EP1084174A1 - Hydrogels a stabilite mecanique - Google Patents

Hydrogels a stabilite mecanique

Info

Publication number
EP1084174A1
EP1084174A1 EP99922121A EP99922121A EP1084174A1 EP 1084174 A1 EP1084174 A1 EP 1084174A1 EP 99922121 A EP99922121 A EP 99922121A EP 99922121 A EP99922121 A EP 99922121A EP 1084174 A1 EP1084174 A1 EP 1084174A1
Authority
EP
European Patent Office
Prior art keywords
hydrogel
ionically crosslinked
hydrogels according
crosslinked hydrogels
gel
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Withdrawn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
EP99922121A
Other languages
German (de)
English (en)
Inventor
Volker Frenz
Rüdiger Funk
Norbert Herfert
Fritz Engelhardt
Ulrich Riegel
Uwe Stüven
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP1084174A1 publication Critical patent/EP1084174A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
    • A61F2013/530481—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having superabsorbent materials, i.e. highly absorbent polymer gel materials
    • 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 present invention relates to ionically crosslinked hydrogels, obtainable by adding aluminates of the formula (I)
  • M is potassium or sodium and n is an integer from 1 to 10,
  • water-insoluble, crosslinked polymers containing carboxyl groups which are capable of swelling and forming hydrogels in aqueous liquids and body fluids, such as e.g. Take up urine or blood and retain the amount of fluid absorbed under a certain pressure.
  • Substances are preferably used which contain two or more groups which can form covalent bonds with the carboxyl groups of the hydrophilic polymers (EP-A-0 349 240).
  • Polyglycidyl ethers, haloepoxy compounds, polyols, polyamines or polyisocyanates can be used as crosslinking agents.
  • DE-A-3 314 019, EP-A-0 317 106 and DE-A-3 737 196 describe polyfunctional azidine compounds, 2
  • EP-A-372 981, JP-A-03 179 008, US-A-5 314 420 and US-A-4 690 971 describe the use of polyvalent metal ions in general for surface crosslinking.
  • the invention thus relates to ionically crosslinked hydrogels, obtainable by adding aluminates of the formula (I)
  • M is potassium or sodium and n is an integer from 1 to 10,
  • the ionic crosslinking by means of aluminate ions takes place homogeneously in the gel form of the polymeric hydrogels before drying to form powders or granules.
  • hydrogel structures are produced by adding aluminumates I, preferably [Al (OH) 4 ] " , to polymers containing carboxyl groups and / or alkali metal or ammonium carboxylate groups, aqueous gels, so-called hydrogels, which can be uncrosslinked or pre-crosslinked by covalent bonds.
  • AI (OH) 3 dissolves as an amphoteric hydroxide both in acid
  • the Alumination [AI (OH) 4 ] is not stable and condenses easily to higher molecular weight oxo compounds under water. Instead of condensation, the Alumination [AKOH 4 )] - like the isolation of sodium salts of the composition 3 Na 2 0 -Al 2 ⁇ 3 -6H 2 0 shows can also be stabilized by taking up 2 OH ions
  • K 2 [H 6 A1 2 0 7 ] K 2 0 • A1 2 0 3 • 3 H 2 0
  • covalently crosslinked hydrogels which are obtained by polymerizing 90-99.99 mol% of a monounsaturated monomer containing carboxyl groups and / or alkali metal or ammonium carboxylate groups and 0.01-10 mol% of a crosslinking agent.
  • Suitable crosslinkers are in particular methylenebisacryl or methacrylamide, esters of unsaturated mono- or polycarboxylic acids of polyols, such as diacrylate or triacrylate, e.g. Butanediol or ethylene glycol diacrylate or methacrylate as well as triethylolpropane triacrylate and allyl compounds such as allyl (meth) acrylate, tri-allylcyanurate, maleic acid diallyl ester, polyallyl ester, tetraallyloxyethane, triallylamine, tetraallyl ethylene diphosphate such as phosphate and allyl ester diamine, for example allyl esters, A-0 343 427.
  • esters of unsaturated mono- or polycarboxylic acids of polyols such as diacrylate or triacrylate, e.g. Butanediol or ethylene glycol diacrylate or methacrylate as well as triethyl
  • hydrogels which are prepared using polyallyl ethers as crosslinking agents and by acidic homopolymerization of acrylic acid are particularly preferred.
  • Suitable crosslinkers are pentaerythritol tri- and tetraallyl ether, polyethylene glycol diallyl ether, monoethylene glycol diallyl ether, glycerol di- and tri-allyl ether, polyallyl ether based on sorbitol, and alkoxylated variants thereof.
  • Monounsaturated monomers are, for example, vinyl acetic acid and preferably acrylic acid and methacrylic acid and their alkali metal or ammonium salts, e.g. Sodium, potassium and ammonium acrylates. Preference is given to ionically crosslinked hydrogel structures which are composed of 50 to 99.99% by weight of structural units which are derived from acrylic acid.
  • Such hydrogels are generally known and are produced by conventional processes.
  • the ionically crosslinked hydrogel structures according to the invention are preferably obtained by free-radically polymerizing aqueous acrylic acid solutions with the addition of polyolefinically unsaturated compounds, for example the above-mentioned crosslinking agents.
  • the polymerization process gives water-containing hydrogels, which are then added to pH values between 3.0 and 9.5, preferably between 4.0 and 7.5, by adding illuminations as described above in connection with bases such as sodium or potassium hydroxide. 5 places.
  • the bases can be added either before the addition of the aluminate or together with the aluminate. In the former case, neutralized or partially neutralized gels are crosslinked. It is also possible to polymerize partially neutralized aqueous acrylic acid solutions, preferably in the presence of a crosslinking agent, and then to crosslink them with aluminates, if appropriate with the addition of a base.
  • the amount of aluminates used is 0.05 to 80 mol%, preferably 0.05 to 30 mol% of aluminum, based on the sum of carboxyl groups and alkali metal or ammonium carboxylate groups, preferably based on the acid units to be neutralized in the hydrogel.
  • the polymerization can be triggered by radical formers, such as organic or inorganic peroxides and azo compounds.
  • radical formers such as organic or inorganic peroxides and azo compounds. Examples are benzoyl peroxide, tert. -Butyl hydroperoxide, cumene hydroperoxide, (H) 2 S 2 08, K 2 S 2 0 ⁇ , H 2 S 2 0 8 , H 2 0 2 or azodiisobutyronitrile.
  • Redox systems are also outstandingly suitable as polymerization initiators.
  • the polymerization can also be triggered by high-energy radiation.
  • compounds of the general formula I are first added to an uncrosslinked pre (co) polymer, this is usually done before drying by homogeneous mixing, for example by kneading an aqueous polymer gel in a kneader.
  • the gel particles are subjected to a drying process to remove the water. 6, then grind and set a desired particle size distribution by sieving.
  • the polymer particles produced in this way are able to absorb many times their own weight in aqueous liquids.
  • Hydrogel particles are formed, which are characterized by special physical properties.
  • hydrogel particles which have been produced in a similar way by polymerizing unsaturated water-soluble acids with the addition of polyolefinically unsaturated compounds, are subjected to repeated mechanical stress, such as exposure to strong shear forces, irreversible degradation of the hydrogel network structure takes place through the destruction of covalent bonds under mechanical stress. This has the result that the mechanical stability of the gel particles that is, the so-called gel ⁇ strength drastically decreases.
  • hydrogel structures according to the invention which in addition to covalent crosslinking elements are crosslinked according to an ionic mechanism, do not show this disadvantage since the ionic crosslinking elements are capable of recombination.
  • hydrogels according to the invention are outstandingly suitable as absorbents for aqueous liquids, for the formulation of cosmetic preparations, as consolidators and / or binders of fibrous sheet-like structures containing reactive groups, and as drilling fluids and cement sludge in the production of petroleum.
  • Hydrogels according to the invention based on acrylic acid are particularly suitable for use as so-called “super absorbing polymers” (SAP) for the use of hygiene articles, for example diapers, tampons or sanitary napkins. These preferably contain 50 to 99.99, in particular up to 98% by weight of structural units which are derived from acrylic acid. Particularly preferred are hydrogels, which are copolymers of acrylic acid and di- or polyunsaturated compounds, which have been prepared in aqueous solution.
  • Hydrogels according to the invention based on carboxymethyl polysaccharides are also outstandingly suitable for use as SAP.
  • hydrogels In addition to high absorption capacity, hydrogels also have high gel strength.
  • the improved mechanical property profile of the hydrogel structures according to the invention compared to conventional covalently crosslinked products can be shown by measuring the gel recovery index.
  • the gel recovery index is measured using a Creep Meter, model RE-3305 from Yamaden Co., Ltd.
  • This device is a penetrometer, which can be used to carry out investigations of changes in structure and consistency over time or due to changing load factors.
  • the centerpiece of the device is a measuring slide that can be moved in the vertical direction with a force transducer and a stamp as a test specimen.
  • the force transducer measures the compressive or tensile forces that act on the test specimen when the slide is moved from the sample.
  • the maximum penetration depth of the test specimen when measuring the force
  • the maximum force absorption when measuring the penetration depth
  • the depth of penetration of the star apex is selected so that the force absorption in the 20th cycle (50 "3%) is the force absorption in the 1st cycle, and must therefore be individually determined for each product through preliminary tests. 8 be averaged.
  • the gel is left on the sample plate for 20 minutes at room temperature. During this time, the gel has the opportunity to recover and repair the network defects caused by the mechanical stress. After this time the test program is repeated (2nd cycle series), the depth of penetration of the stamp remains unchanged.
  • Tables 1 and 2 show the force absorption data for gels that do not have a repair effect or a complete repair effect to clarify the test method.
  • the 0 gel recovery index is calculated as follows:
  • a redox system consisting of 2.2 g 2, 2 '-azobisamidinopropane dihydrochloride, dissolved in 20 g demineralized water, 4 g potassium peroxodisulfate, dissolved in 150 g demineralized water and 0 , 4 g of ascorbic acid, dissolved in 20 g of demineralized water, added in succession and stirred.
  • the reaction solution is then left to stand without stirring, a solid gel being formed by the onset of polymerization, in the course of which the temperature rises to approximately 89.degree.
  • Example 2 The procedure is analogous to Example 1, except that only a 30% aqueous solution of NaOH is used to adjust the acidic gel to a pH of 5.8.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Animal Behavior & Ethology (AREA)
  • Hematology (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des hydrogels à réticulation ionique, caractérisés par l'adjonction de composés de la formule (I) Mn[H2n+2AlnO3n+1], dans laquelle M représente potassium ou sodium et n représente un nombre entier compris entre 1 et 10, ces composés étant destinés à la réticulation et le pH étant réglé sur une valeur comprise entre 3,0 et 9,5.
EP99922121A 1998-04-28 1999-04-22 Hydrogels a stabilite mecanique Withdrawn EP1084174A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19818852 1998-04-28
DE19818852 1998-04-28
PCT/EP1999/002702 WO1999055767A1 (fr) 1998-04-28 1999-04-22 Hydrogels a stabilite mecanique

Publications (1)

Publication Number Publication Date
EP1084174A1 true EP1084174A1 (fr) 2001-03-21

Family

ID=7865977

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99922121A Withdrawn EP1084174A1 (fr) 1998-04-28 1999-04-22 Hydrogels a stabilite mecanique

Country Status (3)

Country Link
EP (1) EP1084174A1 (fr)
JP (1) JP2002513059A (fr)
WO (1) WO1999055767A1 (fr)

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US6562743B1 (en) 1998-12-24 2003-05-13 Bki Holding Corporation Absorbent structures of chemically treated cellulose fibers
DE50102334D1 (de) 2000-03-31 2004-06-24 Stockhausen Chem Fab Gmbh Pulverförmige, an der oberfläche vernetzte polymerisate
US7507475B2 (en) 2001-03-07 2009-03-24 Evonik Stockhausen Gmbh Pulverulent polymers crosslinked on the surface
WO2003043670A1 (fr) 2001-11-21 2003-05-30 Basf Aktiengesellschaft Hydrogels superabsorbants a revetement polyamine reticule
EP1551467B1 (fr) 2002-08-23 2006-03-08 Basf Aktiengesellschaft Polymeres superabsorbants et procede pour les preparer
US8247491B2 (en) 2003-02-10 2012-08-21 Nippon Shokubai Co., Ltd. Water-absorbent resin composition and its production process
EP2260876B1 (fr) 2003-09-19 2021-08-04 Nippon Shokubai Co., Ltd. Composant hydrophile et procede de fabrication associe
ATE548055T1 (de) 2003-10-31 2012-03-15 Basf Se Blut und/oder körperflüssigkeiten absorbierendes hydrogel
EP1696972B1 (fr) 2003-12-19 2016-10-26 Buckeye Technologies Inc. Fibres possedant une mouillabilite variable et materiaux contenant ces fibres
TWI353360B (en) 2005-04-07 2011-12-01 Nippon Catalytic Chem Ind Production process of polyacrylic acid (salt) wate
DE102005018924A1 (de) 2005-04-22 2006-10-26 Stockhausen Gmbh Wasserabsorbierende Polymergebilde mit verbesserten Absorptionseigenschaften
TWI394789B (zh) 2005-12-22 2013-05-01 Nippon Catalytic Chem Ind 吸水性樹脂組成物及其製造方法、吸收性物品
EP1837348B9 (fr) 2006-03-24 2020-01-08 Nippon Shokubai Co.,Ltd. Résine absorbant l'eau et son procédé de fabrication
DE102006019157A1 (de) 2006-04-21 2007-10-25 Stockhausen Gmbh Herstellung von hochpermeablen, superabsorbierenden Polymergebilden
DE102006061005A1 (de) 2006-12-22 2008-07-03 Admedes Schuessler Gmbh Vorrichtung und Verfahren zum Komprimieren von Mikrostents
WO2011040472A1 (fr) 2009-09-29 2011-04-07 株式会社日本触媒 Absorbant particulaire d'eau et son procédé de fabrication
JP6092228B2 (ja) 2012-08-30 2017-03-08 株式会社日本触媒 粒子状吸水剤及びその製造方法
WO2019137833A1 (fr) 2018-01-09 2019-07-18 Basf Se Mélanges de superabsorbants
EP3749376B1 (fr) 2018-02-06 2022-04-20 Basf Se Procédé pour assurer le transport pneumatique de particules de superabsorbants
EP3774999B1 (fr) 2018-04-10 2022-08-03 Basf Se Superabsorbant perméable et procédé pour sa fabrication
EP4004072A1 (fr) 2019-07-24 2022-06-01 Basf Se Superabsorbant perméable et son procédé de production

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GB9322119D0 (en) * 1993-10-27 1993-12-15 Allied Colloids Ltd Superabsorbent polymers and products containing them

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Also Published As

Publication number Publication date
WO1999055767A1 (fr) 1999-11-04
JP2002513059A (ja) 2002-05-08

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