0 3 , NaHC0 3 , KHC0 3 , NH 4 HC0 3 , Mg(HC0 3 ) 2 , Ca(HC0 3 ) 2 , ZnC0 3 , and BaC0 3 .
• other multivalent cations such as Ni, Ba, Cd, Hg would be unacceptable because of potential toxic or skin sensitizing effects.
• a preferred nitrite is ammonium nitrite.
• a preferred peroxide is hydrogen peroxide.
• a preferred aromatic azo compound is one selected from the group consisting of a triazene, arylazosulfones, arylazotriarylmethanes, a hydrazo compound, a diazoether, and diazoami- nobenzene, or a combination of at least two thereof.
• a preferred hydrazine is phenylhydra- zine.
• a preferred azide is a carbonyl azide or a sulfonyl azide or both.
• a preferred ⁇ , ⁇ '- Dinitrosoamide is ,N'-dimethyl-N,N'-dinitrosoterephthalamide.
• the blowing agent is C0 2 or a carbonate, preferably a bicarbonate, which is added to the monomer solution.
• Another preferred blow- ing agent is one selected from the group consisting of C0 2 as a gas, C0 2 as a solid, ethylene carbonate, sodium carbonate, potassium carbonate, ammonium carbonate, magnesium carbonate, magnesium hydroxy carbonate, calcium carbonate, barium carbonate, a bicarbonate, a hydrate of these, other cations, and naturally occurring carbonates, or a combination of at least two thereof.
• the polymer gel being discharged in process step (vii) is a polymer gel sheet; wherein the polymer gel sheet is characterized by a thickness in the range of from 10 to 200 mm, preferably from 10 to 100 mm, more preferably from 15 to 75 mm, most preferably from 15 to 50 mm.
• the polymer gel being discharged in process step (vii) is a polymer gel sheet; wherein the polymer gel sheet is characterized by a width in the range of from 30 to 300 cm, preferably from 50 to 250 cm, more preferably from 60 to 200 cm, most preferably from 80 to 100 cm.
• a device for the preparation of post-treated surface-crosslinked water-absorbent polymer particles in a process stream comprising
• a first container designed to take an aqueous monomer solution, comprising at least one partially neutralized, monoethylenically unsaturated monomer bearing carboxylic acid groups (a 1);
• ii) is designed to comprise the aqueous monomer solution and the at least one crosslinker (a3) during polymerizing the monomers in the aqueous monomer solution, thereby obtaining a polymer gel with a water content in the range from 40 to 60 wt.-% , preferably from 50 to 60 wt.-%, more preferably from 53 to 56 wt.-%, based on the total weight of the polymer gel;
• i) is located down-stream to the polymerization reactor, ii) is designed to comminute the polymer gel;
• ii) designed to dry the polymer gel to a water content in the range from 0.5 to 25 wt.-%, preferably from 1 to 10 wt.-%, more preferably from 3 to 7 wt.-%, based on the total weight of the dried polymer gel;
• ii) designed to be utilized in contacting the sized surface-crosslinked water-absorbent polymer particles with Ag-zeolite particles in an amount in the range from 100 to 5000 wt.-ppm, preferably from 500 to 4500 wt.-ppm, more preferably from 1000 to 4500 wt.-ppm, more preferably from 1500 to 4500 wt.-ppm, more preferably from 2000 to 4000 wt.-ppm, most preferably from 2500 to 3500 wt.-ppm, based on the total weight of the sized surface cross-linked water-absorbent polymer particles, thereby obtaining post-treated surface-crosslinked water- absorbent polymer particles.
• Preferred components or devices or both of the device for the preparation of post- treated surface-crosslinked water-absorbent polymer particles according to the invention are designed according to the process according to the invention.
• Preferred Ag-zeolite particles are Ag-zeolite particles according to the process according to the invention.
• a preferred particle mixing device is the particle mixing device according to the process according to the invention.
• a preferred contacting the sized surface-crosslinked water-absorbent polymer particles with Ag-zeolite particles is such a contacting according to the process according to the invention.
• a contribution to the solution of at least one of the above objects is provided by a process for the preparation of post-treated surface-crosslinked water-absorbent polymer particles in the device according to the invention.
• the process comprises the process steps (i) to (xiii) according to the invention.
• a contribution to the solution of at least one of the above objects is provided by a post-treated surface-crosslinked water-absorbent polymer particle, obtainable by the process according to the invention.
• a contribution to the solution of at least one of the above objects is provided by a plurality of post-treated surface-crosslinked water-absorbent polymer particles, comprising Ag- zeolite particles in an amount in the range from 0.001 to 1 wt.-%, preferably in the range from 0.01 to 0.5 wt.-5, more preferably in the range from 0.05 to 0.45 wt.-%, more preferably in the range from 0.1 to 0.45 wt.-%, more preferably in the range from 0.15 to 0.45 w - %, more preferably in the range from 0.2 to 0.45 wt.-%, most preferably in the range from 0.25 to 0.35 wt.-%, based on the total weight of the plurality of post-treated surface- crosslinked water-absorbent polymer particles.
• a Si0 2 in an amount in the range of from 500 to 3,000 ppm by weight, preferably from 1 ,000 to 2,000 ppm by weight;
• a contribution to the solution of at least one of the above objects is provided by a composite material comprising the post-treated surface-crosslinked water-absorbent polymer particle according to the invention, or the plurality of post-treated surface-crosslinked water-absorbent polymer particles according to the invention.
• the composite material according to the invention comprises one selected from the group consisting of a foam, a shaped article, a fibre, a foil, a film, a cable, a sealing material, a liquid-absorbing hygiene article, a carrier for plant and fungal growth-regulating agents, a packaging material, a soil additive, and a building material, or a combination of at least two thereof.
• a preferred cable is a blue water cable.
• a preferred liquid-absorbing hygiene article is one selected from the group consisting of a diaper, a tampon, and a sanitary towel, or a combination of at least two thereof.
• a preferred diaper is a baby's diaper or a diaper for incontinent adults or both.
• a contribution to the solution of at least one of the above objects is provided by a process for the production of a composite material, wherein the post-treated surface- crosslinked water-absorbent polymer particle according to the invention, or the plurality of post-treated surface-crosslinked water-absorbent polymer particles according to the invention, and a substrate, and optionally an auxiliary substance are brought into contact with one another
• a contribution to the solution of at least one of the above objects is provided by a composite material obtainable by a process according to the invention.
• a contribution to the solution of at least one of the above objects is provided by a use of the post-treated surface-crosslinked water-absorbent polymer particle according to the invention, or the plurality of post-treated surface-crosslinked water-absorbent polymer particles according to the invention in a foam, a shaped article, a fibre, a foil, a film, a cable, a sealing material, a liquid- absorbing hygiene article, a carrier for plant and fungal growth- regulating agents, a packaging material, a soil additive, for controlled release of an active compound, or in a building material.
• test methods are used in the invention.
• the ISO test method for the feature to be measured being closest to the earliest filing date of the present application applies. If no ISO test method is available, the ED ANA test method being closest to the earliest filing date of the present application applies.
• standard ambient temperature and pressure (SATP) as a temperature of 298.15 K (25 °C, 77 °F) and an absolute pressure of 100 kPa (14.504 psi, 0.986 atm) apply.
• SATP standard ambient temperature and pressure
• the water content is determined according to the Karl Fischer method. odor control
• a sample of about 0.5 g of the surface-crosslinked water-absorbent polymer particles are combined with about 30 ml of urine.
• a sniff-test panel of five individuals tests the urine-comprising samples by sniffing and rating the sample on a scale from 1 to 10. An average scale value is calculated over the test panel for each sample. In rating, particular attention is paid to malodors associated with urine and urine degradation. The stronger such malodors are found, the lower the sample is rated on the scale, thus the worse is the odor control of the sample.
• the specific surface area is measured using N 2 according to ISO 9277.
• 0.4299 wt.-parts of water are mixed in an adequate container with 0.27 wt.-parts of acrylic acid and 0.0001 wt.-parts of mono methyl ether hydroquinone (MEHQ).
• 0.2 wt.- parts of an aqueous 48 wt.-% sodium hydroxide solution are added to the mixture.
• a so- dium-acrylate monomer solution with a neutralization ratio of 70 mol-% is achieved.
• the sodium-acrylate monomer solution is degased with nitrogen.
• 1 wt.-part of the monomer solution prepared in step A) is mixed with 0.001 wt.-parts of trimethylol propane triacrylate as crosslinker, 0.001 wt.-parts of sodium peroxodisulfate as first initiator component, 0.000034 wt.-parts of 2,2-dimethoxy-l,2-diphenylethan-l-one (Ciba® Irgacure® 651 by Ciba Specialty Chemicals Inc., Basel, Switzerland) as a second initiator component, up to 0.1 wt.-parts of acrylic acid particles (with a particle size of less than ' 150 ⁇ ) in a container to achieve a mixed solution.
• Ciba® Irgacure® 651 by Ciba Specialty Chemicals Inc.
• sodium carbonate is added to the mixed solution in an amount of 0.1 wt.-part based on the total amount of the mixed solution immediately after adding the second initiator component.
• a sufficient amount of the mixed solution is subjected to further treatment in order to obtain a polymer gel and further downstream water-absorbent polymer particles and further downstream surface-crosslinked water-absorbent polymer particles and further downstream, post-treated surfrace-crosslinked water-absorbent polymer particles. Details of the further treatment are given below.
• the conveyor belt has a length of at least 20 m and a width of 0.8 m.
• the conveyor belt is formed as a trough to keep the solution on the belt prior to and while being polymerized.
• the dimensions of the conveyor belt and the conveying speed of the conveyer belt are selected in a way that a poly-acrylic acid gel is formed at a downstream end of the belt.
• a water- absorbent polymer gel is achieved.
• the polymer gel has a water content of about 52 wt.-%, based on the total weight of the polymer gel.
• the polymer gel forms a polymer gel strand which is discharged from the conveyor belt and comminuted in three steps:
• the rubbery poly-acrylic acid gel is cut into flat gel strips by a knife.
• the gel strips have a length in the range of from 10 to 20 cm, a height in the range of from 10 to 20 mm, and a width in the range of from 10 to 200 mm, then
• a breaker is used to shred the strips into gel pieces having a length in the range from 5 to 50 mm, a height in the range of from 3 to 20 mm, and a width in the range of from 3 to
• the gel pieces are extruded through a mixer with a grinder to mince the gel pieces obtaining gel pieces having a length in the range of from 3 to 20 mm a height in the range of from 3 to 20 mm and a width in the range of from 3 to less than 20 mm.
• the comminuted gel is dried in a belt dryer at a temperature of 180 °C to a water content of 5 wt.-% based on the dried polymer gel.
• the belt of the belt drier provides orifices, where hot air is pressed into the polymer gel via nozzles. Additionally hot air is blown from above the belt onto the gel.
• the dried polymer gel is ground in three steps. First the dried polymer gel is fed through a Herbold Granulator HGM 60/145 (HERBOLD Meckesheim GmbH) and the achieved parts of the dried polymer gel have a size of less than 7 mm and are then kept for 2.5 hours in a container to equalize the humidity content of the polymer gel parts. The dried polymer gel parts are then milled in a roller mill of Bauerffle Type 350.1 x 1800 (3- stage crusher) (Bauermeister Zerklein mecanicstechnik GmbH) to obtain water-absorbent polymer particles having a particle size of less than 1 mm.
• the water absorbent polymer particles are sieved with a tumbler sieves having several screens.
• the mesh sizes of the screens change from 20, 30, 40, 50, 60 to 100 U.S. -mesh.
• At least 50 wt.-% of the obtained water-absorbent polymer particles have a particles size in the range of from 300 to 600 ⁇ .
• Less than 5 wt.-% of the water-absorbent polymer particles of the examples according to the invention are smaller than 150 ⁇ , less than 5 wt.-% of the water-absorbent polymer particles of the examples according to the invention are have a particle size of more than 850 ⁇ .
• the obtained water-absorbent polymer particles are named precursor I. E) Silicon dioxide treatment
• the precursor I is mixed in a disc mixer with silicon dioxide (Si0 2 ) in form of Sipernat ® 22 obtainable from Evonik Industries AG, Essen, Germany.
• Si0 2 silicon dioxide
• the precursor still has a temperature in the range of from 80 °C to 100 °C.
• a precursor II is obtained.
• 0.4 wt.-% of Si0 2 based on the weight of the precursor I are mixed with the precursor I.
• wt.-part of the precursor II is mixed with 0.003 wt.-part (+-10 %) of a surface crosslinker, based on the total weight of the mixture of precursor II and crosslinker.
• the surface crosslinker is composed of 19 wt.-% water, 40 wt.-% ethylene glycol diglycidyl ether, 1 wt.-% Na 2 S0 3 , 40 wt.-% poly ethylene glycol with a molecular weight of 400 g/mol, each based on the total amount of the crosslinker.
• the ingredients of the crosslinker are mixed in a line static mixer.
• the crosslinker is mixed in a ringlayer mixer CoriMix ® CM 350 (Gebruder Lodige Mascheninenbau GmbH, Paderborn, Germany) as shown schematically in figures 8a) and 8b) with precursor II.
• the mixture is heated to a temperature in the range of from 130 to 160 °C.
• the mixture is then dried in a paddle dryer Andritz Gouda Paddle Dryer, preferably of type GPWD12W120, by Andritz AG, Graz, Austria for 45 minutes at a temperature in the range of from 130 to 160°C.
• Surface-cross-linked absorbent polymer particles are obtained.
• a cooling device In a cooling device the temperature of the surface-cross-linked absorbent polymer particles is decreased to below 60 °C, obtaining cooled surface-cross-linked absorbent polymer particles referred as to precursor III.
• a gas propelled fluidized bed cooler which is commercially available by Daesung Industrial Co. Ltd., Korea is used as the cooling device.
• a chelating agent is added to the polymer particles during cooling. 1 ,500 ppm by weight, based on the precursor III, of Na 2 -EDTA are added to the precursor III.
• the mixture is sieved.
• the sieve is selected to separate agglomerates of the cooled surface-cross-linked absorbent polymer particle having a particle size of more than 850 ⁇ ⁇ .
• At least 50 wt.-% of the surface-crosslined absorbent polymer particles have a particles size in the range of from 300 to 600 ⁇ .
• Less than 5 wt.-% of the surface-crosslinked absorbent polymer particles of the examples according to the invention are smaller than 150 ⁇ , less than 5 wt.-% of the surface-crosslinked absorbent polymer particles of the examples according to the invention are have a particle size of more than 850 ⁇ .
• wt.-part of the sized precursor III is then subjected to mixing with Ag-zeolite.
• the amount of the Ag-zeolite is given in table 1 in wt.-ppm based on the total weight of the sized precursor III.
• the mixing with the Ag-zeolite is performed in the mixing device specified in table 1. Post treated surface-crosslinked water-absorbent polymer particles are obtained.
• Table 1 Ag-zeolite mixing efficiency, amount of fine particles produced by the process and odor control of the post-treated surface-crosslinked water-absorbent polymer particles depending on the amount of Ag-zeolite mixed with the surface-crosslinked water-absorbent polymer particles in a mixing device.
• FIG. 1 shows a flow chart diagram depicting the steps 101 to 1 13 of a process 100 for the preparation of post-treated surface-crosslinked water-absorbent polymer particles 504 according to the invention.
• aqueous monomer solution comprising at least one partially neutralized, monoethylenically unsaturated monomer bearing carboxylic acid groups ( l) and at least one crosslinker (a3) is provided.
• the aqueous monomer solution is an aqueous solution of partially neutralized acrylic acid, further comprising crosslinkers.
• fine particles of a water-absorbent polymer may be added to the aqueous monomer solution.
• a polymerization initiator or at least one component of a polymerization initiator system that comprises two or more components is added to the aqueous monomer solution.
• a blowing agent is added to the aqueous monomer solution in an amount of 3000 ppm by weight, based on the total weight of the monoethylenically unsaturated monomers.
• the oxygen content of the aqueous monomer solution is decreased by bubbling nitrogen into the aqueous monomer solution.
• the monomer solution is charged onto a belt of a polymerization belt reactor as a polymerization reactor 704. The belt is an endless conveyor belt.
• the aqueous monomer solution is polymerized to a polymer gel having a water content of about 55 wt.-% based on the weight of the polymer gel.
• a seventh step 107 the polymer gel is discharged from the belt. Subsequently, the polymer gel is comminuted, whereby polymer gel particles are obtained.
• the polymer gel particles are charged onto a belt of a belt dryer 706 and subsequently dried at a temperature of about 180°C. The dried polymer gel particles have a water content of about 5 wt.-% based on the total weight of the dried polymer gel particles. The dried polymer gel particles are discharged from the belt dryer 706 and subsequently in a ninth step 109 ground to obtain water-absorbent polymer particles.
• a tenth step 110 the water-absorbent polymer particles are sized to obtain sized water-absorbent polymer particles 501 having a well defined particle size distribution.
• a crosslinking composition comprising a further crosslinker 505 is added to the sized water-absorbent polymer particles 501 and the sized water-absorbent polymer particles 501 are heated. A portion of the heated water-absorbent polymer particles comprises partially surface-crosslinked surfaces. The heated water-absorbent polymer particles are dried, thereby finalizing a surface-crosslinking reaction and obtaining surface-crosslinked water-absorbent polymer particles 502.
• the surface-crosslinked water-absorbent polymer particles 502 are cooled in a fluidized bed of the surface-crosslinked water- absorbent polymer particles 502.
• the sur- face-crosslinked water-absorbent polymer particles 502 are sized using an appropriate sieve.
• the sized surface-crosslinked water-absorbent polymer particles 503 are mixed with Ag-zeolite particles 508 in an amount of 3000 wt.-ppm, based on the total weight of the sized surface cross-linked water-absorbent polymer particles 503, thereby obtaining post-treated surface-crosslinked water-absorbent polymer particles 504.
• Figure 2 shows a flow chart diagram depicting the steps 101 to 1 13 of a process 100 for the preparation of post-treated surface-crosslinked water-absorbent polymer particles 504 according to the invention.
• the process 100 shown in figure 2 is the same as the process 100 in figure 1 , wherein the third process step 103 and the fourth process step 104 overlap in time. While the polymerization initiator is added to the aqueous monomer solution, nitrogen is bubbled into the aqueous monomer solution in order to decrease its oxygen content.
• Figure 3 shows a flow chart diagram depicting the steps 101 , 103, 105 to 1 13 of a process 100 for the preparation of post-treated surface-crosslinked water-absorbent polymer parti - cles 504 according to the invention.
• the process 100 shown in figure 3 is the same as the process 100 in figure 1 , wherein the optional second step 102, the optional fourth step 104 are not part of the process 100 according to figure 3.
• Figure 4 shows a scheme of a particle mixing device 400 according to the invention.
• the particle mixing device 400 is used to mix a portion of the sized surface-crosslinked water- absorbent polymer particles 503 with Ag-zeolite particles 508, thereby generating a first portion 601 of sized surface-crosslinked water-absorbent polymer particles 503 having a content of Ag-zeolite particles 508 which is more than a content of Ag-zeolite particles 508 in a further portion 602 according to the invention.
• the particle mixing device 400 com- prises a first volume 401 , comprising a first stream 402 of a portion of the sized surface- crosslinked water-absorbent polymer particles 503 in an atmosphere of air having a first gas pressure PSAP-
• the particle mixing device 400 further comprises a further volume 403, comprising a further stream 404 of Ag-zeolite particles 508 in an atmosphere of air having a further gas pressure pA g z- Therein, the further volume 403 is fluid-conductively connected to the first volume 401.
• the first volume 401 is a tube conducting the portion of the sized surface-crosslinked water-absorbent polymer particles 503.
• the further volume 403 is another tube having a smaller diameter and conducting into a centre of the tube which is the first volume 401. Therefor, the further stream 404 is conducted into the first stream 402. A movement of the Ag-zeolite particles 508 is driven by a pressure difference.
• the first gas pressure PSAP is less than the further gas pressure pA g z- This pressure difference is caused by the Bernoulli Effect.
• FIG. 5 shows a flow chart diagram depicting the process steps (xi) to (xiii) of a process 100 according to the invention.
• Sized water-absorbent polymer particles 501 are mixed with a crosslinking composition, comprising a further crosslinker 505. The mixing is performed in the further mixing device 709 shown in the figures 8a) and 8b) below.
• the sized water- absorbent polymer particles 501 are heated in said further mixing device 709, thereby starting a surface-crosslinking reaction.
• the sized water-absorbent polymer particles 501 are dried and the surface-crosslinking reaction is finalized.
• Surface-crosslinked water-absorbent polymer particles 502 are obtained.
• the surface-crosslinked water- absorbent polymer particles 502 are sieved by a tumbler sieve, thereby separating fine surface-crosslinked water-absorbent polymer particles 506 and oversized surface-crosslinked water-absorbent polymer particles 507 from the surface-crosslinked water-absorbent polymer particles 502. Sized surface-crosslinked water-absorbent polymer particles 503 having a well defined particle size distribution are obtained.
• the sized surface-crosslinked water- absorbent polymer particles 503 are mixed with Ag-zeolite particles 508 in an amount of 2500 wt.-ppm, based on the total weight of the sized surface cross-linked water-absorbent polymer particles 503, thereby obtaining post-treated surface-crosslinked water-absorbent polymer particles 504.
• Figure 6 shows a flow chart diagram depicting the process steps (xi) to (xiii) of another process 100 according to the invention.
• Sized water-absorbent polymer particles 501 are mixed with a crosslinking composition, comprising a further crosslinker 505 and a reducing agent. The mixing is performed in the further mixing device 709 shown in the figures 8a) and 8b) below.
• the sized water-absorbent polymer particles 501 are heated in said further mixing device 709, thereby starting a surface-crosslinking reaction. Subsequently, the sized water-absorbent polymer particles 501 are dried and the surface-crosslinking reaction is finalized. Surface-crosslinked water-absorbent polymer particles 502 are obtained. The sur- face-crosslinked water-absorbent polymer particles 502 are cooled in a fluidized bed cooler. During cooling water and a chelating agent are added to the surface-crosslinked water- absorbent polymer particles 502.
• the surface-crosslinked water-absorbent polymer particles 502 are sieved by a vibrating sieve, thereby separating fine surface- crosslinked water-absorbent polymer particles 506 and oversized surface-crosslinked water- absorbent polymer particles 507 from the surface-crosslinked water- absorbent polymer par- tides 502. Sized surface-crosslinked water-absorbent polymer particles 503 having a well defined particle size distribution are obtained. The sized surface-crosslinked water- absorbent polymer particles 503 are divided into two portions. By mixing with with Ag- zeolite particles 508 a first portion 601 is generated. Said mixing is performed in the particle mixing device 400 shown in figure 4. A further portion 602 does not comprise Ag-zeolite particles 508.
• the first portion 601 and the further portion 602 are mixed, thereby obtaining post-treated surface-crosslinked water-absorbent polymer particles 504 having an Ag-zeolite particle 508 content of about 0.299 wt.-%, based on the post-treated surface-crosslinked water-absorbent polymer particles 504.
• the sized surface- crosslinked water-absorbent polymer particles 503 have been mixed with Ag-zeolite parti- cles 508 in an amount of 3000 wt.-ppm, based on the total weight of the sized surface cross- linked water-absorbent polymer particles 503.
• Figure 7 shows a block diagram of a device 700 for the preparation of post-treated surface- crosslinked water-absorbent polymer particles 504 according to the invention.
• the arrows show a direction of a process stream 71 1 of the preparation of post-treated surface- crosslinked water-absorbent polymer particles 504.
• the device 700 comprises a first container 701 , a further container 702, downstream a first mixing device 703, downstream a polymerization reactor 704, downstream a comminuting device 705, downstream a belt dryer 706, downstream a grinding device 707, downstream a first sizing device 708, down- stream a further mixing device 709, downstream a further sizing device 710 and downstream a particle mixing device 400 each according to the invention.
• Figure 8a shows a scheme of a longitudinal cross section of a further mixing device 709 according to the invention.
• the further mixing device 709 comprises an inlet 801 , a mixing chamber 802 which is limited by a mixing chamber wall 803, and an outlet 804.
• the sized water- absorbent polymer particles 501 are fed via the inlet 801 into the mixing chamber 802.
• a rotating shaft 807 with mixing tools 808 (not shown in figure 8a)) rotate at a speed in the range of from 500 to 1200 rpm. Due to a centrifugal force the polymer particles distribute over the mixing chamber wall 803, thereby forming an annular layer 805 of the sized water-absorbent polymer particles 501.
• FIG 8b A cross section at the axial position 806 of the mixing chamber 802 is shown in figure 8b).
• the further mixing device 709 is a high- performance ringlayer mixer CoriMix® CM 350 by Gebriider Lodige Maschinenbau GmbH, Paderborn, Germany.
• Figure 8b) shows a scheme of a transversal cross section of the further mixing device 709 in figure 8a).
• the transversal cross section is taken at the axial position 806 is figure 8a).
• Figure 8b) additionally shows the rotating shaft 807 and one of a plurality of mixing tools 808.
• the mixing tool 808 is a paddle.

Priority Applications (4)

Applications Claiming Priority (1)

Publications (1)

Family

ID=54332674

Family Applications (1)

Country Status (4)

Cited By (4)

Families Citing this family (1)

Citations (4)

• 2014
  • 2014-04-25 CN CN201480078204.5A patent/CN106232691B/zh active Active
  • 2014-04-25 KR KR1020167032639A patent/KR20170002470A/ko not_active Application Discontinuation
  • 2014-04-25 WO PCT/KR2014/003680 patent/WO2015163522A1/en active Application Filing
  • 2014-04-25 EA EA201691519A patent/EA031991B1/ru unknown

Patent Citations (4)

Also Published As

Similar Documents

Legal Events