EP0394298A1 - Polymerisate mit hoher aufnahmegeschwindigkeit für wässrige flüssigkeiten - Google Patents
Polymerisate mit hoher aufnahmegeschwindigkeit für wässrige flüssigkeitenInfo
- 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
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 36
- 238000010521 absorption reaction Methods 0.000 title claims description 17
- 239000012530 fluid Substances 0.000 title abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000005054 agglomeration Methods 0.000 claims abstract description 30
- 230000002776 aggregation Effects 0.000 claims abstract description 30
- 210000002700 urine Anatomy 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000007858 starting material Substances 0.000 claims abstract description 6
- 210000001124 body fluid Anatomy 0.000 claims abstract description 5
- 239000010839 body fluid Substances 0.000 claims abstract description 5
- 239000000654 additive Substances 0.000 claims abstract description 3
- 229920005615 natural polymer Polymers 0.000 claims abstract 4
- 229920001059 synthetic polymer Polymers 0.000 claims abstract 4
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 239000002250 absorbent Substances 0.000 claims description 9
- 230000002745 absorbent Effects 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000010419 fine particle Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 235000013339 cereals Nutrition 0.000 description 21
- 239000000047 product Substances 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 8
- 229920002125 Sokalan® Polymers 0.000 description 7
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000004584 polyacrylic acid Substances 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 230000002572 peristaltic effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 229920000881 Modified starch Polymers 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 235000019426 modified starch Nutrition 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- 150000004804 polysaccharides Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229920001938 Vegetable gum Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229920006322 acrylamide copolymer Polymers 0.000 description 2
- 239000000783 alginic acid Substances 0.000 description 2
- 235000010443 alginic acid Nutrition 0.000 description 2
- 229920000615 alginic acid Polymers 0.000 description 2
- 229960001126 alginic acid Drugs 0.000 description 2
- 150000004781 alginic acids Chemical class 0.000 description 2
- 229920013820 alkyl cellulose Polymers 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- 239000000230 xanthan gum Substances 0.000 description 2
- 229920001285 xanthan gum Polymers 0.000 description 2
- 235000010493 xanthan gum Nutrition 0.000 description 2
- 229940082509 xanthan gum Drugs 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- MZNSQRLUUXWLSB-UHFFFAOYSA-N 2-ethenyl-1h-pyrrole Chemical compound C=CC1=CC=CN1 MZNSQRLUUXWLSB-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 235000019759 Maize starch Nutrition 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- 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
- 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
- C08J3/12—Powdering or granulating
- C08J3/16—Powdering or granulating by coagulating dispersions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/14—Water soluble or water swellable polymers, e.g. aqueous gels
Definitions
- the 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)
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)
Families Citing this family (39)
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US5171781A (en) * | 1987-01-30 | 1992-12-15 | Allied Colloids Limited | Polymeric compositions |
US5061259A (en) * | 1987-08-19 | 1991-10-29 | The Procter & Gamble Company | Absorbent structures with gelling agent and absorbent articles containing such structures |
EP0326382B1 (en) * | 1988-01-28 | 1997-04-23 | Ciba Specialty Chemicals Water Treatments Limited | Polymeric compositions |
JPH0710923B2 (ja) * | 1989-05-24 | 1995-02-08 | 日本合成化学工業株式会社 | 高吸水性樹脂の造粒法 |
US5149335A (en) * | 1990-02-23 | 1992-09-22 | Kimberly-Clark Corporation | Absorbent structure |
US5180622A (en) * | 1990-04-02 | 1993-01-19 | The Procter & Gamble Company | Absorbent members containing interparticle crosslinked aggregates |
AU656133B2 (en) * | 1990-04-02 | 1995-01-27 | Procter & Gamble Company, The | Absorbent members containing interparticle crosslinked aggregates |
US5140076A (en) * | 1990-04-02 | 1992-08-18 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Method of treating the surface of an absorbent resin |
US5124188A (en) * | 1990-04-02 | 1992-06-23 | The Procter & Gamble Company | Porous, absorbent, polymeric macrostructures and methods of making the same |
US5492962A (en) * | 1990-04-02 | 1996-02-20 | The Procter & Gamble Company | Method for producing compositions containing interparticle crosslinked aggregates |
CA2038779A1 (en) * | 1990-04-02 | 1991-10-03 | Takumi Hatsuda | Method for production of fluid stable aggregate |
US5164459A (en) * | 1990-04-02 | 1992-11-17 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Method for treating the surface of an absorbent resin |
US5149334A (en) * | 1990-04-02 | 1992-09-22 | The Procter & Gamble Company | Absorbent articles containing interparticle crosslinked aggregates |
US5300565A (en) * | 1990-04-02 | 1994-04-05 | The Procter & Gamble Company | Particulate, absorbent, polymeric compositions containing interparticle crosslinked aggregates |
DE4015085C2 (de) * | 1990-05-11 | 1995-06-08 | Stockhausen Chem Fab Gmbh | Vernetztes, wasserabsorbierendes Polymer und Verwendung zur Herstellung von Hygieneartikeln, zur Bodenverbesserung und in Kabelummantelungen |
DE4021847C2 (de) * | 1990-07-09 | 1994-09-08 | Stockhausen Chem Fab Gmbh | Verfahren zur Herstellung wasserquellbarer Produkte unter Verwendung von Feinstanteilen wasserquellbarer Polymerer |
DE4029593C2 (de) * | 1990-09-19 | 1994-07-07 | Stockhausen Chem Fab Gmbh | Verfahren zur Herstellung von Absorptionsmaterial auf Polymerbasis mit verbesserter Abbaubarkeit und Absorption von Wasser, wäßrigen Lösungen und Körperflüssigkeiten und die Verwendung in Hygieneartikeln und zur Bodenverbesserung |
DE4029591C2 (de) * | 1990-09-19 | 1995-01-26 | Stockhausen Chem Fab Gmbh | Verfahren zur Herstellung von Absorptionsmaterial auf Polymerbasis mit Zusatz von wasserlöslichen Substanzen und Verwendung dieses Absorptionsmaterials zur Aufnahme und/oder zur nachfolgenden Abgabe von Wasser oder wäßrigen Lösungen |
DE4029592C2 (de) * | 1990-09-19 | 1994-07-14 | Stockhausen Chem Fab Gmbh | Quellmittel und Absorptionsmittel auf Polymerbasis mit verbesserter Abbaubarkeit und verbesserter Absorption von Wasser, wäßrigen Lösungen und Körperflüssigkeiten sowie ihre Verwendung zur Herstellung von Hygieneartikeln und zur Bodenverbesserung |
TR27601A (tr) * | 1991-05-17 | 1995-06-13 | Procter & Gamble | Tanecikler arasi capraz baglanmis külcecikler ihtiva eden tanecikli absorplayici polimerik terkipler. |
CA2114815C (en) | 1993-02-24 | 2005-06-14 | Mark Kevin Melius | Absorbent composite |
AU3799593A (en) * | 1993-02-26 | 1994-09-14 | Dow Chemical Company, The | Suspension polymerized aqueous absorbent polymer particles |
US5536264A (en) * | 1993-10-22 | 1996-07-16 | The Procter & Gamble Company | Absorbent composites comprising a porous macrostructure of absorbent gelling particles and a substrate |
US5713881A (en) * | 1993-10-22 | 1998-02-03 | Rezai; Ebrahim | Non-continuous absorbent composites comprising a porous macrostructure of absorbent gelling particles and a substrate |
US5868724A (en) * | 1993-10-22 | 1999-02-09 | The Procter & Gamble Company | Non-continuous absorbent cores comprising a porous macrostructure of absorbent gelling particles |
US5372766A (en) * | 1994-03-31 | 1994-12-13 | The Procter & Gamble Company | Flexible, porous, absorbent, polymeric macrostructures and methods of making the same |
DE69630441T3 (de) * | 1995-12-27 | 2019-02-28 | Nippon Shokubai Co. Ltd. | Wasser-Absorbierungsmittel und Verfahren und Vorrichtung zu dessen Herstellung |
US6228930B1 (en) | 1997-06-18 | 2001-05-08 | Nippon Shokubai Co., Ltd. | Water-absorbent resin granule-containing composition and production process for water-absorbent resin granule |
DE10334271B4 (de) * | 2003-07-25 | 2006-02-23 | Stockhausen Gmbh | Verfahren zur Agglomeration von Superabsorberfeinteilchen, daraus erhältliche Superabsorberpartikel, deren Verwendung sowie diese beinhaltende Verbunde |
JP5064032B2 (ja) * | 2005-03-25 | 2012-10-31 | 株式会社日本触媒 | 吸水性樹脂造粒物の製造方法および吸水性樹脂造粒物 |
TWI353360B (en) | 2005-04-07 | 2011-12-01 | Nippon Catalytic Chem Ind | Production process of polyacrylic acid (salt) wate |
TWI394789B (zh) | 2005-12-22 | 2013-05-01 | Nippon Catalytic Chem Ind | 吸水性樹脂組成物及其製造方法、吸收性物品 |
EP1837348B9 (en) | 2006-03-24 | 2020-01-08 | Nippon Shokubai Co.,Ltd. | Water-absorbing resin and method for manufacturing the same |
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 |
WO2011040472A1 (ja) | 2009-09-29 | 2011-04-07 | 株式会社日本触媒 | 粒子状吸水剤及びその製造方法 |
WO2016056867A1 (ko) | 2014-10-08 | 2016-04-14 | 주식회사 엘지화학 | 고흡수성 수지 조립체의 제조 방법 |
US20210290453A1 (en) * | 2018-08-01 | 2021-09-23 | Basf Se | Fluid-absorbent core |
JP2021532868A (ja) * | 2018-08-01 | 2021-12-02 | ビーエイエスエフ・ソシエタス・エウロパエアBasf Se | 生理用吸収性物品 |
JP7116796B2 (ja) | 2018-09-28 | 2022-08-10 | 株式会社日本触媒 | 吸水性樹脂粉末の製造方法および吸水性樹脂粉末 |
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FR2277838A1 (fr) * | 1974-07-11 | 1976-02-06 | Solvay | Granules de sels d'acides poly-a-hydroxyacryliques et leur procede de fabrication |
US4043952A (en) * | 1975-05-09 | 1977-08-23 | National Starch And Chemical Corporation | Surface treatment process for improving dispersibility of an absorbent composition, and product thereof |
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US4558091A (en) * | 1983-05-13 | 1985-12-10 | Grain Processing Corporation | Method for preparing aluminum and polyhydric alcohol modified liquid absorbing composition |
US4734478A (en) * | 1984-07-02 | 1988-03-29 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Water absorbing agent |
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-
1987
- 1987-12-04 DE DE19873741158 patent/DE3741158A1/de active Granted
-
1988
- 1988-12-01 EP EP88910033A patent/EP0394298A1/de active Pending
- 1988-12-01 ES ES88120065T patent/ES2010960T3/es not_active Expired - Lifetime
- 1988-12-01 DE DE3853266T patent/DE3853266D1/de not_active Expired - Fee Related
- 1988-12-01 AT AT88120065T patent/ATE119556T1/de not_active IP Right Cessation
- 1988-12-01 BR BR888807830A patent/BR8807830A/pt unknown
- 1988-12-01 WO PCT/EP1988/001090 patent/WO1989005327A1/de not_active Application Discontinuation
- 1988-12-01 JP JP63509443A patent/JPH03501493A/ja active Pending
- 1988-12-01 EP EP88120065A patent/EP0318989B1/de not_active Revoked
-
1995
- 1995-03-09 GR GR950400278T patent/GR3015344T3/el unknown
Non-Patent Citations (1)
Title |
---|
See references of WO8905327A1 * |
Also Published As
Publication number | Publication date |
---|---|
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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