EP0394298A1 - Polymerisate mit hoher aufnahmegeschwindigkeit für wässrige flüssigkeiten - Google Patents

Polymerisate mit hoher aufnahmegeschwindigkeit für wässrige flüssigkeiten

Info

Publication number
EP0394298A1
EP0394298A1 EP88910033A EP88910033A EP0394298A1 EP 0394298 A1 EP0394298 A1 EP 0394298A1 EP 88910033 A EP88910033 A EP 88910033A EP 88910033 A EP88910033 A EP 88910033A EP 0394298 A1 EP0394298 A1 EP 0394298A1
Authority
EP
European Patent Office
Prior art keywords
water
agglomeration
polymers
organic solvent
aid
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.)
Pending
Application number
EP88910033A
Other languages
German (de)
English (en)
French (fr)
Inventor
Miroslav Chmelir
Karl-Heinz Stukenbrock
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.)
Stockhausen GmbH and Co KG
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6341897&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0394298(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Chemische Fabrik Stockhausen GmbH filed Critical Chemische Fabrik Stockhausen GmbH
Publication of EP0394298A1 publication Critical patent/EP0394298A1/de
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/12Powdering or granulating
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/60Liquid-swellable gel-forming materials, e.g. super-absorbents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/12Powdering or granulating
    • C08J3/16Powdering or granulating by coagulating dispersions
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00Characterised by the use of unspecified polymers
    • C08J2300/14Water soluble or water swellable polymers, e.g. aqueous gels

Definitions

  • the invention relates to polymers which rapidly absorb water and aqueous liquids, e.g. find use in absorbent, disposable products for hygiene articles (diapers and sanitary napkins) and for other medical purposes, or also as water-storing soil improvers, and a process for their preparation and their use as absorbents for water and aqueous liquids.
  • starch such as starch-acrylonitrile graft polymers (US Pat. No. 3,997,404; 3,661, 815; 4,155,808; 3,935,099), gelatinized starch derivatives (DE-OS 27 02 701) or cellulose-based, such as derivatives of alkyl or HydroxyIkylcellulose (J PP S 77 / 125.401), Carboxymethylcellulose (BE-PS 862,130; GB-PS 1, 159,949) and based on polysaccharide (DE-OS 26 50 377).
  • starch-acrylonitrile graft polymers US Pat. No. 3,997,404; 3,661, 815; 4,155,808; 3,935,09
  • DE-OS 27 02 701 gelatinized starch derivatives
  • cellulose-based such as derivatives of alkyl or HydroxyIkylcellulose (J PP S 77 / 125.401), Carboxymethylcellulose (BE-PS 862,130; GB-PS 1, 159,949)
  • the fully synthetic absorbents described in numerous patents include crosslinked polymers and copolymers based on acrylic or methacrylic acid (DE-OS 24 29 236; DE-OS 26 14 662; US-P S 4,018,951; US-P S 3,926,091; US-PS 4,066,503 ; US-PS 4,062,817; D E-OS 27 12 043; DE-OS 26 53 135; DE-OS 26 50 377; DE-OS 28 13 634), maleic acid derivatives (US-PS 4,041, 220) or acrylamidopropanesulfonic acid copolymers (DE- PS 31 24 008).
  • DE-OS 28 13 634 describes an acrylic acid / acrylonitrile / stearyl methacrylate mixture polymer which absorbs 38 times its own weight in artificial urine within 30 seconds.
  • the acceleration of the liquid absorption can be achieved by adding various water-soluble substances such as sugars, urea or aluminum sulfate.
  • a partial improvement in the blood uptake rate was achieved according to DE-OS 28 44 956 and EP-PS 0009977 in that a partially synthetic or fully synthetic absorbent in powder form subsequently with polyethers (DE-OS 28 44 956) or with fatty alcohols, fatty acids or esters ( EP-PS 0 009 977), mostly dissolved in organic solvents, is treated.
  • the object of the invention is to improve the known polymers used as absorbents with regard to their absorption rate for water and aqueous liquids such as urine or blood, and to increase the solubility and dissolution rate of water-soluble polymers. It has now surprisingly been found that the uptake rate for water and aqueous solutions can be significantly increased if a finely ground polymer having a particle size distribution of ⁇ 0.2 mm, preferably less than 0.1 mm and particularly preferably less than 0.05 mm, by conventional methods agglomerated and thereby a coarser grain than the original product had, a grain distribution of 0.1 to 0.5 and particularly 0.2 to 1.0 mm being preferred in the agglomerated polymer. However, it is also possible to produce end products with particles that are larger than 1 mm.
  • the agglomeration is preferably carried out with an aqueous solution or a water-containing mixture of the agglomeration aid, in that the agglomeration aid is brought together in a suitable manner with the polymer to be agglomerated.
  • the agglomeration aid is preferably sprayed onto the polymer to be agglomerated in aqueous solution or dispersion while it is kept in motion.
  • the agglomeration aid can also be dissolved or dispersed in a water-miscible or immiscible organic solvent or a mixture of water and such a solvent.
  • the fluidized bed which can be operated by means of a suitable inert gas, preferably air, is suitable for this.
  • the air is advantageously heated immediately to remove the water from the system and to dry the type of agglomer.
  • a fluidized bed dryer has proven to be particularly advantageous for carrying out the method.
  • the individual process parameters as stated The amount of polymer, amount of air, amount of agglomeration aid and air temperature and duration of the agglomeration treatment can be determined by simple experiments.
  • the agglomeration can also be carried out in a mixer equipped with a spraying device and with a rotating mixing tool equipped with guide vanes which thoroughly scrape the walls of the mixer. After a certain speed of the agitator is reached, the individual granules are thrown out of the material mass when the rotating guide vanes of the mixing tool emerge, and a fluidized-bed powder is formed in this way. At this stage, the dispersed or dissolved agglomeration aid is sprayed on with a nozzle.
  • the device can be operated at room temperature or with an existing heating or cooling jacket at higher or lower temperatures.
  • the polymers that can be agglomerated in this way are both the water-soluble and water-swellable polymers based on polysaccharides, such as cellulose, cellulose derivatives such as carboxymethyl cellulose, alkyl or hydroxyalkyl cellulose, starch and starch derivatives and vegetable gum (xanthan gum, alginic acid) and their salts the polymers or copolymers based on (meth) acrylic acid or (meth) acrylic acid derivatives are also suitable, these being primarily the homo- or copolymers of acrylic, methacrylic, acrylamidomethyl propane sulfonic acid, the salts of these acids , the acrylic or methacrylamide with each other or with Vinyl pyrrole idon and / or vinyl acetate.
  • the above polymers can also be crosslinked by means of an at least bi-functional crosslinker so that they are only swellable but not soluble in water. All of these polymers are made by known methods.
  • the starting material itself i.e. the water-soluble or water-swellable polymers are used on a synthetic or natural basis (polysaccharide base in dissolved or swollen state).
  • water-soluble or water-swellable polymers on a natural basis are starch, in particular maize starch, cellulose derivatives such as carboxymethyl cellulose, alkyl or hydroxyalkyl cellulose, starch and starch derivatives and vegetable gum (xanthan gum, alginic acid) and their salts, and the polymers or copolymers based on them on a synthetic basis of (meth) acrylic acid or (meth) -acrylic acid derivatives such as the homo- or copolymers of acrylic, methacrylic, acrylamidomethylpropanesulfonic acid, the salts of these acids, of acrylic or methacrylamide with each other or with vinyl pyrrolidone and / or vinyl acetate and polyvinyl alcohol.
  • the above polymers can also
  • oil phase usually consists of water-immiscible organic solvents such as aliphatic or aromatic carbon water (eg hexane, toluene).
  • polymers which can form oil-in-water emulsions are polymers of butadiene, styrene, isoprene, chloroprene, acrylonitrile, vinyl acetate, vinyl and vinylidene chloride, alkyl acrylate and methacrylate and copolymers of these monomers with one another and also with one another Methylstyrene, isobutylene or ethylene.
  • polymers that are used in water-in-oil emulsions the above-mentioned. water-soluble or water-swellable polymers or /. Copolymers based on (meth) acrylic acid derivatives, which can be uncrosslinked or crosslinked.
  • agglomeration aids can also be used in products which, according to DE-PS 31 28 100, are added to the polymers to improve the rate of liquid absorption.
  • the uptake of model urine is carried out according to the demand absorbency test (WF hose, lecture index 1978, Amsterdam) and the uptake rate after 60 seconds as well as the maximum uptake and retention 20 or 40 minutes determined.
  • the measuring device consists of a burette, which is filled with the model urine solution (2.0% urea, 0.9% NaCl, 0.1% MgSO 4 and 0.06% CaCl 2 dissolved in distilled water), and a sample table, which is provided with an opening for the model urine solution outlet connected to the measuring burette.
  • 0.5 g of the product according to the invention is mixed with 5 mg of Aerosil 200 in the form of a circular surface of 4.5 cm in diameter, centered over the liquid outlet, sprinkled uniformly on the sample table covered with a thin fleece (10 ⁇ 13.5 cm).
  • Aerosil 200 By closing the hose and applying slight pressure, the model urine solution is brought into contact with the powder product so that the model urine solution can be absorbed by the product according to the invention.
  • the absorbing amount of the model urine solution is read after 60 seconds and after 20-30 minutes the first maximum value.
  • the retention was then determined by loading the swollen gel with a weight of 10 g / cm 2 ; the time of exposure was 5 minutes.
  • the 60 second, maximum and retention values determined are summarized in the examples in tables.
  • the invention further relates to disposable products for hygiene articles, such as diapers or sanitary napkins, containing a polymer according to claim 1 as an absorbent for body fluids, such as water and urine.
  • the agglomeration of the powdery polymer was carried out in a fluidized bed dryer.
  • the device consists of a vertical conical metal cylinder, which is closed at the lower end with a sieve bottom and provided with a device for sucking in air.
  • An adjustable amount of air flows through the granular product to be treated in this cylinder until the individual granules start to move, as a result of which the fluidized or fluidized bed is thoroughly mixed.
  • the dissolved agglomeration aid is sprayed on using a nozzle.
  • the amount of the auxiliary, the amount of air and the air temperature can be varied within certain limits.
  • the device was filled with 1000 g of finely ground, powdery, partially crosslinked polyacrylic acid, with 90% by weight grain fraction, below 90 ⁇ and a model urine uptake rate of 15 ml / g (DAT 60 sec value) and to 110 ° C warmed with the air flow.
  • the polymer was then agglomerated in the fluidized bed within 5 to 15 minutes by spraying on the aqueous solutions of low molecular weight polyacrylic acids.
  • the test conditions and the results are summarized in the table below.
  • a yield of the agglomerated particles of 89-95% by weight of the grain fraction 90-630 ⁇ m was obtained, the agglomerated product showing an improvement in the initial absorption rate (DAT-60-Sec value) from 15 to 230 ml and more .
  • the test conditions and the results are listed in Table 3.
  • the solution of the agglomeration aid was metered in with a peristaltic pump and sprayed under pressure.
  • a finely ground, high molecular weight, water-soluble polyacrylamide with 92% by weight grain size below 90 ⁇ and a molecular weight of 4.10 6 was agglomerated at 65 ° C. with an aqueous solution of polyacrylic acid in a fluidized bed dryer.
  • the solution was dosed with a peristaltic pump and sprayed under nitrogen pressure. There was a yield of the grain fraction 90-300 ⁇ m of 55-65 Gevi. -% and obtained on the grain fraction of 300-800 microns from 32 - 42 wt .-%.
  • Table 6 The results and test conditions are summarized in Table 6.
  • a finely ground acrylic acid polymer as in Examples 20-22 was sprayed at 80 ° C. in a fluidized bed dryer with a solution of a water-soluble compound (component B) according to DE-PS 31 28 100.
  • the solution was dosed with a peristaltic pump and sprayed with compressed air.
  • Table 7 The results and test conditions are summarized in Table 7.
  • a finely ground, partially crosslinked acrylic acid copolymer with 91.5% by weight grain size below 90 ⁇ and a model absorption rate of 18 ml / g (15 sec tea bag test) was at 40 ° C. with an aqueous dispersion of polyacrylic acid ester or polyvinyl acetate in the same device as in the previous examples agglomerated.
  • the dispersion of the agglomeration aid possibly diluted with water, was metered in with a peristaltic pump and sprayed under pressure. There was a yield of 90 to 300 ⁇ m in the grain fraction of 50 to 88% by weight and in the grain fraction of 300 to 800 ⁇ m from 10 to 50% by weight. -% receive.
  • Table 8 The results and test conditions are summarized in Table 8 below.
  • the agglomeration of the powdery polymer was carried out in a mixer with a rotating mixing tool.
  • the device consists of a vertical or horizontal metal cylinder (volume 6000 ml), the mixing tool of which is equipped with guide vanes, which scrape the walls of the mixer thoroughly, and a device for spraying. After a certain speed (300 rpm) of the agitator has been reached, a powder fluidized bed forms over the entire length of the metal cylinder when the rotating guide vanes of the mixing tool emerge from the individual granules of the bulk material that have been thrown out. At this stage, the dispersed or dissolved agglomeration aid was sprayed on with a nozzle. The device was operated at room temperature.
  • the device was filled with 1000 g of finely ground, powdery, partially crosslinked polyacrylic acid, which had a grain weight of 88% by weight below 90 ⁇ and a model urine absorption capacity of 16.5 ml / g (15 sec teabag test) Stir at normal temperature within 5 -15 minutes by spraying the aqueous solutions and / or dispersions agglomerated.
  • the test conditions and the results are summarized in Table 9 below.
  • a good yield of the agglomerated particles (84-99% by weight of the grain fraction 90-800 ⁇ m) was obtained, the agglomerated product improving the initial absorption rate (15 sec teabag test) from 16 (starting product) to 32 to 45 ml / G showed.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Animal Behavior & Ethology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hematology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
  • Orthopedics, Nursing, And Contraception (AREA)
  • Materials For Medical Uses (AREA)
EP88910033A 1987-12-04 1988-12-01 Polymerisate mit hoher aufnahmegeschwindigkeit für wässrige flüssigkeiten Pending EP0394298A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873741158 DE3741158A1 (de) 1987-12-04 1987-12-04 Polymerisate mit hoher aufnahmegeschwindigkeit fuer wasser und waessrige fluessigkeiten, verfahren zu ihrer herstellung und verwendung als absorptionsmittel
DE3741158 1987-12-04

Publications (1)

Publication Number Publication Date
EP0394298A1 true EP0394298A1 (de) 1990-10-31

Family

ID=6341897

Family Applications (2)

Application Number Title Priority Date Filing Date
EP88910033A Pending EP0394298A1 (de) 1987-12-04 1988-12-01 Polymerisate mit hoher aufnahmegeschwindigkeit für wässrige flüssigkeiten
EP88120065A Revoked EP0318989B1 (de) 1987-12-04 1988-12-01 Polymerisate mit hoher Aufnahmegeschwindigkeit für wässrige Flüssigkeiten

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP88120065A Revoked EP0318989B1 (de) 1987-12-04 1988-12-01 Polymerisate mit hoher Aufnahmegeschwindigkeit für wässrige Flüssigkeiten

Country Status (8)

Country Link
EP (2) EP0394298A1 (enrdf_load_stackoverflow)
JP (1) JPH03501493A (enrdf_load_stackoverflow)
AT (1) ATE119556T1 (enrdf_load_stackoverflow)
BR (1) BR8807830A (enrdf_load_stackoverflow)
DE (2) DE3741158A1 (enrdf_load_stackoverflow)
ES (1) ES2010960T3 (enrdf_load_stackoverflow)
GR (1) GR3015344T3 (enrdf_load_stackoverflow)
WO (1) WO1989005327A1 (enrdf_load_stackoverflow)

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KR101522046B1 (ko) * 2007-06-19 2015-05-20 스미또모 세이까 가부시키가이샤 과립 형상 카르복실기 함유 중합체 입자의 제조 방법 및 과립 형상 카르복실기 함유 중합체 입자
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DE3853266D1 (de) 1995-04-13
EP0318989B1 (de) 1995-03-08
EP0318989A1 (de) 1989-06-07
ES2010960T3 (es) 1995-05-01
WO1989005327A1 (en) 1989-06-15
JPH03501493A (ja) 1991-04-04
ES2010960A4 (es) 1989-12-16
ATE119556T1 (de) 1995-03-15
GR3015344T3 (en) 1995-06-30
BR8807830A (pt) 1990-10-09
DE3741158C2 (enrdf_load_stackoverflow) 1990-03-08
DE3741158A1 (de) 1989-06-15

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