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WO2001040335A1 - POLYMERES HYDROPHILES FORMANT DE L'HYDROGEL, COMPORTANT DES LIAISONS 1,4-α-D-GLYCOSIDIQUES - Google Patents

POLYMERES HYDROPHILES FORMANT DE L'HYDROGEL, COMPORTANT DES LIAISONS 1,4-α-D-GLYCOSIDIQUES Download PDF

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Publication number
WO2001040335A1
WO2001040335A1 PCT/EP2000/011276 EP0011276W WO0140335A1 WO 2001040335 A1 WO2001040335 A1 WO 2001040335A1 EP 0011276 W EP0011276 W EP 0011276W WO 0140335 A1 WO0140335 A1 WO 0140335A1
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Prior art keywords
forming polymer
acid
hydrophilic hydrogel
water
polymer according
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PCT/EP2000/011276
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German (de)
English (en)
Inventor
Friedrich Engelhardt
Volker Frenz
Norbert Herfert
Ulrich Riegel
Matthias Weismantel
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Basf Aktiengesellschaft
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Publication of WO2001040335A1 publication Critical patent/WO2001040335A1/fr

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    • 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
    • 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
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • 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

  • Hydrophilic hydrogel-forming polymers with 1,4- ⁇ -D-glycosidic bonds are Hydrophilic hydrogel-forming polymers with 1,4- ⁇ -D-glycosidic bonds
  • the present invention relates to hydrophilic hydrogel-forming polymers with acid groups and / or their alkali metal or ammonium salts and 1,4- ⁇ -D-glycosidic bonds which are post-crosslinked and
  • Hydrogels for hygiene articles are often pure acrylic acid polymers.
  • hydrogels with starch as a graft matrix are also known, onto which polyacrylate chains are grafted.
  • Such hydrogels are described, for example, in DE-A-2 612 846, US-A-4 155 888, DE-A-2 840 010, DE-A-3 801 633, EP-A-455 965,
  • the degree of crosslinking achieved by the graft matrix is low, since the grafting efficiency of acrylic acid on starch is extremely low.
  • the present invention was therefore based on hydrogel-forming polymers with both good transport properties and a high final absorption capacity.
  • the base polymers which are subsequently post-crosslinked, are crosslinked polymers with acid groups, which are predominantly present in the form of their salts, generally alkali metal or ammonium salts. Such polymers swell to form gels on contact with aqueous liquids.
  • Such base polymers are, for example, graft (co) polymers of one or more hydrophilic monomers on a suitable graft base c) crosslinked cellulose ethers and esters bearing acid groups, crosslinked carboxymethyl cellulose, or natural products swellable in aqueous liquids with acid groups, for example alginates and carrageenans.
  • Suitable graft bases c) can be of natural or synthetic origin. Examples are cellulose or cellulose derivatives and other polysaccharides and oligosaccharides, polyvinyl alcohol, polyalkylene oxides, in particular polyethylene oxides and polypropylene oxides, polyamines, polyamides and hydrophilic polyesters.
  • Suitable polyalkylene oxides have, for example, the formula
  • R 1 and R 2 independently of one another are hydrogen, alkyl, alkenyl or aryl,
  • X is hydrogen or methyl
  • n is an integer from 1 to 10,000.
  • R 1 and R 2 are preferably hydrogen, (C ⁇ -C) alkyl, (C 2 -C 6 ) alkenyl or phenyl.
  • Polymers obtained by crosslinking polymerization or copolymerization of monoethylenically unsaturated monomers bearing acid groups or their salts are preferred. It is also possible to (co) polymerize these monomers without crosslinking agents and to crosslink them subsequently.
  • Monoethylenically unsaturated monomers a) bearing acid groups are, for example, monoethylenically unsaturated C 3 -C 5 -carboxylic acids or anhydrides such as acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and aconitic acid.
  • monoethylenically unsaturated monomers a) bearing acid groups are, for example, monoethylenically unsaturated C 3 -C 5 -carboxylic acids or anhydrides such as acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, a
  • monoethylenically unsaturated sulfonic or phosphonic acids for example vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, vinylphosphonic acid, vinylphosphonic acid. phosphonic acid, styrene sulfonic acid and 2-acrylamido-2-methylpropane sulfonic acid.
  • the monomers can be used alone or as a mixture with one another.
  • Monomers used with preference are acrylic acid, methacrylic acid, vinylsulfonic acid, acrylamidopropanesulfonic acid or mixtures of these acids, for example mixtures of acrylic acid and methacrylic acid, mixtures of acrylic acid and acrylamidopropanesulfonic acid or mixtures of acrylic acid and vinylsulfonic acid.
  • additional monoethylenically unsaturated compounds b) which do not carry an acid group but are copolymerizable with the monomers bearing acid groups.
  • monoethylenically unsaturated compounds b) which do not carry an acid group but are copolymerizable with the monomers bearing acid groups.
  • these include, for example, the amides and nitriles of monoethylenically unsaturated carboxylic acids, for example acrylamide, methacrylamide and N-vinylformamide, N-vinyl acetamide, N-methyl-N-vinyl acetamide, acrylonitrile and methacrylonitrile.
  • suitable compounds are, for example, vinyl esters of saturated C to C carboxylic acids such as vinyl formate, vinyl acetate or vinyl propionate, alkyl vinyl ethers with at least 2 C atoms in the alkyl group, such as ethyl vinyl ether or butyl vinyl ether, esters of monoethylenically unsaturated C to C 6 carboxylic acids , for example esters from monovalent C 1 -C 4 -alcohols and acrylic acid, methacrylic acid or maleic acid, half-esters of maleic acid, for example monomethyl maleate, N-vinyl lactarne such as N-vinyl pyrrolidone or N-vinyl caprolactam, acrylic acid and methacrylic acid esters of alkoxylated monohydric, saturated alcohols For example, alcohols with 10 to 25 carbon atoms, which have been reacted with 2 to 200 moles of ethylene oxide and / or propylene oxide per mole of alcohol, and monoacrylic acid esters
  • These monomers not bearing acid groups can also be used in a mixture with other monomers, e.g. Mixtures of vinyl acetate and 2-hydroxyethyl acrylate in any ratio. These monomers not carrying acid groups are added to the reaction mixture in amounts between 0 and 50% by weight, preferably less than 20% by weight.
  • Crosslinked polymers from monoethylenically unsaturated monomers bearing acid groups are preferred, which are optionally converted into their alkali metal or ammonium salts before or after the polymerization, and from 0-50% by weight, based on their total weight, of monoethylenically unsaturated monomers bearing no acid groups.
  • Crosslinked polymers of monoethylenically unsaturated C -C carboxylic acids and / or their alkali metal or ammonium salts are preferred.
  • crosslinked polyacrylic acids are preferred, the acid groups of which are 25-100% in the form of alkali or ammonium salts.
  • Water-soluble polymers are also selected as crosslinker d)
  • 1, 4 - ⁇ -D-glycosidic bonds such as starch, glycogen, dextrin and / or cyclodextrin derivatives.
  • Preferred crosslinkers d) are starch, glycogen, dextrin and / or cyclodextrin derivatives with at least two copolymerizable double bonds.
  • Starch derivatives such as allyl starch, meth (acrylate) starch are particularly preferred.
  • crosslinking agents e) are also used which have no 1,4- ⁇ -D-glycosidic bonds.
  • Compounds which have at least 2 ethylenically unsaturated double bonds can function as crosslinking agents e).
  • Examples of compounds of this type are N, N '-methylene bisacrylamide, polyethylene glycol diacrylates and polyethylene glycol dimethacrylates, which are each derived from polyethylene glycols with a molecular weight of 106 to 8500, preferably 400 to 2000, trimethylol propane triacrylate, trimethylol propane trimethacryla, ethylene glycol propylene glycol diacrylate, diacrylate, Butanediol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, allyl methacrylate, diacrylates and dimethacrylates of block copolymers of ethylene oxide and propylene oxide, polyhydric alcohols esterified two or more times with acrylic acid or methacrylic acid, such as glycerol or pentaerythramyldihylly
  • water-soluble crosslinking agents for example N, N '-methylene bisacrylamide, polyethylene glycol diacrylates and polyethylene glycol dimethacrylates, which differ from addition products of 2 to 400 moles of ethylene oxide to 1 mole of a diol or Derive polyols, vinyl ethers of addition products of 2 to 400 moles of ethylene oxide to 1 mole of a diol or polyol, ethylene glycol diacrylate, ethylene glycol dimethacrylate or triacrylates and trimethacrylates of addition products of 6 to 20 moles of ethylene oxide to 1 mole of glycerol, and / or divinyl urea.
  • N, N '-methylene bisacrylamide polyethylene glycol diacrylates and polyethylene glycol dimethacrylates
  • vinyl ethers of addition products of 2 to 400 moles of ethylene oxide to 1 mole of a diol or polyol
  • Suitable crosslinking agents e) are compounds which contain at least one polymerizable ethylenically unsaturated group and at least one further functional group.
  • the functional group of these crosslinkers must be able to react with the functional groups, essentially the acid groups of the monomers.
  • Suitable functional groups are, for example, hydroxyl, amino, epoxy and aziridino groups.
  • N-vinylimidazole, l-vinyl-2-methylimidazole and N-vinylimidazolines such as N-vinylimidazoline, l-vinyl-2-methylimidazoline, l-vinyl-2-ethylimidazoline or l-vinyl-2-propylimidazoline, which are in the form of the free bases , can be used in quaternized form or as a salt in the polymerization.
  • Dialkylaminoalkyl acrylates and dialkylaminoalkyl methacrylates such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate,
  • Diethylaminoethyl acrylate and diethylaminoethyl methacrylate are preferably used in quaternized form or as a salt. Furthermore e.g. Glycidyl (meth) acrylic lat can also be used.
  • the crosslinkers are present in the reaction mixture, for example from 0.001 to 20% by weight and preferably from 0.01 to 14% by weight.
  • the polymerization is initiated as usual by an initiator. It is also possible to initiate the polymerization by the action of electron beams on the polymerizable, aqueous mixture. However, the polymerization can also be initiated in the absence of initiators of the type mentioned above by the action of high-energy radiation in the presence of photoinitiators. All compounds which decompose into free radicals under the polymerization conditions can be used as polymerization initiators, for example peroxides, hydroperoxides, hydrogen peroxide, persulfates, azo compounds and the so-called redox catalysts. The use of water-soluble initiators is preferred.
  • mixtures of different polymerization initiators for example mixtures of hydrogen peroxide and sodium or potassium peroxodisulfate.
  • Mixtures of hydrogen peroxide and Sodium peroxodisulfate can be used in any ratio.
  • Suitable organic peroxides are, for example, acetylacetone peroxide, methyl ethyl ketone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert. -Amylperpivalate, tert-butylperpivalate, tert. Butyl perneohexanoate, tert. -Butylperisobuty- rat, tert.
  • Particularly suitable polymerization initiators are water-soluble azo starters, for example 2,2′-azobis- (2-amidinopropane) dihydrochloride, 2,2′-azobis- (N, N′-dimethylene) isobutyramidine-dihydrochloride, 2- (carbamoylazo) isobutyronitrile , 2, 2 '-azobis [2- (2' - imidazolin-2-yl) propane] dihydrochloride and 4, 4 '-azobis (4-cyano-valeric acid).
  • the polymerization initiators mentioned are used in customary amounts, for example in amounts of 0.01 to 5, preferably 0.1 to 2.0% by weight, based on the monomers to be polymerized.
  • Redox catalysts are also suitable as initiators.
  • the redox catalysts contain at least one of the above-mentioned per compounds as the oxidizing component and, for example, ascorbic acid, glucose, sorbose, ammonium or alkali metal hydrogensulfite, sulfite, thiosulfate, hyposulfite, pyrosulfite or sulfide as the reducing component , Metal salts, such as iron (II) ions or sodium hydroxymethyl sulfoxylate.
  • Ascorbic acid or sodium sulfite is preferably used as the reducing component of the redox catalyst. Based on the amount of monomers used in the polymerization, for example 3-10 -6 to 1 mol% of the reducing component of the redox catalyst system and 0.001 to 5.0 mol% of the oxidizing component of the redox catalyst are used.
  • photoinitiators are usually used as initiators. These can be, for example, so-called ⁇ -splitters, H-abstracting systems or also azides.
  • initiators are benzophenone derivatives such as Michlers ketone, phenanthrene derivatives, fluorene derivatives, anhraquinone derivatives, thioxanone derivatives, coumarin derivatives, benzoin ethers and their derivatives, azo compounds such as the radical formers mentioned above, substituted hexaarylbisimidazoles or acylphosphine oxides.
  • azides examples include: 2- (N, N-dimethylamino) ethyl 4-azidocinnamate, 2- (N, N-dimethylamino) ethyl 4-azidonaphthyl ketone, 2- (N, N-dimethylamino) ethyl 4-azidobenzoate, 5-azido-1-naphthyl-2 '- (N, N-dimethylamino) ethylsulfone, N- (4-sulfonyl azidophenyl) maleimide , N-acetyl-4-sulfonylazidoaniline, 4-sulfonylazidoaniline, 4-azidoaniline, 4-azidophenacyl bromide, p-azidobenzoic acid, 2, 6-bis (p-azidobenzylidene) cyclohexanone and 2, 6-bis (p-azidobenzylid
  • crosslinking agents e) which have at least two groups which are reactive toward acid groups. These crosslinkers can be added before, during or after the radical polymerization. The reaction can take place at room temperature or at elevated temperatures up to 200 ° C., depending on the reactivity of the crosslinking agent. Depending on this, there is a subsequent crosslinking of polymers which have been produced by the polymerization of the abovementioned monoethylenically unsaturated acids and, if appropriate, monoethylenically unsaturated comonomers and which have a molecular weight greater than 5000, preferably greater than 50,000, or a crosslinking which takes place parallel to chain growth.
  • crosslinking agents are ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerol, polyglycerol, propylene glycol, polypropylene glycol, block copolymers of ethylene oxide and propylene oxide, ethanolamine, sorbitan fatty acid ester, ethoxylated sorbitan fatty acid ester, trimethylol-3-propylene ester, trimethylol-3-propylene ester, trimethylol-3-propylene ester, trimethylol-3-propylene ester, trimethylol-1-propylene ester, trimethylol-3-fatty acid ester, trimethylol-3-fatty acid ester, trimethylol-3-fatty acid ester, trimethylol-1-fatty acid ester, trimethylol-3-fatty acid ester, trimethylol-3-fatty acid ester, trimethylol-1-fatty acid ester, trimethylol-3-fatty acid ester, trimethylo
  • crosslinkers e) are polyvalent metal ions which are able to form ionic crosslinks.
  • examples of such crosslinkers are magnesium, calcium, barium and aluminum ions.
  • These crosslinkers are added, for example, as hydroxides, carbonates or hydrogen carbonates to the aqueous polymerizable solution.
  • crosslinkers e) are multifunctional bases which are also able to form ionic crosslinks, for example polyamines or their quaternized salts.
  • polyamines are ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine and polyethyleneimines, and also polyvinylamines with molecular weights of up to 4,000,000 each.
  • the crosslinking agents e) are added to the acid-bearing polymers or salts in amounts of 0.1 to 25% by weight, preferably 0.1 to 15% by weight, based on the amount of the polymer used.
  • the crosslinked polymers are preferably used in neutralized form. However, the neutralization can also have been carried out only partially. The degree of neutralization is preferably 25 to 100%, in particular 50 to 100%. Alkali metal bases or ammonia or amines can be used as neutralizing agents. Sodium hydroxide solution or potassium hydroxide solution are preferably used. However, the neutralization can also be carried out with the aid of sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate or other carbonates or hydrogen carbonates. Furthermore, prim. , sec. and tert. Amines can be used.
  • Polymerization in aqueous solution is preferred as so-called gel polymerization. 10 to 70% by weight aqueous solutions of the monomers and, if appropriate, a suitable one Graft base polymerized in the presence of a radical initiator using the Trommsdorff-Norrish effect.
  • the polymerization reaction can be carried out in the temperature range between 0 and 150.degree. C., preferably between 10 and 100.degree. C., both under normal pressure and under elevated or reduced pressure.
  • the polymerization can also be carried out in a protective gas atmosphere, preferably under nitrogen.
  • the quality properties of the polymers can be improved further by reheating the polymer gels for several hours in the temperature range from 50 to 130 ° C., preferably from 70 to 100 ° C.
  • the surface postcrosslinking can take place in a manner known per se with dried, ground and sieved polymer particles.
  • compounds which can react with the functional groups of the polymers with crosslinking are preferably applied to the surface of the hydrogel particles in the form of a water-containing solution.
  • the water-containing solution can contain water-miscible organic solvents. Suitable solvents are alcohols such as methanol, ethanol, i-propanol or acetone.
  • Di- or polyglycidyl compounds such as phosphonic acid diglycidyl ether or ethylene glycol diglycidyl ether, bischlorohydrin ether of polyalkylene glycols,
  • Polyols such as ethylene glycol, 1,2-propanediol, 1,4-butanediol, glycerol, methyltriglycol, polyethylene glycols with an average molecular weight M w of 200-10000, di- and polyglycerol, pentaerythritol, sorbitol, the oxyethylates of these poly- oils and their esters with carboxylic acids or carbonic acid such as ethylene carbonate or propylene carbonate,
  • Carbonic acid derivatives such as urea, thiourea, guanidine, dicyandiamide, 2-oxazolidinone and its derivatives, bisoxazoline, polyoxazolines, di- and polyisocyanates,
  • Di- and poly-N-methylol compounds such as methylene bis (N-methylol methacrylamide) or melamine-formaldehyde resins,
  • Compounds with two or more blocked isocyanate groups such as trimethylhexamethylene diisocyanate blocked with 2,2,3,6-tetramethyl-piperidinone-4.
  • Suitable surface postcrosslinkers are also ions of polyvalent metals, as already listed under e).
  • acidic catalysts such as p-toluenesulfonic acid, phosphoric acid, boric acid or ammonium dihydrogen phosphate can be added.
  • Particularly suitable surface postcrosslinking agents are di- or polyglycidyl compounds such as n-propylphosphonic acid diglycidyl ether and monoethylene glycol diglycidyl ether.
  • the crosslinking agent solution is preferably applied by spraying on a solution of the crosslinking agent in conventional reaction mixers or mixing and drying systems.
  • a temperature treatment step can follow, preferably in a downstream dryer, at a temperature of 80 to 230 ° C, and preferably 100-160 ° C, over a period of 5 minutes to 6 hours, preferably 10 minutes to 2 hours and particularly preferably 10 minutes to 1 hour, it being possible for both cleavage products and solvent fractions to be removed.
  • drying can also take place in the mixer itself, by heating the jacket or by blowing in a preheated carrier gas.
  • the outstanding properties of the polymers according to the invention can be explained by the 1,4- ⁇ -D-glycosidic bonds of the crosslinking sites. These bonds can be released by the amylase that occurs in the urine. It is thus possible to produce a highly cross-linked polymer which can change its properties depending on the application.
  • the polymers according to the invention are notable for good transport properties, especially in the initial phase, and yet have a high final absorption capacity.
  • the present invention further relates to hygiene articles comprising
  • (E) optionally a receiving layer located between (A) and (C).
  • Hygiene articles mean both incontinence pads and incontinence pants for adults and diapers for babies.
  • the liquid-permeable cover (A) is the layer that has direct skin contact.
  • the material is conventional synthetic and semi-synthetic fibers or films such as polyester, polyolefms, rayon or natural fibers such as cotton. In the case of non-woven materials, the fibers are usually connected by binders such as polyacrylates. Preferred materials are polyester, rayon and their blends, polyethylene and polypropylene.
  • the liquid-impermeable layer (B) generally consists of a film made of polyethylene or polypropylene.
  • the core (C) contains, in addition to the hydrogel-forming polymer (CD, hydrophilic fiber material (C2).
  • Hydrophilic is understood to mean that aqueous liquids are rapidly distributed over the fiber.
  • the fiber material is usually cellulose, modified cellulose , Rayon, polyester such as polyethylene terephthalate. Cellulose fibers such as cellulose are particularly preferred.
  • the fibers generally have a diameter of 1 to 200 ⁇ m, preferably 10 to 10 ⁇ m. Furthermore, the fibers have a minimum length of 1 mm.
  • the proportion of the hydrophilic fiber material based on the total amount of the core is preferably 10-80% by weight, particularly preferably 40-70% by weight.
  • the structure and shape of diapers is generally known and is described, for example, in EP-A-0 316 518 and EP-A-0 202 127.
  • the CRC parameter is determined by measuring the CRC in two different test solutions:
  • hydrogel-forming polymer (grain fraction 106 - 850 ⁇ m) is weighed into a 60 x 85 mm tea bag, which is then sealed. The tea bag is then added to an excess of 0.9% by weight saline solution (at least 0.83 1 saline solution / 1 g hydrogel-forming polymer). After 4 hours of swelling, the tea bag is removed from the saline solution and centrifuged at 250 G for three minutes. The amount of liquid held by the hydrogel-forming polymer is determined by weighing the centrifuged tea bag.
  • the determination of the CRC II is carried out analogously to the determination of the CRC I, but a 0.9 wt. % sodium chloride solution, which additionally contains 0.56 g of amylase (BAN 240 from Novo Nordisc A / S) contains per 1000 ml of saline solution, so that the amylase activity is 250 U / 1.
  • the test apparatus for determining the vertical absorption consists of measuring cells and a liquid container.
  • the measuring cells represent a cylindrical Plexiglas tube with an inner diameter of 2.6 cm and a length of 15 cm.
  • the upper end of the tube is open, the lower end of the tube has a 36 ⁇ m
  • the tube At a height of 3 cm (from the lower end of the tube) the tube has a support ring.
  • the liquid container is a plexiglass box 28.5 cm long, 20.5 cm wide and 3.8 cm high.
  • the plexiglass case has a removable lid, which is provided with 6 circular holes, each with a diameter of 3.2 cm.
  • 1 g of hydrogel-forming polymer is weighed into a measuring cell, hydrogel-forming polymer particles being evenly distributed on the sieve bottom.
  • the hydrogel-forming polymer particles are covered with a plexiglass disk that can go through the wall and a plexiglass cylinder with a metal handle that goes through the wall is introduced, the total weight of the plexiglass disk and the cylinder with a handle being 100 g, so that a pressure of 20 g / cm is applied to the polymer particles 2 burdens.
  • the liquid container is 0.9 wt. -% sodium chloride solution, which is colored with 10 mg of the dye Amido Blue A-PW (Hoechst AG), filled, so that the upper liquid level is 1 cm outside the lid.
  • the measuring cell is then immersed in the liquid through a hole in the lid (immersion depth: 1.5 cm), the measuring cell being held by the support ring.
  • measuring cells Up to 6 measuring cells can be measured at the same time.
  • the measuring cells are left in the liquid container for 60 minutes, the hydrogel-forming polymer particles swelling to absorb liquid against gravity under additional weight. Due to the very high area coverage of hydrogel-forming polymer particles, a high permeability of the gel layer and a high capillarity are necessary to achieve a high swelling height.
  • the measuring cell is removed from the liquid container and the quantity of liquid taken up is determined by weighing.
  • 300 g of starch flour were 50 wt.
  • a stirred autoclave in 1800 ml. -% aqueous isopropanol suspended.
  • the suspension was heated to 50 ° C. for 1 hour while passing nitrogen through stirred at this temperature and with 25 g 50 wt. -% sodium hydroxide solution and mixed with 1.5 g of benzyltrimethylammonium hydroxide as a phase transfer catalyst.
  • After adding 12 g of allyl chloride the reaction mixture was stirred at 50 ° C. for 8 hours, cooled and neutralized with acetic acid.
  • the starch derivative was filtered off, twice with 50 wt. - Washed once and with 100% isopropanol and air dried. The degree of substitution was 0.05.
  • Starch types were suspended in 1055.7 g of water, heated to 70-75 ° C., held at this temperature for 30 minutes and then cooled again to room temperature). Furthermore, the amount of methylene bisacrylamide was halved (1.04 g). The products obtained were modified by post-crosslinking analogously to the comparative example. Their application properties are shown in Table 1.
  • the initiator system consisting of 2.5 g of 2,2'-azobisamidinopropane dihydrochloride, dissolved in 20 g of deionized water, 4 g of potassium peroxodisulfate, dissolved in 50 g of deionized water and 0.4 g of ascorbic acid, dissolved in 20 g, was added demineralized water one after the other with stirring.
  • the reaction solution was left to stand without stirring, a solid gel being formed as a result of the polymerization which began, in the course of which the temperature rose to approximately 90.degree.

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  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Hematology (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne des polymères hydrophiles formant de l'hydrogel, comportant des groupes acides et/ou leurs sels alcalins ou d'ammonium, et des liaisons 1,4-α-D-glycosidiques, ces polymères étant post-réticulés en surface et présentant a) un paramètre de capacité de rétention centrifuge (CRC) 1,10 et b) une absorption verticale d'au moins 12 g/g. L'invention concerne également un procédé de fabrication de ces polymères, ainsi que leur utilisation pour l'absorption de liquides aqueux, en particulier pour l'absorption de liquides corporels dans des articles d'hygiène pour adultes et bébés.
PCT/EP2000/011276 1999-11-29 2000-11-15 POLYMERES HYDROPHILES FORMANT DE L'HYDROGEL, COMPORTANT DES LIAISONS 1,4-α-D-GLYCOSIDIQUES WO2001040335A1 (fr)

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US45094899A 1999-11-29 1999-11-29
US09/450,948 1999-11-29

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010144575A1 (fr) 2009-06-09 2010-12-16 William Chambers Matériau absorbant biodégradable et procédé de fabrication
CN102093513A (zh) * 2010-12-20 2011-06-15 昆明理工大学 马铃薯淀粉接枝丙烯酸制备吸水树脂的方法
TWI621633B (zh) * 2010-06-09 2018-04-21 威廉 錢伯斯 生物可降解吸收材料及其製造方法
AU2016340267B2 (en) * 2015-10-15 2021-07-01 Tryeco, Llc Biodegradable absorbent material and method of manufacture

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DE3801633A1 (de) * 1988-01-21 1989-07-27 Starchem Gmbh Verfahren zur herstellung von wasserabsorbierenden und wasserquellbaren polysaccharid-pfropfpolymeren
USH1032H (en) * 1989-04-20 1992-03-03 A. E. Staley Manufacturing Company Process for manufacturing starch-based compositions
WO1995027739A1 (fr) * 1994-04-11 1995-10-19 Hoechst Celanese Corporation Polymeres super-absorbants et produits fabriques avec eux
DE19630131A1 (de) * 1995-09-04 1997-03-06 Sanyo Chemical Ind Ltd Verfahren zur Herstellung von wasserabsorbierenden Harzen
EP0881238A2 (fr) * 1997-05-28 1998-12-02 Clariant GmbH Composition de polymère hydrophile gonflabe à l'eau
WO1999064485A1 (fr) * 1998-06-08 1999-12-16 Stockhausen Gmbh & Co. Kg Polymeres hydro-absorbants avec des molecules creuses supramoleculaires, leur procede de preparation et leur utilisation

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DE3801633A1 (de) * 1988-01-21 1989-07-27 Starchem Gmbh Verfahren zur herstellung von wasserabsorbierenden und wasserquellbaren polysaccharid-pfropfpolymeren
USH1032H (en) * 1989-04-20 1992-03-03 A. E. Staley Manufacturing Company Process for manufacturing starch-based compositions
WO1995027739A1 (fr) * 1994-04-11 1995-10-19 Hoechst Celanese Corporation Polymeres super-absorbants et produits fabriques avec eux
DE19630131A1 (de) * 1995-09-04 1997-03-06 Sanyo Chemical Ind Ltd Verfahren zur Herstellung von wasserabsorbierenden Harzen
EP0881238A2 (fr) * 1997-05-28 1998-12-02 Clariant GmbH Composition de polymère hydrophile gonflabe à l'eau
WO1999064485A1 (fr) * 1998-06-08 1999-12-16 Stockhausen Gmbh & Co. Kg Polymeres hydro-absorbants avec des molecules creuses supramoleculaires, leur procede de preparation et leur utilisation

Non-Patent Citations (1)

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Title
HELLER J ET AL: "DEVELOPMENT OF ENZYMATICALLY DEGRADABLE PROTECTIVE COATINGS FOR USE IN TRIGGERED DRUG DELIVERY SYSTEMS: DERIVATIZED STARCH HYDROGELS", BIOMATERIALS,GB,ELSEVIER SCIENCE PUBLISHERS BV., BARKING, vol. 11, no. 5, 1 July 1990 (1990-07-01), pages 345 - 350, XP000140305, ISSN: 0142-9612 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010144575A1 (fr) 2009-06-09 2010-12-16 William Chambers Matériau absorbant biodégradable et procédé de fabrication
EP2440590A1 (fr) * 2009-06-09 2012-04-18 William Chambers Matériau absorbant biodégradable et procédé de fabrication
EP2440590A4 (fr) * 2009-06-09 2013-12-04 William Chambers Matériau absorbant biodégradable et procédé de fabrication
TWI621633B (zh) * 2010-06-09 2018-04-21 威廉 錢伯斯 生物可降解吸收材料及其製造方法
CN102093513A (zh) * 2010-12-20 2011-06-15 昆明理工大学 马铃薯淀粉接枝丙烯酸制备吸水树脂的方法
CN102093513B (zh) * 2010-12-20 2012-10-31 昆明理工大学 马铃薯淀粉接枝丙烯酸制备吸水树脂的方法
AU2016340267B2 (en) * 2015-10-15 2021-07-01 Tryeco, Llc Biodegradable absorbent material and method of manufacture

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