EP1210129A1 - Polymeres absorbant l'eau dotes de composes a espaces vides - Google Patents

Polymeres absorbant l'eau dotes de composes a espaces vides

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Publication number
EP1210129A1
EP1210129A1 EP00954615A EP00954615A EP1210129A1 EP 1210129 A1 EP1210129 A1 EP 1210129A1 EP 00954615 A EP00954615 A EP 00954615A EP 00954615 A EP00954615 A EP 00954615A EP 1210129 A1 EP1210129 A1 EP 1210129A1
Authority
EP
European Patent Office
Prior art keywords
polymer
weight
water
zeolite
silicon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00954615A
Other languages
German (de)
English (en)
Inventor
Helmut Brehm
Jörg HARREN
Jörg ISSBERNER
Richard Mertens
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Stockhausen GmbH and Co KG
Chemische Fabrik Stockhausen GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Stockhausen GmbH and Co KG, Chemische Fabrik Stockhausen GmbH filed Critical Stockhausen GmbH and Co KG
Publication of EP1210129A1 publication Critical patent/EP1210129A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/18—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing inorganic materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria

Definitions

  • the invention relates to absorbents for water and aqueous liquids based on water-swellable but not water-soluble polymers, in which silicon-rich zeolites are ionically and / or incorporated due to mechanical inclusions.
  • the commercially available superabsorbent polymers are essentially crosslinked polyacrylic acids, crosslinked starch / acrylic acid graft copolymers, crosslinked hydrolyzed starch / acrylonitrile graft copolymers, crosslinked poly (maleic anhydride-co-isobutylene) or mixtures of various aforementioned crosslinked polymers in which the carboxyl groups are partially neutralized with sodium and / or potassium ions.
  • Such polymers are used e.g. in hygiene articles that contain body fluids such as Can soak up urine or menstrual fluid or in absorbent pads in food packaging. There they take large amounts of aqueous fluids and body fluids, such as e.g. Urine or blood. It is also necessary that the amount of liquid absorbed is retained under the pressure typical of the application. In the course of the technical development of superabsorbent polymers, the requirement profile for these products has changed significantly over the years.
  • Inorganic ions are present: Na + (5.9 g), K + (2.7 g), NH 4 + (0.8 g), Ca 2+ (0.5 g), Mg 2+ (0.4 g), Cf (8 , 9 g), PO 4 3 - (4.1 g), S0 2 ⁇ (2.4 g)
  • the dryness is between 50 and 72 g.
  • the volatile components of the urine include alkyl furans, ketones, lactones, pyrrole , Allyl isothiocyanate and dimethyl sulfone
  • the volatile components are mostly molecules with a molecular weight below approx. 1000 g / mol, which have a high vapor pressure.
  • Menstrual fluid can also make you uncomfortable Get smell. This smell is caused, among other things, by microbial breakdown of proteins that are excreted.
  • the typical odor substances in the menstrual fluid and the odors caused by the breakdown of blood constituents do not differ significantly from the odors of the constituents found in the urine.
  • Mainly nitrogen-containing heterocycles such as pyrrole, pyridine and their derivatives can be mentioned.
  • vaginal secretions and menstrual fluid were examined by G. Huggins and G. Preti (Clinical Obstetrics and Gynecology, Vol. 24, No. 2, June 1981, 355-377). Low molecular weight substances with a molecular weight below 500 g / mol were found. To be emphasized here are fatty acids (e.g. butyric acid, isovaleric acid) and some aromatic compounds such as Pyridine, indole and thymine, which contribute particularly to the bad smell. The amount of volatile fatty acids varies over the period of the menstrual cycle (Human Vaginal Secretions: Volatile FattyAcid Content, Richard P. Michael, R. W.
  • zeolites When heated, most zeolites release their water continuously and without changing the crystal structure. As a result, they can absorb other compounds and then function, for example, as catalysts or ion exchangers. Zeolites also show a sieving effect by taking up molecules with a smaller cross-section than the pore openings in the channel system of the lattice. Larger molecules are excluded.
  • zeolites The synthesis of zeolites is described in great detail in: Zeolite Synthesis, ACS Symposium Series 398, Eds. ML Ocelli and HE Robson (1989) pages 2-7.
  • the synthesis of hydrophobic zeolites with a silicon dioxide / aluminum oxide ratio of the framework of> 100 and a high hydrothermal stability and resistance to aqueous alkaline solutions is disclosed in patent application DE 19532500A1.
  • the zeolites have a grain size of well below 150 ⁇ m.
  • US 4795482 teaches the use of hydrophobic zeolites to suppress and avoid organic odors. The decrease in odors was measured by means of head space gas chromatography.
  • the zeolite is dispersed together with a binder in water and applied to the superabsorber in a coating process.
  • a binder in water and applied to the superabsorber in a coating process.
  • the present invention is therefore based on the object of providing an absorbent polymer for water and aqueous liquids which has a substance with which odorous organic compounds, such as those e.g. occur in the urine or other excretory fluids of the body, are bound to be made available, in which: the odor-causing substances released into the steam room are significantly reduced in the application, there is an almost even distribution of the odor-binding substance in the absorbent, and there is segregation in the state and as far as possible is avoided during use, the absorbent has good retention and swelling properties
  • Has pressure and the odor-binding modification is ensured with the smallest possible amounts of the odor-binding substance.
  • the present invention is also based on the object of providing a process for producing the odor-absorbing absorbents, in which: in particular the problems when mixing dry substances which differ significantly in terms of particle size, such as e.g.
  • Granules and powders can be avoided, no dust is generated and clumping of the particles during production is avoided.
  • the object is achieved according to the invention by an absorbent polymer composed of crosslinked monoethylenically unsaturated monomers bearing partially neutralized acid groups and containing silicon-rich zeolites ionically or mechanically bound or bound.
  • Silicon rich in the sense of the invention means that the silicon dioxide / aluminum oxide ratio is> 10, preferably> 20, particularly preferably> 50, and very particularly preferably> 100. Most preferred is a silica / alumina ratio> 500.
  • Crosslinked in the sense of the invention means that the polymer is crosslinked and / or surface crosslinked.
  • the zeolites to be used according to the invention are dealuminated, hydrophobic (organophilic) zeolite variants with a silicon dioxide / aluminum oxide ratio of the framework of> 10, preferably> 20, particularly preferably> 50 and very particularly preferably> 100. A ratio> 500 is most preferred.
  • the amount used, based on the total amount of adsorbent, is 0.01-10% by weight, preferably 0.1-5% by weight and particularly preferably 0.70-3% by weight.
  • Such zeolites are marketed, for example, by Degussa AG under the brand name Flavith ® or by UOP under the name Abscents ® . Flavith ® is specified in the product data sheet KC-CZ 42-1 -05-1098 T&D. This product information sheet is hereby introduced as a reference and is therefore considered part of the disclosure.
  • the polymerization of the polymer according to the invention which may have superabsorbent properties
  • several methods are possible, for example bulk polymerization, solution polymerization, spray polymerization, inverse emulsion polymerization and inverse suspension polymerization.
  • the solution polymerization is preferably carried out in water as the solvent.
  • the solution polymerization can be carried out continuously or batchwise.
  • the patent literature shows a wide range of possible variations with regard to the concentration ratios, temperatures, type and amount of the initiators also of the post-catalysts.
  • the acid group-containing unsaturated monomers to be used according to the invention are, for example, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, vinyl acetic acid, vinyl sulfonic acid, methallylsulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid and their alkali and / or ammonium salts.
  • Acrylic acid and its alkali and / or ammonium salts and mixtures thereof are preferably used.
  • comonomers which are soluble in the aqueous polymerization batch, such as, for example, acrylamide, methacrylamide, acrylonitrile, (meth) allyl alcohol ethoxylates and the mono (meth) acrylic acid esters of alcohols or ethoxylates, can optionally be used to modify the polymer properties.
  • Crosslinking monomers are, for example, bi- or polyfunctional monomers, for example amides such as methylene bisacryl or methacrylamide or ethylene bisacrylamide, and also allyl compounds such as allyl (meth) acrylate, alkoxylated allyl (meth) acrylate reacted with preferably 1 to 30 mol of ethylene oxide, triallyl cyanurate , Maleic acid diallyl esters, polyallyl esters, tetraallyloxiethan, triallyl amine, tetraallyl ethylenediamine, allyl esters of phosphoric acid or phosphorous acid, also crosslinkable monomers, such as the N-methylol compounds of amides such as methacrylamide or acrylamide and those derived therefrom Ethers
  • Triallylamine, acrylates of polyhydric alcohols or their alkoxylates and methallyl alcohol acrylates or their alkoxylates are preferably used.
  • the proportion of the crosslinking comonomers is from 0.01 to 3.0% by weight, preferably from 0.05 to 2.0% by weight and particularly preferably from 0.05 to 1.5% by weight, based on the total of the monomers.
  • the acidic monomers are preferably neutralized.
  • the neutralization can be carried out in various ways. On the one hand, the polymerization can be carried out directly with the acidic monomers in accordance with the teaching of US Pat. No. 4,654,039, the neutralization then taking place subsequently in the polymer gel. This patent is hereby introduced as a reference and is therefore considered part of the disclosure.
  • the acidic monomer components are neutralized to 20-95%, preferably 50-80%, before the polymerization and are then already present as sodium, potassium and / or ammonium salts at the start of the polymerization.
  • Sodium hydroxide solution and / or potassium hydroxide solution and or ammonia, particularly preferably sodium hydroxide solution are preferably used, the addition of sodium carbonate, potassium carbonate or sodium bicarbonate having an additional positive effect, as taught by US Pat. No. 5,314,420 and US Pat. No. 5,154,713.
  • the polymers according to the invention can contain water-soluble polymers as a graft base in amounts of up to 40% by weight. These include partially or fully hydrolyzed polyvinyl alcohols, starch or starch derivatives, cellulose or cellulose derivatives, polyacrylic acids, polyglycols or mixtures thereof.
  • the molecular weights of the polymers added as the graft base must be adapted to the conditions of the polymerization conditions. For example, in the case of aqueous solution polymerization, it may be necessary to use only low- or medium-molecular-weight polymers for reasons of the viscosity of the polymer solution, whereas this factor plays a subordinate role in suspension polymerization.
  • polymers which can be obtained by crosslinking polymerization of partially neutralized acrylic acid preference is given to those which contain additional proportions of graft-polymerized starch or of polyvinyl alcohol.
  • the polymerization can be initiated by various conditions, e.g. by radiation with radioactive, electromagnetic or ultraviolet rays or by redox reaction of two compounds, e.g. Sodium hydrogen sulfite with potassium persulfate or ascorbic acid with hydrogen peroxide.
  • a so-called radical starter such as, for example, azobisisobutyronitrile, sodium peroxydisulfate, t-butyl hydroperoxide or dibenzoyl peroxide can also be used as the start of polymerization.
  • a so-called radical starter such as, for example, azobisisobutyronitrile, sodium peroxydisulfate, t-butyl hydroperoxide or dibenzoyl peroxide can also be used as the start of polymerization.
  • a so-called radical starter such as, for example, azobisisobutyronitrile, sodium peroxydisulfate, t-butyl hydroperoxide or dibenzoyl peroxid
  • the polymer is produced in principle by two methods:
  • the partially neutralized acrylic acid in aqueous solution in the presence of the crosslinking agent and, if appropriate, the polymer additives is converted into a gel by free-radical polymerization, which is then comminuted and dried and ground to a powdery, free-flowing state and sieved to the desired particle size.
  • the solution polymerization can be carried out continuously or batchwise.
  • the inverse suspension and emulsion polymerization process can also be used to prepare the polymer.
  • an aqueous, partially neutralized acrylic acid solution is dispersed in a hydrophobic, organic solvent with the aid of protective colloids and / or emulsifiers, and the polymerization is started by radical initiators.
  • the crosslinkers are either dissolved in the monomer solution and are metered in together with it, or are added separately and, if appropriate, subsequently.
  • Any polymeric graft bases present are added via the monomer solution or by direct introduction into the oil phase.
  • the water is then removed azeotropically from the mixture and the polymer product is filtered off and optionally comminuted and dried and ground to a powdery, free-flowing state and sieved to the desired particle size.
  • the properties of the polymers according to the invention may be improved by the process of subsequent surface crosslinking, in particular also in their liquid absorption under pressure, so that the known phenomenon of "gel blocking" is suppressed, in which swollen polymer particles stick together and further liquid absorption and liquid distribution e.g. hinder in the diaper.
  • the carboxyl groups of the polymer molecules on the surface of the superabsorbent particles are crosslinked with crosslinking agents at an elevated temperature. Post-crosslinking processes are described in several documents, e.g. DE 40 20 780, EP 317 106 and WO 94/9043.
  • the postcrosslinking agents known to the person skilled in the art can all advantageously be combined in accordance with the invention can be used with a pre-crosslinker or a combination of crosslinkers.
  • the abovementioned publications are hereby introduced as a reference and are therefore considered part of the disclosure.
  • the compounds generally contain at least two functional groups which are capable of reacting with carboxylic acid or carboxyl groups. Alcohol, amine, aldehyde and carbonate groups are preferred, crosslinking molecules with several different functions also being used. Polyols, polyamines, polyamino alcohols, polyepoxides and alkylene carbonates are preferably used.
  • one of the following post-crosslinking agents is used: ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerin, polyglycerol, propylene glycol, diethanolamine, triethanolamine, polypropylene glycol, block copolymers of ethylene oxide and propylene oxide, sorbitan fatty acid esters, ethoxylated sorbitan fatty acid trimethyl, propylene ethylenedipro trimethylolated trimethyl ester, trimethylated propylene ethoxylated trimethylated propylene ethylenediaminophenoxy trimethylated trimethylated propylene oxide, trimethylated propylene ethoxylated trimethylsulfonated trimethane, pentoxol ethoxylated trimethylsulfonate, trimethylated propane, trimethylated propane, trimethylated propane, trimethylated propane, pentoxolated, ethoxylated, sorbitan, it pan
  • postcrosslinking agents it is particularly preferred to use polyols and ethylene carbonate as postcrosslinking agents.
  • the post-crosslinking agent is used in an amount of 0.01 to 30 percent by weight, preferably 0.1-10 percent by weight, based on the polymer to be post-crosslinked.
  • the polymer Before the postcrosslinking, the polymer is preferably dried, ground and sieved to the particle size fraction which is favorable for the particular application and then fed to the postcrosslinking reaction. In some cases, however, it has also proven useful to add the postcrosslinkers before the polymer gel is dried or before the partially or predominantly dried polymer is comminuted. Postcrosslinking to be carried out according to the invention is described, for example, in US Pat. No. 4,666,983 and DE 40 20 780. These writings are hereby introduced as a reference and are therefore considered part of the disclosure. The addition of the post-crosslinking agent is frequently also advantageously carried out in the form of a solution in water, organic solvents or mixtures thereof, in particular when small amounts of post-crosslinking agent are used.
  • Suitable mixing units for applying the postcrosslinking agent are, for example, Patterson-Kelley mixers, DRAIS turbulence mixers, Lödige mixers, Ruberg mixers, screw mixers, Plate mixers and fluidized bed mixers, as well as continuously operating vertical mixers in which the powder is mixed at high frequency using rotating knives (Schugi mixers).
  • the postcrosslinking reaction is heated to temperatures of 60 to 250 ° C., preferably to 135 to 200 ° C. and particularly preferably to 150 to 185 ° C.
  • the duration of the reheating is limited by the point at which the desired property profile of the polymer is destroyed again as a result of heat damage.
  • different sieve fractions are used to process the polymers, e.g. for diapers between 100 and 1000 ⁇ m, preferably between 150 and 850 ⁇ m.
  • This grain fraction is generally produced by grinding and sieving before and / or after the post-crosslinking.
  • the zeolite component can only be extracted to a reduced extent by the liquid to be absorbed or can only be separated to a reduced extent in the dry state.
  • the zeolites also do not partially lose their ability to bind odors due to the close linkage with the crosslinked polymer carrying acid groups. This results in an effective reduction in the vapor space concentration of substances that pollute odors.
  • the odor-binding substances are applied, for example, from a suspension. This avoids any dust problem during manufacture. It has also been shown that the zeolites also do not lose their ability to absorb odors when they are applied from an aqueous suspension.
  • the polymer according to the invention is eminently suitable for the storage of active substances, these active substances being able to be released again in a controlled manner if necessary.
  • the shelf life of sensitive active ingredients is significantly improved by incorporation into the polymer according to the invention.
  • Another object of the present invention is a method for producing the absorbent polymers according to the invention.
  • the absorbent polymer according to the invention is prepared by: radical polymerization of an aqueous solution of ethylenically unsaturated acid groups, optionally partially neutralized
  • the zeolite is preferably added in suspension.
  • Silicon rich in the sense of the invention means that the silicon dioxide / aluminum oxide ratio is> 10, preferably> 20, particularly preferably> 50, and very particularly preferably> 100. Most preferred is a silica / alumina ratio> 500.
  • the zeolite is used in suspension.
  • a preferred liquid phase is water, but mixtures of water and organic solvents are also used.
  • the zeolite can be added according to the invention in various process stages in the preparation of the powdery polymer.
  • the zeolite is added directly to the aqueous monomer solution before the polymerization. Is the absorbent polymer through
  • suspension polymerization it is also possible to introduce all or part of the zeolite in the oil phase and to meter in the monomer solution. If only part of the cellulite is initially charged, the remainder must be added via the monomer solution.
  • the zeolite is applied to the comminuted polymer gel suspended in water or an organic solvent or mixtures thereof.
  • the polymer gel is furthermore preferably at least partially dried and the zeolite is then suspended in the water or an organic solvent or mixtures thereof and applied to the powder.
  • the resulting product can be dried directly and surface-crosslinked.
  • the zeolite is used in the post-crosslinking processing step.
  • Suitable mixing units for applying the post-crosslinking agent are, for example, Patterson-Kelley mixers, DRAIS turbulence mixers, Lödige mixers, Ruberg mixers, screw mixers, plate mixers and fluidized bed mixers, as well as continuously operating vertical mixers in which the powder is mixed at high frequency using rotating knives (Schugi- Mixer).
  • the zeolite is also preferably introduced at several points in the manufacturing process of the absorbent polymers in order to optimize the action of the zeolite and to use synergies.
  • the absorbent polymer according to the invention is prepared by: radical polymerization of an aqueous solution of ethylenically unsaturated acid groups, optionally partially neutralized monomers and crosslinking monomers by the solution or suspension polymerization process to give a hydrogel, optionally isolation, comminution followed by drying , Grinding, optionally sieving, the silicon-rich zeolite being added to the polymer when it still has at least a water-water content of 10% by weight.
  • the zeolite is preferably added in suspension.
  • the water content must not have been reduced below 10% by weight before the silicon-rich zeolite has been added before the silicon-rich zeolite is added.
  • the water content before the addition of the silicon-rich zeolite should preferably not have been reduced below 30% by weight, particularly preferably not below 50% by weight and very particularly preferably not below 65% by weight.
  • the zeolite is preferably added to the polymer from a suspension.
  • Absorbent polymers are obtained by the process according to the invention, in which the zeolite is integrated in the synthetic polymer in such a way that the zeolite is no longer completely removed from the polymer even after mechanical stress, for example in a ball mill at 95 rpm and for 6 minutes is to be separated.
  • mechanical stress for example in a ball mill at 95 rpm and for 6 minutes is to be separated.
  • less than 80%, as a rule 40-60% of the total amount of zeolite applied to the polymer detaches again after such exposure.
  • the polymers according to the invention have a better absorption of odor-damaging compounds compared to powdery absorbents without zeolite.
  • the polymer according to the invention is used e.g. in hygiene articles that contain body fluids such as Can soak up urine or in the packaging area of e.g. Meat and fish products. There they take large amounts of aqueous fluids and body fluids, such as e.g. Urine, blood or meat juice. These uses are therefore also the subject of the present invention.
  • the polymers according to the invention are incorporated directly as powders into the structures for absorbing liquids or are previously fixed in foamed or non-foamed fabrics.
  • Such constructions for absorbing liquids are, for example, baby diapers, incontinence products or absorbent inserts in packaging units for food.
  • the binding of the zeolite to the polymer is obviously so strong in the absorbent polymer according to the invention that even under mechanical stress e.g. Promotion of the absorbent polymer no significant separation and segregation of polymer and zeolite can be observed and therefore in particular the problems of handling very fine particles do not arise.
  • the polymer according to the invention is used in plant breeding and pest control in agriculture.
  • plant breeding the polymers in the vicinity of plant roots ensure an adequate supply of liquid and previously stored nutrients and are able to store and release them over a longer period of time.
  • active ingredients can be stored individually or in a combination of several active ingredients in the polymer, which are then released in a time-controlled and quantity-controlled manner.
  • Test method 1 The retention is given according to the teabag method and as an average of three measurements. About 200 mg of polymer are sealed in a tea bag and immersed in 0.9% NaCl solution for 30 minutes. The tea bag is then spun in a centrifuge (23 cm diameter, 1,400 rpm) for 3 minutes and weighed. a Tea bags without water-absorbing polymer are allowed to run as a blank value.
  • Test method 2 liquid absorption under pressure (AAP test, EP 0 339 461)
  • the absorption under pressure (pressure load 50 g / cm 2 ) is determined by a method described in EP 0 339 461, page 7. This document is hereby introduced as a reference and is therefore part of the disclosure. Approx. 0.9 g superabsorbent is weighed into a cylinder with a sieve bottom. The evenly sprinkled superabsorbent layer is loaded with a stamp which exerts a pressure of 50 g / cm 2 . The previously weighed cylinder is then placed on a glass filter plate, which is in a bowl with 0.9% NaCl solution, the liquid level of which corresponds exactly to the height of the filter plate. After the cylinder unit has been sucked for 0.9% NaCI solution for 1 hour, it is weighed back and the AAP is calculated as follows:
  • AAP Weighing out (cylinder unit + super absorber) - Weighing out (cylinder unit + fully absorbed super absorber) / Weighing out super absorber
  • 0.1 g of powdery absorbent is mixed with 2 ml of an aqueous solution (contains 5% by weight of ethanol) of the odor- nuisancesance compound and sealed in a 5 ml sample vessel. It is left to stand at 23 ° C. for 12 hours and the head-space GC is used to quantitatively examine the content of the odor-causing compound in the vapor space above the liquid against a zero sample.
  • Test method 4 The silicon content of the absorbent polymers is determined by converting the silicate to molybdenum blue and subsequent photometric analysis. Silicon is previously quantitatively dissolved in alkaline Transferred silicate. (Photometric analysis, authors: B. Lange, Zdenek, J. Vejdelek, S., edition 1987, p. 383, VCH)
  • This example explains the preparation of a polymer gel with superabsorbent properties.
  • a solution of 1300 g acrylic acid, 2115.9 g dist. Water, 2.7 g of polyethylene glycol monoally ether acrylate and 1.25 g of polyethylene glycol diacrylate. While stirring and cooling, 899.10 g of 50% sodium hydroxide solution are partially neutralized (degree of neutralization (NG) 60%). The solution is cooled to 7-8 ° C and with nitrogen for about 20 min. bubbled. Then 0.45 g of azo-bis (2-amodinopropane) dihydrochloride dissolved in 22.5 g of dist. Water, 1.35 g sodium peroxodisulfate, dissolved in 25 g dist.
  • a solution of 1300 g acrylic acid, 2015.9 g dist. Water, 6.5 g of polyethylene glycol monoally ether acrylate and 3.9 g of polyethylene glycol diacrylate. With stirring and cooling, 997.10 g of 50% sodium hydroxide solution are partially neutralized (NG 70%). The solution is cooled to 7-8 ° C and with nitrogen for about 20 min. bubbled. Then 0.45 g of azo-bis (2- amidinopropane) dihydrochloride dissolved in 22.5 g of dist. Water, 1.35 g sodium peroxodisulfate, dissolved in 25 g dist. Water, and 0.315 g of hydrogen peroxide (35%) dissolved in 22.5 g of dist. Add water. The polymerization is then started by adding 0.0675 g of ascorbic acid dissolved in 9 g of water, whereupon a significant increase in temperature takes place. A gel-like product is obtained, the further processing of which is described in the examples below.
  • This example illustrates the preparation of another polymer gel with superabsorbent properties.
  • 500 g of the gels obtained from Examples 1b-c) are bulged and with the amounts of a suspension of Flavith ® S 108 (Degussa AG, SiO 2 / Al 2 O 3 ratio approx. 500) or Flavith ® listed in the table below D (Degussa AG SiO 2 / Al 2 O 3 ratio approx. 56) or zeolite A (SiO 2 / Al 2 O 3 ratio ⁇ 5) evenly sprayed in water and then up to a residual water content of ⁇ 10% at 150 ° C in dried in a convection oven.
  • Examples e and f are comparative examples, since the zeolite A used is not a silicon-rich zeolite.
  • This example examines retention and fluid uptake under pressure of a polymer with superabsorbent properties in the absence of zeolite.
  • 50 g of the dried, ground and sieved to 150-850 ⁇ m polymer from Examples 1a-c) are wetted with vigorous mixing with a solution of 0.5 g of ethylene carbonate and 1.5 g of water in a plastic vessel and with a commercially available household Hand mixer (Krups) mixed well.
  • the wetted polymer is then heated in an oven to a temperature of 180 ° C. for 30 minutes.
  • the surface crosslinking takes place after the addition of zeolite.
  • 50 g of the dried, ground and sieved to 150-850 ⁇ m polymers from Example 2a-f) are each individually, with vigorous mixing, wetted with a solution of ethylene carbonate (EC) and water in a plastic vessel and with a commercially available household hand mixer (Krups ) mixed well.
  • the solution contains 0.25 g EC per 1.8 g water.
  • the wetted polymer is then heated to 170 ° C. in an oven for 30 minutes.
  • Example 5 In this example, zeolite is added during surface crosslinking.
  • Example 1a 50 g of the bulged, dried, ground and sieved to 150-850 ⁇ m polymer from Example 1a) are mixed vigorously with a solution of 0.25 g ethylene carbonate, 1.5 g water and with the amount listed in the table below (details in% dry matter based on acrylic acid) Flavith ® S 108 (Degussa AG) wetted as a suspension in a plastic container and mixed well with a standard household hand mixer (Krups). The wetted polymer is then heated in an oven to a temperature of 180 ° C. for 30 minutes.
  • Comparative Example 3b (analogous to WO 91/12029) 0.25 g of methyl cellulose (Walocel VP-M 20678) are dispersed with 1 g of Flavith ® S108 and 5 g of water using a high-speed mixer and then mixed in a laboratory mixer with 50 g of a commercially available superabsorbent (Favor ® SXM 6860 from Stockhausen) and dried in a fluidized bed dryer at 60 ° C and constant air flow for 20 min.
  • Flavith ® S108 1 g of Flavith ® S108 and 5 g of water using a high-speed mixer and then mixed in a laboratory mixer with 50 g of a commercially available superabsorbent (Favor ® SXM 6860 from Stockhausen) and dried in a fluidized bed dryer at 60 ° C and constant air flow for 20 min.
  • zeolite is added after surface crosslinking.
  • 50 g of the product obtained from Example 4 are suspended in water under thorough mixing, sprayed with the one indicated in the following table the amount of zeolite (Flavith ® S108, Fa. Degussa-Huels).
  • the product is dried in a drying cabinet to a residual water content of ⁇ 4%.
  • Example 6 The product obtained from comparative examples 3) and 4) is sieved and the fraction with a particle size of 150-850 ⁇ m is subjected to a ball mill stability test. The product is loaded in a ball mill for 6 minutes at 95 rpm. The product obtained from Example 2b was also subjected to the same ball mill stability test. The products were sieved again and the fraction with a grain size of ⁇ 150 ⁇ m was tested for the silicon content according to test method 4. Since the zeolite used has a grain size of significantly less than 150 ⁇ m, this method can be used to determine how much zeolite is bound or enclosed in the polymer with superabsorbent properties. The following amounts of silicon, based on the total amount of dry matter, were found for the samples:
  • SAP superabsorbent from Stockhausen (FAVOR ® SXM 6860) and 1 g Flavith ® S108 were mixed with a kitchen mixer from Krups. After addition of 15 g water, clumping of the material was observed. Drying 120 min. At 60 ° C.
  • the products according to the invention have significantly less silicon in the fraction of the particles ⁇ 150 ⁇ m than a product manufactured according to the prior art. This proves that the binding of the zeolite to the polymer is significantly stronger in the products according to the invention.
  • the composite materials produced in accordance with the patent specifications WO 91/12029 and WO 91/12031 are also significantly more unstable than the products according to the invention, which is evidenced by the increased SiO 2 content in the fine dust before and after the ball mill stability test.
  • Comparative example V4a shows that even when using small amounts of zeolite (2%) the binding in processes according to the prior art is significantly worse than in the process according to the invention (Example 2b).
  • the reduction in the vapor space concentration of odor-causing compounds was investigated.
  • a polymer without zeolite was examined as a blank sample in accordance with test specification 2) and the vapor space concentration found was equated with 100% of the odor-causing substance.
  • zeolite-containing samples were examined and the vapor space concentration of the odor-causing substance was determined.
  • the information in the right-hand column is calculated according to: 100 * (found amount of odor substance from polymer containing zeolite / amount of odor substance found from polymer free of zeolite).
  • the absorbent polymers according to the invention show a clear absorption of odor-damaging substances.
  • the comparative examples show that zeolites with a low silicon dioxide / aluminum oxide ratio do not lead to a satisfactory decrease in the vapor space concentration of odorous substances.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Veterinary Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hematology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Orthopedics, Nursing, And Contraception (AREA)

Abstract

L'invention concerne des agents d'absorption de l'eau et des liquides aqueux, à base de polymères susceptibles de gonfler à l'eau, mais non solubles dans l'eau, dans lesquels des zéolithes riches en silicium sont encastrées ioniquement et/ou par suite d'inclusions mécaniques.
EP00954615A 1999-08-20 2000-08-09 Polymeres absorbant l'eau dotes de composes a espaces vides Withdrawn EP1210129A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19939661 1999-08-20
DE19939661 1999-08-20
PCT/EP2000/007742 WO2001013965A1 (fr) 1999-08-20 2000-08-09 Polymeres absorbant l'eau dotes de composes a espaces vides

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EP1210129A1 true EP1210129A1 (fr) 2002-06-05

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AU (1) AU6701000A (fr)
BR (1) BR0013468A (fr)
CA (1) CA2381930A1 (fr)
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WO (1) WO2001013965A1 (fr)

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ATE319485T1 (de) 2002-08-23 2006-03-15 Supersaugfähige polymere und verfahren zu ihrer herstellung
AU2003250155A1 (en) * 2002-08-23 2004-03-11 Basf Aktiengesellschaft Superabsorbent polymers and method of manufacturing the same
BE1016334A3 (nl) * 2004-12-01 2006-08-01 Zweetverband.
BE1017212A3 (nl) * 2006-07-10 2008-05-06 Everaerts Louis Jozeph Zweetband en nieuw gebruik van een zweetband.
JP2011505436A (ja) 2007-11-15 2011-02-24 ビーエーエスエフ ソシエタス・ヨーロピア 表面に図示記号を有する超吸収性発泡体
CN111471136B (zh) * 2020-06-01 2022-08-30 玉林师范学院 一种淀粉抑尘剂及其制备方法

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AU7259791A (en) * 1990-02-12 1991-09-03 Procter & Gamble Company, The Mixed odor controlling compositions
IT1273087B (it) * 1994-03-25 1997-07-04 P & G Spa Articolo assorbente con materiale per il controllo dell'odore, relativo uso e composizione
JP3665797B2 (ja) * 1994-12-22 2005-06-29 ユニ・チャーム株式会社 消臭性樹脂組成物およびその製法
EP0933086A1 (fr) * 1997-12-18 1999-08-04 The Procter & Gamble Company Particules compactées pour le contrÔle d'odeurs dans les produits absorbants

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WO2001013965A1 (fr) 2001-03-01
JP2003507535A (ja) 2003-02-25
CA2381930A1 (fr) 2001-03-01
BR0013468A (pt) 2002-06-04
TWI282742B (en) 2007-06-21
AU6701000A (en) 2001-03-19

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