EP0791020A1 - Materiau absorbant - Google Patents

Materiau absorbant

Info

Publication number
EP0791020A1
EP0791020A1 EP95940681A EP95940681A EP0791020A1 EP 0791020 A1 EP0791020 A1 EP 0791020A1 EP 95940681 A EP95940681 A EP 95940681A EP 95940681 A EP95940681 A EP 95940681A EP 0791020 A1 EP0791020 A1 EP 0791020A1
Authority
EP
European Patent Office
Prior art keywords
superabsorbent
cationic
functional groups
superabsorbent material
polysaccharide
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Withdrawn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
EP95940681A
Other languages
German (de)
English (en)
Other versions
EP0791020A4 (fr
Inventor
Gianfranco Palumbo
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.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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 Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0791020A1 publication Critical patent/EP0791020A1/fr
Publication of EP0791020A4 publication Critical patent/EP0791020A4/fr
Withdrawn legal-status Critical Current

Links

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

Definitions

  • the present invention relates to an absorbent material, more particularly a material of the type commonly referred to as a "superabsorbent".
  • superabsorbents are typically slightly cross-linked hydrophilic polymers.
  • the polymers may differ in their chemical nature but they share the property of being capable of absorbing and retaining even under moderate pressure amounts of aqueous fluids equivalent to many times their own weight.
  • superabsorbents can typically absorb up to 100 times their own weight or even more of distilled water.
  • Superabsorbents have been suggested for use in many different industrial applications where advantage can be taken of their water absorbing and/or retaining properties and examples include agriculture, the building industry, the production of alkaline batteries and filters.
  • the primary field of application for superabsorbents is in the production of hygienic and/or sanitary products such as disposable sanitary napkins and disposable diapers either for children or for incontinent adults.
  • superabsorbents are used, generally in combination with cellulose fibres, to absorb body fluids such as menses or urine.
  • body fluids such as menses or urine.
  • the absorbent capacity of superabsorbents for body fluids is dramatically lower than for deionised water. It is generally believed that this effect results from the electrolyte content of body fluids and the effect is often referred to as "salt poisoning" .
  • the water absorption and water retention characteristics of superabsorbents are due to the presence in the polymer structure of ionisable functional groups. These groups are usually carboxyl groups, a high proportion of which are in the salt form when the polymer is dry but which undergo dissociation and solvation upon contact with water. In the dissociated state, the polymer chain will have a series of functional groups attached to it which groups have the same electric charge and thus repel one another. This leads to expansion of the polymer structure which, in turn, permits further absorption of water molecules although this expansion is subject to the constraints provided by the cross-links in the polymer structure which must be sufficient to prevent dissolution of the polymer.
  • Japanese Patent Application OPI No. 57-45,057 discloses an absorbent which comprises a mixture of a superabsorbent such as a cross-linked polyacrylate with an ion exchange resin in powder or granular form.
  • EP-A-0210756 relates to an absorbent structure comprising a superabsorbent and an anion exchanger, optionally together with a cation exchanger, wherein both ion exchangers are in fibrous form.
  • Combining a superabsorbent with an ion exchanger attempts to alleviate the salt poisoning effect by using the ion exchanger, generally as a combination of both an anion exchanger and a cation exchanger, to reduce the salt content of the liquid.
  • the ion exchanger has no direct effect on the performance of the superabsorbent and it may not be possible to reduce the salt content sufficiently to have the desired effect on the overall absorption capacity of the combination.
  • the ion exchanger has no absorbing effect itself and thus acts as a diluent to the superabsorbent .
  • An object of the present invention is to provide a superabsorbent with improved performance in the presence of electrolyte, for example in the case of menses or urine.
  • the present invention provides a superabsorbent material which comprises a combination of
  • the cationic superabsorbent preferably has from 50 to 100%, more preferably substantially 100% of the functional groups in basic form.
  • the cation exchanger preferably nas substantially 100% of the functional groups in acid form.
  • a combination of a cationic absorbent in basic form with a cation exchange in acid form is particularly effective as a superabsorbent in the case of electrolyte containing solutions, for example menses and urine.
  • the functional groups in cationic superabsorbents are typically quaternary ammonium groups which are strong ion exchangers.
  • an electrolyte solution for example a saline solution
  • it swells and the OH " ions from the superabsorbent are replaced in part with Cl " from solution and the pH of the solution will become strongly basic.
  • the cation exchange resin prevents the solution becoming strongly basic by displacing the equilibrium reaction in favour of the complete conversion of the cationic superabsorbent into the salt from.
  • the cationic superabsorbent can be any material having superabsorbent properties in which the functional groups are cationic.
  • the functional groups are attached to a slightly cross-linked acrylic base polymer.
  • the base polymer may be a polyacrylamide, polyvinyl alcohol, ethylene maleic anhydride copolymer, polyvinylether, polyvinyl sulphonic acid, polyacrylic acid, polyvinylpyrrolidone and polyvinylmorpholine. Copolymers of these monomers can also be used.
  • Starch and cellulose based polymers can also be used including hydroxypropyl cellulose, carboxymethyl cellulose and acrylic grafted starches.
  • Particular base polymers include cross-linked polyacrylates, hydrolysed acrylonitrile grafted starch, starch polyacrylates, and isobutylene maleic anhydride copolymers.
  • Particularly preferred base polymers are starch polyacrylates and cross-linked polyacrylates.
  • Suitable cationic functional groups include quaternary ammonium groups or primary, secondary or tertiary amines which should be present in base form.
  • DS degree of substitution
  • the degree of substitution (DS) of the derivative with the functional group is defined as the number of functional groups (generally quaternary ammonium groups) per anhydroglucose units of cellulose.
  • the DS is generally from
  • the DS for synthetic polymers may be defined as the number of functional groups per monomer or comonomer unit.
  • the DS is generally 1, for example 1 quaternary ammonium group per monomer unit of polyacrylate.
  • Preferred base polymers include polysaccharides and polymers based on dimethyldiallyl ammonium chloride.
  • the cationic superabsorbent can be a polysaccharide superabsorbent obtained by reacting a fibrous polysaccharide such as cellulose with an excess of a quaternary ammonium compound containing at least one group capable of reacting with polysaccharide hydroxyl groups and having a degree of substitution of 0.5 to l.l.
  • the quaternary ammonium compound may have the general formula:
  • n is an integer from 1 to 16;
  • X is halogen,- Z is an anion such as halide or hydroxyl; and
  • R, R 1 , R 2 and R 3 which may be the same or different, are each hydrogen, alkyl, hydroxyalkyl, alkenyl or aryl and may additionally represent a residue of formula
  • the cationic superabsorbent may be a cross-linked cellulose based superabsorbent, in particular a fibrous cationic polysaccharide having superabsorbent characteristics, the polysaccharide being substituted by quaternary ammonium groups and having a ds of at least 0.5 and the polysaccharide being cross-linked to a sufficient extent that it remains insoluble in water.
  • superabsorbents of this type are described in more detail in our co-pending patent application No (internal reference DR44) .
  • the cationic superabsorbent may be a water-swellable, water-insoluble polymer comprising units derived from a diallylic quaternary • ammonium salt monomer, cross-linked by a suitable polyfunctional vinyl compound, characterised in that the polymer has been produced by radical polymerisation in an aqueous phase using a free radical catalyst.
  • a suitable polyfunctional vinyl compound characterised in that the polymer has been produced by radical polymerisation in an aqueous phase using a free radical catalyst.
  • Ion exchange is the reversible interchange of ions between a solid and liquid in which there is no permanent change in the structure of the solid, which is the ion- exchange material.
  • Ion exchange occurs in a variety of substances - e.g. silicates, phosphates, fluorides, humus, cellulose, wool, proteins, alumina, resins, lignin, cells, glass, barium sulphate, and silver chloride.
  • Ion exchange materials that depend on properties other than the interchange of ions between liquid and solid phase.
  • Ion exchange has been used on an industrial basis since 1910 with the introduction of water softening using natural and, later, synthetic zeolites.
  • the introduction of synthetic organic ion exchange resins in 1935 resulted from the synthesis of phenolic condensation products containing either sulfonic or amine groups which could be used for the reversible exchange of cations or anions.
  • Inorganic ion exchange materials include both the naturally occurring macerials such as the mineral zeolites
  • the green sands and clay e.g. the montmorillonite group
  • synthetic products such as the gel zeolites, the hydrous oxides of polyvalent metals and the insoluble salts of polybaric acids with polyvalent metals.
  • Synthetic organic products include cation and anion ion exchange resins both of strong and weak type.
  • the weak acid, cation-exchange resins are based primarily on acrylic or methacrylic acid that has been crosslinked with a disfunctional monomer - e.g. DVB (divinylbenzene) .
  • DVB divininylbenzene
  • Other weak acid resins have been made with phenolic of phosphonic functional groups.
  • the weak acid resin has a high affinity for the hydrogen ion and, thus is easily regenerated with strong acids.
  • the property limits the region in which salt splitting can occur to above pH 4.
  • the strong acid resins of commercial significance are sulfonated copolymer of styrene and DVB, sulfonic acid, sulfur trioxide, and chlorosulfonic acid have each been utilized for sulfonation.
  • the cation exchanger is preferably a cation resin containing functional groups in acid form. Suitable functional groups include carboxylic or sulphonic acid groups.
  • cationic exchange resins may be used in the practise of the present invention:
  • Amberlite IR 120 which is a strong cation exchanger having sulfonic acid functionality which is available in H* form.
  • the total exchange capacity is 4.4 meq/g for the dry resin.
  • Amberlite IRC 76 which is a weak cation exchanger having carboxylic functionality which is available in acid form.
  • the total exchange capacity is 10 meq/g for dry resin.
  • Dowex 50W YZ which is a strong cation exchanger which is available in H + form having sulfonic acid functionality.
  • the total exchange capacity is 5 meq/g for dry resin.
  • the weight ratio cationic superabsorbent to cation exchanger is in the range 1:20 to 1:1 preferably 1:3 to 1:1 depending on molecular weight and ion exchange capacity.
  • the absorbent material according to the invention is particularly suitable for use in applications where it is desired to absorb electrolyte containing aqueous liquids.
  • liquids include in particular menses and urine and the absorbent material can be used as the filling in catamenials and diapers generally in admixture with a fibrous absorbent such as cellulose fluff.
  • the absorbent according to the invention can be present as granules or fibres.
  • the absorbent materials according to the invention show particularly good absorption of electrolyte containing aqueous liquids as is demonstrated below in the following examples by tests carried out using saline solution ( 1 % NaCl) and synthetic urine.
  • the monomer solution was disareated by vacuum using a vacuum pump.
  • the solid product formed was cut using a spatula and transferred in 5 litre beaker containing 4 litres of distilled water, after two hours the swelled gel was filtered with a nonwoven tissue fabric filter.
  • the gel was dried in a ventilated oven at 60°C for 12 hours.
  • 60g of dried polymer was collected and called Fai 7 Cl.
  • 20g of Fai 7 Cl was placed in a 10 litre beaker and swelled by adding 4 litres of ix distilled water, under continuous stirring.
  • 500 ml of 0.01 M NaOH solution was added and after 30 minutes the gel was filtered using a nonwoven fabric tissue filter.
  • a 1% NaCl solution (150ml) was placed in contact with 2.23g of the cation exchange resin IR120 (H*) in a 250ml beaker for 2 hours under continuous stirring.
  • the sodium ions in the solution should be replaced by the H + ions from the resin.
  • the solution was drawn up with a Pasteur pipette and dropped into another 250ml beaker containing O.llg of Fai 7 OH under stirring; the addition is stopped when the gel swells no more. At this point the gel is placed into a nonwoven tissue "tea bag" small envelope and the absorbency after centrifugation at 60 x g for 10 minutes was measured as follows:
  • Wdry weight of the envelope containing the dry AGM in
  • weight of the AGM used in the test in g.
  • 1% NaCl represents a stringent test of the superabsorbent. Studies in the literature show that the salt content of urine varies depending on a number of factors but 1% by weight represents the maximum likely to the encountered in practice.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Hematology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

L'invention porte sur un matériau superabsorbant fait d'une combinaison (1) d'un superabsorbant cationique dans lequel 20 à 100 % des groupes fonctionnels se présentent sous forme de bases, et (2) d'un échangeur cationique dans lequel 5 à 100 % des groupes fonctionnels se présentent sous forme d'acides. Ladite combinaison s'avère particulièrement efficace comme superabsorbant de solutions contenant un électrolyte telles que le flux menstruel et l'urine.
EP95940681A 1994-11-10 1995-11-13 Materiau absorbant Withdrawn EP0791020A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ITTO940890 1994-11-10
IT94TO000890A IT1267495B1 (it) 1994-11-10 1994-11-10 Materiale assorbente, ad esempio di tipo superassorbente, e relativo uso.
PCT/US1995/014677 WO1996015163A1 (fr) 1994-11-10 1995-11-13 Materiau absorbant

Publications (2)

Publication Number Publication Date
EP0791020A1 true EP0791020A1 (fr) 1997-08-27
EP0791020A4 EP0791020A4 (fr) 2000-07-12

Family

ID=11412880

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95940681A Withdrawn EP0791020A4 (fr) 1994-11-10 1995-11-13 Materiau absorbant

Country Status (10)

Country Link
EP (1) EP0791020A4 (fr)
JP (1) JPH10509752A (fr)
KR (1) KR970707183A (fr)
CN (1) CN1171797A (fr)
AU (1) AU4234996A (fr)
BR (1) BR9509650A (fr)
CZ (1) CZ140897A3 (fr)
HU (1) HUT77843A (fr)
IT (1) IT1267495B1 (fr)
WO (1) WO1996015163A1 (fr)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6951895B1 (en) 1996-12-02 2005-10-04 Kimberly-Clark Worldwide, Inc. Absorbent composition
US6232520B1 (en) 1997-02-19 2001-05-15 The Procter & Gamble Company Absorbent polymer compositions having high sorption capacities under an applied pressure
US6342298B1 (en) 1997-11-19 2002-01-29 Basf Aktiengesellschaft Multicomponent superabsorbent fibers
US6623576B2 (en) 1998-10-28 2003-09-23 Basf Aktiengesellschaft Continuous manufacture of superabsorbent/ion exchange sheet material
US6087448A (en) * 1997-11-19 2000-07-11 Amcol International Corporation Solid superabsorbent material containing a poly(vinylguanidine) and an acidic water-absorbing resin
US6222091B1 (en) 1997-11-19 2001-04-24 Basf Aktiengesellschaft Multicomponent superabsorbent gel particles
US5981689A (en) 1997-11-19 1999-11-09 Amcol International Corporation Poly(vinylamine)-based superabsorbent gels and method of manufacturing the same
US6072101A (en) 1997-11-19 2000-06-06 Amcol International Corporation Multicomponent superabsorbent gel particles
US5962578A (en) * 1997-11-19 1999-10-05 Amcol International Corporation Poly(dialkylaminoalkyl (meth)acrylamide)-based superabsorbent gels
ZA9810779B (en) 1997-12-12 1999-09-21 Kimberly Clark Co Structure having balanced pH profile.
US6639120B1 (en) 1997-12-12 2003-10-28 Kimberly-Clark Worldwide, Inc. Structure having balanced pH profile
US6121509A (en) * 1998-01-07 2000-09-19 The Procter & Gamble Company Absorbent polymer compositions having high sorption capacities under an applied pressure and improved integrity when wet
KR20010031078A (ko) 1998-08-13 2001-04-16 다나카 쇼소 수팽윤성 가교 중합체 조성물 및 그의 제법
US6534554B1 (en) 1999-10-27 2003-03-18 Basf Aktiengesellschaft Multicomponent ion exchange resins
US7696401B2 (en) * 2003-07-31 2010-04-13 Evonik Stockhausen, Inc. Absorbent materials and absorbent articles incorporating such absorbent materials
CN103665411B (zh) * 2012-09-24 2018-08-24 浙江卫星石化股份有限公司 一种高耐盐高吸水倍率的高吸水树脂及其制备方法
CN104475065B (zh) * 2014-12-16 2017-01-18 湖南科技大学 一种高效重金属离子吸附材料及其制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0161763A1 (fr) * 1984-03-26 1985-11-21 Pony Industries Incorporated Polymères gonflables à l'eau avec capacité d'absorbance d'eau élevée
EP0210756A2 (fr) * 1985-06-28 1987-02-04 The Procter & Gamble Company Structures absorbantes et articles absorbants jetables les contenant
WO1992019652A1 (fr) * 1991-05-03 1992-11-12 Società Consortile Ricerche Angelini S.P.A. Polysaccharides cationiques

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2586883A (en) * 1947-06-02 1952-02-26 American Cyanamid Co Stable combination of cation- and anion-exchange resins
US3558744A (en) * 1968-01-05 1971-01-26 Amicon Corp Process for making polyelectrolyte complex resin
JPS51125468A (en) * 1975-03-27 1976-11-01 Sanyo Chem Ind Ltd Method of preparing resins of high water absorbency
JPS5745057A (en) * 1980-09-02 1982-03-13 Shinko Chem Water absorbing material
US4489180A (en) * 1983-12-12 1984-12-18 Exxon Research And Engineering Co. Drag reduction agent utilizing water soluble interpolymer complexes
US5091443A (en) * 1990-02-07 1992-02-25 Becton, Dickinson And Company Composition for gelling liquids
DE4029592C2 (de) * 1990-09-19 1994-07-14 Stockhausen Chem Fab Gmbh Quellmittel und Absorptionsmittel auf Polymerbasis mit verbesserter Abbaubarkeit und verbesserter Absorption von Wasser, wäßrigen Lösungen und Körperflüssigkeiten sowie ihre Verwendung zur Herstellung von Hygieneartikeln und zur Bodenverbesserung

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0161763A1 (fr) * 1984-03-26 1985-11-21 Pony Industries Incorporated Polymères gonflables à l'eau avec capacité d'absorbance d'eau élevée
EP0210756A2 (fr) * 1985-06-28 1987-02-04 The Procter & Gamble Company Structures absorbantes et articles absorbants jetables les contenant
WO1992019652A1 (fr) * 1991-05-03 1992-11-12 Società Consortile Ricerche Angelini S.P.A. Polysaccharides cationiques

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch, Week 198216 Derwent Publications Ltd., London, GB; Class A96, AN 1982-32174E XP002137966 & JP 57 045057 A (SHINKO KAGAKU KOGYO KK), 13 March 1982 (1982-03-13) *
See also references of WO9615163A1 *

Also Published As

Publication number Publication date
KR970707183A (en) 1997-12-01
IT1267495B1 (it) 1997-02-05
CN1171797A (zh) 1998-01-28
ITTO940890A1 (it) 1996-05-10
WO1996015163A1 (fr) 1996-05-23
BR9509650A (pt) 1997-09-16
EP0791020A4 (fr) 2000-07-12
HUT77843A (hu) 1998-08-28
CZ140897A3 (en) 1997-10-15
JPH10509752A (ja) 1998-09-22
ITTO940890A0 (it) 1994-11-10
MX9703444A (es) 1998-07-31
AU4234996A (en) 1996-06-06

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