WO1994025521A1 - Compositions polymeres, production de compositions polymeres, notamment de materiaux absorbants, et leur utilisation - Google Patents

Compositions polymeres, production de compositions polymeres, notamment de materiaux absorbants, et leur utilisation Download PDF

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Publication number
WO1994025521A1
WO1994025521A1 PCT/EP1993/001062 EP9301062W WO9425521A1 WO 1994025521 A1 WO1994025521 A1 WO 1994025521A1 EP 9301062 W EP9301062 W EP 9301062W WO 9425521 A1 WO9425521 A1 WO 9425521A1
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WIPO (PCT)
Prior art keywords
water
component
acid
weight
components
Prior art date
Application number
PCT/EP1993/001062
Other languages
German (de)
English (en)
Inventor
Uwe Günther
Helmut Klimmek
Helmut Brüggemann
Original Assignee
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
Priority claimed from DE19924206850 external-priority patent/DE4206850C2/de
Priority to ES93909539T priority Critical patent/ES2107021T3/es
Priority to US08/535,070 priority patent/US5736595A/en
Priority to KR1019950704846A priority patent/KR100292923B1/ko
Priority to PCT/EP1993/001062 priority patent/WO1994025521A1/fr
Priority to RU95122614A priority patent/RU2146270C1/ru
Priority to PL93311586A priority patent/PL174749B1/pl
Priority to JP6523786A priority patent/JPH08509511A/ja
Priority to EP93909539A priority patent/EP0701587B1/fr
Priority to AU40296/93A priority patent/AU677581B2/en
Priority to DE59307096T priority patent/DE59307096D1/de
Application filed by Chemische Fabrik Stockhausen Gmbh filed Critical Chemische Fabrik Stockhausen Gmbh
Priority to CA002161904A priority patent/CA2161904C/fr
Priority to SK1316-95A priority patent/SK280641B6/sk
Priority to TW082103723A priority patent/TW311922B/zh
Publication of WO1994025521A1 publication Critical patent/WO1994025521A1/fr
Priority to FI955226A priority patent/FI955226A/fi
Priority to BG100175A priority patent/BG62857B1/bg

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/26—Cellulose ethers
    • C08L1/28—Alkyl ethers
    • C08L1/286—Alkyl ethers substituted with acid radicals, e.g. carboxymethyl cellulose [CMC]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00

Definitions

  • the invention relates to polymer material compositions and the production of a polymer composition and, in particular, absorption materials which are based predominantly on renewable raw materials and are therefore in principle also biodegradable. Due to the predominantly native origin, the absorbers contain no or significantly smaller amounts of residual monomers than polyacrylate-based absorbers.
  • the absorbers according to the invention have a comparatively high absorption capacity and speed, even under pressure, for water and aqueous solutions, show no tendency to gel blocking (gel blocking: when in contact with water, the outer layers of the absorber stick together and prevent another Penetration of the liquid into the absorber) and are mechanically stable (with respect to the separation into the individual components). When swollen, they separate into individual particles, they are not aqueous and have a very high gel stability.
  • the invention further relates to a process for their production and their use as fiber, film, powder or granulate for the absorption of water, aqueous solutions or aqueous dispersions and body fluids, in hygiene agents such as tampons or diapers and animal hygiene articles, in chemical -technical products such as packaging materials, in particular for meat and fish, in culture vessels and for soil improvement and as cable sheathing.
  • Most of the absorption materials used today also called superabsorbers, which are able to absorb large amounts of liquids (water, urine) in a short time, are primarily weakly cross-linked polyacrylates and are therefore not based on renewable raw materials and are comparatively inadequate or not biodegradable at all.
  • polysaccharides into the polymerization gel of polyacrylates, as described in DE-OSs 40 29 591, 40 29 592 and 40 29 593, the polyacrylates can only be used up to max. 25% can be replaced without a significant deterioration in the absorption capacity and other properties of the resulting superabsorbers, even if various auxiliary substances such as fibers and e.g. Aluminum crosslinkers are added.
  • the polysaccharides are seen as building blocks for the absorbers in order to obtain biodegradable units.
  • DE-PS 3132976 describes the mixing of polyacrylic acid with polysaccharides in powder form and in solution, the shell of the absorber particles of the mixtures being crosslinked with aluminum crosslinking agents such as Al (OH) 2 OOCCH 3 * 1/3 H 3 B0 3 . Accordingly, no superabsorbers can be produced with this method, which consist of over 60% of renewable raw materials. In the processes described so far according to the current state of the art, the polysaccharides have no decisive contribution as an absorption component.
  • absorbers have good absorption properties, but show block phenomena.
  • absorbers are easily separated by mechanical loads, such as screening or conveying, so that they are no longer present as a homogeneous product, which greatly limits their possible uses.
  • EP-PS 0 201 895 also describes the production of an absorber based on carboxymethyl cellulose. However, the manufacture of these absorbers is carried out in an aqueous solution in which the carboxymethyl cellulose is only present in a low concentration
  • REPLACEMENT LEAF is present. Furthermore, larger amounts of organic solvents such as acetone, methanol, etc. are required in the production. The production of these carboxymethyl cellulose absorbers also requires a great deal of time. The absorbers themselves show block phenomena and a low gel strength.
  • the object of the present invention was to provide and produce a polymer composition, in particular an absorber, which does not have the deficiencies described above and which has the following properties: a)
  • the absorber should consist predominantly of components of native origin and thus basically also be biodegradable.
  • the absorbers should have a high mechanical strength, they may become sieved or e.g. do not separate them into their individual components when conveying screws.
  • the absorbers should have a comparatively high absorption speed and capacity for water and aqueous solutions.
  • the content of residual monomers should be significantly lower than in conventional absorbers based on polyacrylates.
  • the absorbers should have a very high gel stability when swollen; the absorber grains should be separated and be present in individual particles. f) You must not be prone to gel blocking. g) The absorbers should have a high absorption rate and absorption capacity under pressure for water and aqueous solutions. Another object is to provide an active ingredient composition, its production and use.
  • the first object is achieved by a polymer composition and a production process for a polymer composition, in particular an absorbent, which essentially consists of four components:
  • component B which consists of a special water-soluble polymer
  • the present invention relates to a polymer composition, in particular absorbent material composition, consisting essentially of
  • ком ⁇ онент A based on water-soluble and / or water-swellable polymers based on polysaccharides, and their derivatives, which may have been modified by crosslinking and
  • a component B based on water-swellable synthetic polymers and / or copolymers based on (meth) acrylic acid, (meth) acrylonitrile, (meth) acrylamide, vinyl acetate, vinyl pyrrolidone, vinyl pyridine, Maleic acid (anhydride), itaconic acid (anhydride), fumaric acid, vinyl sulfonic acid and / or 2-acrylamido-2-methylpropanesulfonic acid as well as the amides, N-alkyl derivatives, the N, N'-dialkyl derivatives, hydroxyl group-containing esters and amino group-containing esters of these polymerizable acids, where
  • REPLACEMENT LEAF Components as well as 0.1-30% by weight, based on these polymer components, of a matrix material with a melting point or softening point below 180 ° C to prevent segregation and gel blocking
  • the present invention thus further relates to a process for producing a polymer composition, in particular an absorber material, consisting essentially of 70-99.99% by weight of a component A based on water-soluble and / or water-swellable polymers based on Polysaccharides and their derivatives, which may have been modified by crosslinking and 0.01-30% by weight of a component B, based on water-swellable synthetic polymers and / or copolymers based on (meth) acrylic acid, (meth) Acrylonitrile, (meth) acrylamide, vinyl acetate, vinyl pyrrolidone, vinyl pyridine, maleic acid (anhydride), itaconic acid (anhydride), fumaric acid, vinyl sulfonic acid and / or 2-acrylamido-2-methylpropanesulfonic acid and the amides, N-alkyl derivatives, the N, N ⁇ dialkyl derivatives, hydroxyl group-containing esters and amino group-containing esters of these polyme
  • component B acrylic acid of such an absorber is significantly lower than that of polyacrylate-based absorbers.
  • component B is achieved, for example, by swelling them together in water or in an aqueous solution and subsequent drying. Surprisingly, this method leads to a significant increase in the AUL value; moreover, surprisingly, the proportion of component B can be significantly reduced without impairing the absorption properties of the product.
  • these absorbers have a gel strength which is significantly higher than that of absorbers which are based on polyacrylic acid.
  • Suitable as component A are water-soluble and water-swellable polymers based on polysaccharides and their derivatives, such as guar, carboxymethyl guar, xanthan, alginates, gum arabic, hydroxyethyl or hydroxypropyl cellulose, carboxymethyl cellulose and other cellulose derivatives, starch and starch derivatives such as carboxymethyl starch and mixtures thereof the individual polysaccharides.
  • the preferred polymers are guar and the anionic derivatives of starch, guar and cellulose, carboxymethyl cellulose being a particularly preferred material.
  • the listed polymers of component A can be modified by crosslinking in order to reduce their water solubility and to achieve better swelling properties.
  • the crosslinking can take place both in the entire polymer or else only on the surface of the individual polymer particles.
  • the polymers can be reacted with ionic crosslinking agents such as calcium, aluminum, zirconium, iron (III) and titanium compounds.
  • ionic crosslinking agents such as calcium, aluminum, zirconium, iron (III) and titanium compounds.
  • polyfunctional carboxylic acids such as citric acid, mucic acid, tartaric acid, malic acid, malonic acid, succinic acid, glutaric acid, adipic acid, with alcohols such as polyethylene glycols, glycerol, pentaerythritol, propanediols, sucrose, with carbonic acid esters such as ethylene and propylene carbonate
  • Amines such as polyoxypropylene amines, with epoxy compounds such as ethylene glycol diglydcidyl ether, glycol di- or triglycidyl ether and epichlorohydrin, with acid anhydrides such as succinic anhydride and maleic anhydride, with aldehydes and multifunctional (activated) ole
  • water-swellable synthetic polymers or copolymers are primarily based on (meth) acrylic acid and also on the basis of (meth) acrylonitrile, (meth) acrylamide, vinyl acetate, vinyl pyrrolidone, vinyl pyridine, maleic acid, maleic anhydride, Itaconic acid, itaconic anhydride, fumaric acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and also the amides, their N and N, N'-dialkyl derivatives, hydroxyl-containing esters and aminogroup-containing esters of the polymerizable acids are suitable.
  • Crosslinked, partially neutralized polyacrylates are preferred. Up to 98%, preferably 50-80%, of the acid groups can be neutralized.
  • the polymers can be crosslinked by an at least bifunctional crosslinker.
  • polymers are prepared by known processes (DE-PS 27 06 135, DE-OS 40 15 085).
  • a particularly preferred material as component B are polyacrylates, for example the FAVOR R types manufactured by Chemische Fabrik Stockhausen GmbH.
  • Components A and B can be chemical, i.e. via ester linkages or by one of the crosslinkers mentioned or physically, i.e. in the sense of an "Interpenetrating Network” (IPN).
  • IPN Interpenetrating Network
  • Suitable as a matrix are organic solids that melt or soften below 180 ° C and preferably have a soft consistency at room temperature, e.g. Triglycerine monostearate. Highly viscous liquids such as Castor oil suitable.
  • Polycaprolactones such as TONE 0230 and 0240 from Union Carbide, which can also be modified, such as e.g. by reaction with maleic anhydride.
  • the matrix presumably gives the absorber system greater mechanical strength through chemical and / or physical interactions, as a result of which the individual components are separated by transport processes, such as by means of a Screw conveyor, or is greatly reduced by screening processes.
  • an absorption medium can be produced which not only has high absorption values, but is also present in its area of use as a more homogeneous and thus more effective system after assembly or incorporation.
  • the embedding of the absorption material in the matrix surprisingly brings about a significant reduction or a complete elimination of the gel blocking, thus ensuring a high absorption rate in the entire absorber.
  • the crosslinker is firmly fixed to the surface of the individual absorber particles by the matrix.
  • the granulation of superabsorbent fines by agglomeration aids is described in the examples of DE-PS 37 41 157 and DE-PS 39 17 646.
  • the products thus produced have a high absorption rate for water and aqueous solutions. However, these products consist only of polyacrylates and are consequently comparatively inadequate or not biodegradable at all.
  • the agglomeration agents only serve to granulate a product and never as a matrix material.
  • the anti-blocking agents also reduce gel blocking; they therefore effect a faster and better absorption of liquid and ensure that the gels separate, i.e. exist in individual particles.
  • Suitable anti-blocking agents are known (see. DE-PS 31 41 098 and DE-PS 33 13 344) fiber materials and other materials with a large surface area.
  • the fibers can be natural or synthetic fibers, e.g. Wool, cotton, silk and cellulose fibers, or polyamide, polyester, polyacrylonitrile, polyurethane fibers, fibers of olefins and their substitution products as well as polyvinyl alcohol and their derivatives. Examples for anor
  • REPLACEMENT LEAF ganic materials are bentonites, zeolites, aerosils and activated carbons.
  • Suitable crosslinking agents are compounds which convert the polymers described above into a state in which the water solubility is reduced, the absorbency is improved and the blocking phenomena are reduced.
  • Metal compounds which can interact with the functional groups of the polymers are suitable as ionic crosslinkers.
  • Preferred carboxylic acids are acetic acid, lactic acid, salicylic acid, propionic acid, benzoic acid, fatty acids, malonic acid, succinic acid, glutaric acid, adipic acid, citric acid, tartaric acid, malic acid and mucic acid.
  • Preferred inorganic anions are chlorides, bromides, hydrogen sulfates, sulfates, phosphates, borates, nitrates, hydrogen carbonates and carbonates.
  • the water-soluble crosslinking agent brings about crosslinking of components A and B, both with one another and between one another, particularly on the surface, as a result of which, as in DE-PS 31 32 976, DE-PS 26 09 144 and US Pat. No. 4 959 341, the absorption properties are improved.
  • Polyfunctional carboxylic acids, alcohols, amines, epoxy compounds, carboxylic anhydrides and aldehydes and their derivatives are suitable as covalent crosslinking agents.
  • Examples are Ci tronic acid, mucic acid, tartaric acid, malic acid, malonic acid, succinic acid, glutaric acid, adipic acid, polyethylene glycols, glycerol, propanediols, polyoxypropylene amines, epichlorohydrin, ethylene glycol diglycidyl ether, glycol diglycidyl ether, succinic acid carbonate and ethylene carbonate anhydride, maleic acid anhydride, maleic acid anhydride, maleic acid anhydride, maleic acid anhydride, maleic acid anhydride, maleic acid anhydride, maleic acid anhydride, maleic acid anhydride, maleic acid anhydride, maleic acid anhydride, maleic acid anhydride, maleic acid anhydride, maleic acid anhydride, maleic acid anhydr
  • Natural derivatives of the compound classes mentioned are also suitable, as are heterofunctional compounds with different functional groups of the compound classes mentioned above.
  • the proportion of component A in the ratio of component A to component B is 70 to 99.99% by weight, preferably 75 to 95% by weight.
  • the proportion of component B is 0.01 to 30% by weight, preferably 5-25% by weight.
  • component B brings about a strong improvement in the absorption properties, especially in the absorbency. This enables a surprisingly significant improvement in the absorption properties compared to pure carboxymethyl cellulose material (CMC material).
  • CMC material carboxymethyl cellulose material
  • the amount of anti-blocking agent is preferably between 0.5 and 50% by weight, particularly preferably 5 to 15% by weight, based on components A and B.
  • the amount of crosslinker in the absorber is 0.001-10% by weight, preferably 3-7% by weight, based on components A and B.
  • matrix material based on components A and B, should be between 0.1-30% by weight, preferably between 2.5 and 7.5% by weight.
  • the matrix material prevents the absorption material from falling apart, as is the case with pure physical mixtures such as e.g. US-A-4 952 550 is observed and additionally prevents gel blocking.
  • Step 1) Component A and component B are mixed physically in dry form at room temperature. Then they are allowed to swell with stirring in water or in an aqueous solution together. After 15 to 360 minutes, the material obtained is dried at 40 ° C. to 180 ° C. in a drying cabinet. The product obtained is then ground.
  • Step 2) The material obtained is mixed with the anti-blocking agent and the matrix component until a homogeneous mixture is obtained.
  • the components are mixed in suitable mixers such as screw mixers, fluidized bed mixers, disk mixers or belt mixers.
  • the heat treatment takes place at 25 ° C to 180 ° C, preferably at 100 ° C - 120 ° C.
  • the heating time is 5 to 60 minutes, preferably 20 to 40 minutes.
  • Ordinary dryers or heating ovens e.g. disc dryers, belt dryers, fluidized bed dryers or infrared dryers are used for the heat treatment of the product.
  • Step 3 The ionic crosslinking agent, preferably aluminum dihydroxyacetate, stabilized with boric acid, is then mixed vigorously with the material obtained at room temperature until a homogeneous mixture is obtained. To fix the crosslinker through the matrix, the mixture is heated again to 25 ° C. to 180 ° C., preferably to 50 ° C. to 80 ° C., for 5 to 60 minutes in order to melt the matrix material.
  • ionic crosslinking agent preferably aluminum dihydroxyacetate, stabilized with boric acid
  • component A can be swelled in component B (for example swollen with water) or component B in swollen component A or (for example swollen with water) the component A (for example swollen with water) is incorporated into the component B (for example swollen with water), optionally with the addition of water or an aqueous solution.
  • the product After grinding (stage 1), the product can be sieved, preferably to a particle size of 90-630 ⁇ m.
  • the matrix components are preferably incorporated at room temperature, but the matrix component can also be used as a melt.
  • the mixture in stage 2 can be mixed with a preferably water / isopropanol mixture before the thermal modification in order to have a solubilizer.
  • water / isopropanol mixture water and other mixtures of water with water-soluble organic solvents can also be used.
  • EP-PS 0 083 022 describes the crosslinking of an absorber, which consists of polyacrylic acid, with crosslinking agents which contain at least two functional groups and are able to react with the carboxyl groups of the polyacrylate. The reaction takes place on the surface of the absorber particles.
  • DE-PS 33 14 019 and DE-PS 35 23 617 also describe the surface crosslinking of polyacrylates with the aid of crosslinking agents which have at least two functional groups.
  • the ionic crosslinking agent can also be incorporated directly into the physical mixture of stage 2), whereupon at 25 ° C. to 180 ° C., preferably at 100 ° C. to 120 ° C., for 5 to 120 minutes, preferably for 20 to 60 Minutes is warmed.
  • the covalent crosslinker can be added to the polymer mixture before or after the matrix addition.
  • the covalent crosslinker is dissolved in a preferably alcohol / water mixture, if appropriate, and added dropwise to the polymer mixture with rapid stirring.
  • the amount of solvent is between 1 and 10% based on the polymer mixture.
  • the mixture is then heated to 25 ° C to 180 ° C for 5 to 120 minutes. Water and mixtures of water with water-soluble organic solvents can be used as the solvent.
  • the antiblocking agents as well as the equivalent crosslinking agent can already be added in stage 1).
  • the absorption material according to the invention shows good biodegradability compared to products based on a polyacrylic acid base, with a significantly improved absorption and absorbency for 0.9% cooking compared to previously known absorption materials on a native basis salt solution, even under pressure, with a surprisingly very high gel strength.
  • Products A, B, C, D, F and G cross-linked, partially neutralized polyacrylates
  • Product E cross-linked, partially neutralized polyacrylate starch graft polymer
  • the polymer composition according to the invention can be used in particular as an absorption material as fiber, film, powder or granulate to absorb water or aqueous liquids, such as urine and blood, and is therefore particularly suitable for use in diapers, tampons, surgical products, ⁇ cable sheaths, Culture vessels, packaging materials for meat or fish and absorbent garments are suitable.
  • the material is suitable as a storage medium for the successive release of active substances, such as medicaments, pesticides (US 4,818,534; US 4,983,389; US 4,983,390; US 4,985,251) and fragrances, with the advantage that the storage medium is degradable.
  • the active substance-containing depot materials can be produced by absorption, preferably concentrated, aqueous or water-containing solutions in the largely dry absorber and, if necessary, drying them again.
  • the active ingredient can also be added directly or as a solution or dispersion in any preliminary stages of the manufacturing process of the absorber composition.
  • the active ingredient-containing depot materials are in powder form or as a dispersion in hydrophobic media, and the dispersion-stabilizing agents such as emulsifiers or stabilizers may contain, or used in a mixture with other substances such as polysaccharides.
  • bactericidal depot materials for example, the addition of such bactericidal depot materials to cellulose, guar or starch products or their derivatives, such as carboxymethyl cellulose, prevents the degradation of these substances over a long period of time when stored and used in aqueous media, and thereby by the depot effect Larger amounts of free active ingredient in the solution can be avoided.
  • a tea bag test was carried out to determine the absorbency.
  • An aqueous 0.9% NaCl solution was used as the test solution.
  • 0.2 g of a test substance (sieved between 90 and 630 ⁇ m), which was weighed into a tea bag, was allowed to swell in the test solution for 10 or 30 minutes. After five minutes of dripping (maximum value), a centrifuge, e.g. in a commercial spin dryer, spun at 1400 rpm. The liquid intake was determined gravimetrically and converted to 1 g of substance. (Retention value).
  • test substance 0.16 g was allowed to swell in 0.9% NaCl solution by capillary action for 60 minutes under a pressure of 1.55 kN / m 2 (99.8 g / in 2 ) .
  • Measuring conditions plate-plate system, diameter 60 mm, plate spacing 2 mm, temperature 20 ° C, torque 1000 - 4000 ⁇ Nm, amplitude 1.5 - 5 mrad, frequency 10.0 Hz, 28 ml 0.9% NaCl / g absorber. The information is given in N / m.
  • the flow test was used to determine how quickly the products absorbed the test liquid, whether they showed block phenomena, were completely swollen and were wetted everywhere. It was also examined whether the gels were solid, sticky or loose and separated.
  • the mixtures listed below are stirred in at room temperature (15 to 20 ° C.) in 360 ml of water and left to stand for three hours.
  • the gels obtained are then dried in a forced-air drying cabinet at 100 ° C. for two hours, then ground and sieved to a particle size of 90-630 ⁇ m.
  • CMC Walocel 40000 sodium carboxymethyl cellulose, Wolff Walsrode
  • SAB A polyacrylate superabsorber
  • Example 1 100 g of the product obtained in Example 1 are mixed with 100 ml of a 0.125% aqueous solution of 3,7-bis (dimethyl-a ino) phenothiazinium chloride and then dried at 60 ° C. in a forced-air drying cabinet for 2 h. 200 mg of the product thus obtained are placed in a tea bag. This is suspended in a beaker with 50 ml of 0.2% saline. The tea bag is removed after one hour. The color of the saline solution is assessed, then the process is repeated with new NaCl solution.
  • the blue color of the saline solution indicates the release of the active ingredient from the polymer composition which acts as the storage medium.
  • 60 g of CMC 40000 are mixed vigorously with 1.5 g of ethylene carbonate, 1.5 ml of water and 1.5 ml of isopropanol; then heated to 120 ° C in the oven for 60 min.
  • 8 g of this product are mixed with 2 g Favor R 953 (cross-linked, partially neutralized polyacrylate from Stockhausen GmbH), 0.5 g TONE 230, 0.5 g fiber BE 600/30 and with 0.5 g AI (OH) 2 OOCCH 3 * 1/3 H 3 B0 3 vigorously mixed using 2 ml isopropanol and 1 ml water and heated to 120 ° C in the oven for 60 min.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Hematology (AREA)
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  • Engineering & Computer Science (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
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  • Absorbent Articles And Supports Therefor (AREA)
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Abstract

L'invention concerne une composition polymère et son procédé de production, notamment un matériau absorbant sensiblement constitué d'un composant spécial A à base de matières premières renouvelables en polysaccharides, un composant spécial B en un polymère gonflant dans l'eau, un matériau à matrice, un agent réticulant ionique et/ou covalent ou un agent anti-blocage. On produit cette composition en mélangeant le polymère gonflant dans l'eau avec le polymère de polysaccharide, en séchant et en broyant ceux-ci, en ajoutant les autres composants jusqu'à obtenir un mélange homogène et en soumettant le mélange à un traitement thermique. Lorsqu'un agent réticulant est ajouté, celui-ci peut être fixé dans la matrice après le traitement thermique par un traitement thermique supplémentaire. L'invention concerne également l'utilisation de cette composition polymère, des produits hygiéniques (pour animaux) et des produits chimiques industriels contenant ladite composition polymère.
PCT/EP1993/001062 1992-03-05 1993-05-03 Compositions polymeres, production de compositions polymeres, notamment de materiaux absorbants, et leur utilisation WO1994025521A1 (fr)

Priority Applications (15)

Application Number Priority Date Filing Date Title
SK1316-95A SK280641B6 (sk) 1993-05-03 1993-05-03 Polymérna kompozícia, spôsob jej výroby a jej použ
DE59307096T DE59307096D1 (de) 1993-05-03 1993-05-03 Polymerzusammensetzungen, herstellung von polymerzusammensetzungen, insbesondere absorptionsmaterialien und deren verwendung
AU40296/93A AU677581B2 (en) 1993-05-03 1993-05-03 Polymer compositions and their production, in particular absorbent materials, and their use
PCT/EP1993/001062 WO1994025521A1 (fr) 1992-03-05 1993-05-03 Compositions polymeres, production de compositions polymeres, notamment de materiaux absorbants, et leur utilisation
US08/535,070 US5736595A (en) 1993-05-03 1993-05-03 Polymer composition, absorbent material composition, their production and their use
PL93311586A PL174749B1 (pl) 1993-05-03 1993-05-03 Sposób wytwarzania kompozycji polimerowej materiału absorpcyjnego
JP6523786A JPH08509511A (ja) 1993-05-03 1993-05-03 ポリマー組成物、ポリマー組成物の製造方法、特に吸収材組成物、およびその使用
ES93909539T ES2107021T3 (es) 1993-05-03 1993-05-03 Composiciones polimericas, fabricacion de las composiciones polimericas, en especial de materiales de absorcion y su utilizacion.
KR1019950704846A KR100292923B1 (ko) 1993-05-03 1993-05-03 중합체 조성물, 흡수제 조성물, 이들의 제조 방법 및 사용 방법
RU95122614A RU2146270C1 (ru) 1993-05-03 1993-05-03 Полимерные композиции и способы их получения
EP93909539A EP0701587B1 (fr) 1993-05-03 1993-05-03 Compositions polymeres, production de compositions polymeres, notamment de materiaux absorbants, et leur utilisation
CA002161904A CA2161904C (fr) 1993-05-03 1993-05-03 Compositions polymeriques et leur preparation, notamment pour l'obtention de produits absorbants; leur utilisation
TW082103723A TW311922B (fr) 1993-05-03 1993-05-12
FI955226A FI955226A (fi) 1993-05-03 1995-11-01 Polymeerikoostumuksia ja niiden valmistus, erityisesti absorptiomateriaaleja sekä niiden käyttö
BG100175A BG62857B1 (bg) 1993-05-03 1995-11-29 Полимерни състави, производство на полимерни състави,по-специално на абсорбционни материали, и тяхното приложение

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19924206850 DE4206850C2 (de) 1992-03-05 1992-03-05 Polymerzusammensetzungen, Herstellgung von Polymerzusammensetzungen, insbesondere Absorptionsmaterialien und deren Verwendung
PCT/EP1993/001062 WO1994025521A1 (fr) 1992-03-05 1993-05-03 Compositions polymeres, production de compositions polymeres, notamment de materiaux absorbants, et leur utilisation

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US5951970A (en) * 1996-06-19 1999-09-14 Haarmann & Reimer Gmbh Drying composition comprising an odoriferous substance
WO2001000258A1 (fr) * 1999-06-29 2001-01-04 Stockhausen Gmbh & Co. Kg Polymeres superabsorbants presentant des caracteristiques d'absorption d'eau differee
WO2001000259A1 (fr) * 1999-06-29 2001-01-04 Stockhausen Gmbh & Co. Kg Fabrication de bande continue en polymere et fibre superabsorbants

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EP0405993A2 (fr) * 1989-06-28 1991-01-02 James River Corporation Of Virginia Pansemet superabsorbant
DE4029591A1 (de) * 1990-09-19 1992-03-26 Stockhausen Chem Fab Gmbh Verfahren zur herstellung von absorptionsmaterial auf polymerbasis mit zusatz von wasserloeslichen substanzen und verwendung dieses absorptionsmaterials zur aufnahme und/oder zur nachfolgenden abgabe von wasser oder waessrigen loesungen
DE4029593A1 (de) * 1990-09-19 1992-03-26 Stockhausen Chem Fab Gmbh Verfahren zur herstellung von absorptionsmaterial auf polymerbasis mit verbesserter abbaubarkeit und absorption von wasser, waessrigen loesungen und koerperfluessigkeiten und die verwendung in hygieneartikeln und zur bodenverbesserung
EP0481225A1 (fr) * 1990-09-19 1992-04-22 Chemische Fabrik Stockhausen GmbH Agent de gonflement et d'adsorption d'eau à base du polymère et son utilisaton pour fabriquer des articles hygièniques et dans l'amélioration des sols
US5137563A (en) * 1991-01-28 1992-08-11 Valkanas George N Controlled release fertilizer
DE4206850A1 (de) * 1992-03-05 1993-09-09 Stockhausen Chem Fab Gmbh Polymerzusammensetzungen, herstellgung von polymerzusammensetzungen, insbesondere absorptionsmaterialien und deren verwendung

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EP0405993A2 (fr) * 1989-06-28 1991-01-02 James River Corporation Of Virginia Pansemet superabsorbant
DE4029591A1 (de) * 1990-09-19 1992-03-26 Stockhausen Chem Fab Gmbh Verfahren zur herstellung von absorptionsmaterial auf polymerbasis mit zusatz von wasserloeslichen substanzen und verwendung dieses absorptionsmaterials zur aufnahme und/oder zur nachfolgenden abgabe von wasser oder waessrigen loesungen
DE4029593A1 (de) * 1990-09-19 1992-03-26 Stockhausen Chem Fab Gmbh Verfahren zur herstellung von absorptionsmaterial auf polymerbasis mit verbesserter abbaubarkeit und absorption von wasser, waessrigen loesungen und koerperfluessigkeiten und die verwendung in hygieneartikeln und zur bodenverbesserung
EP0481226A1 (fr) * 1990-09-19 1992-04-22 Chemische Fabrik Stockhausen GmbH Procédé pour la fabrication de matériau d'absorption d'eau à base de polymère et son utilisation
EP0481225A1 (fr) * 1990-09-19 1992-04-22 Chemische Fabrik Stockhausen GmbH Agent de gonflement et d'adsorption d'eau à base du polymère et son utilisaton pour fabriquer des articles hygièniques et dans l'amélioration des sols
US5137563A (en) * 1991-01-28 1992-08-11 Valkanas George N Controlled release fertilizer
DE4206850A1 (de) * 1992-03-05 1993-09-09 Stockhausen Chem Fab Gmbh Polymerzusammensetzungen, herstellgung von polymerzusammensetzungen, insbesondere absorptionsmaterialien und deren verwendung

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Publication number Priority date Publication date Assignee Title
US5951970A (en) * 1996-06-19 1999-09-14 Haarmann & Reimer Gmbh Drying composition comprising an odoriferous substance
WO2001000258A1 (fr) * 1999-06-29 2001-01-04 Stockhausen Gmbh & Co. Kg Polymeres superabsorbants presentant des caracteristiques d'absorption d'eau differee
WO2001000259A1 (fr) * 1999-06-29 2001-01-04 Stockhausen Gmbh & Co. Kg Fabrication de bande continue en polymere et fibre superabsorbants
CN100335140C (zh) * 1999-06-29 2007-09-05 施托克赫森两合公司 网状超吸收性聚合物和纤维的制造

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