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WO2014072130A1 - Agent superabsorbant pour câbles - Google Patents

Agent superabsorbant pour câbles Download PDF

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Publication number
WO2014072130A1
WO2014072130A1 PCT/EP2013/070509 EP2013070509W WO2014072130A1 WO 2014072130 A1 WO2014072130 A1 WO 2014072130A1 EP 2013070509 W EP2013070509 W EP 2013070509W WO 2014072130 A1 WO2014072130 A1 WO 2014072130A1
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WO
WIPO (PCT)
Prior art keywords
water
polymer structure
absorbing polymer
method described
test method
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.)
Ceased
Application number
PCT/EP2013/070509
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German (de)
English (en)
Inventor
Martin Tennie
Nadine BARTELS
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.)
Evonik Industries AG
Original Assignee
Evonik Industries AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evonik Industries AG filed Critical Evonik Industries AG
Publication of WO2014072130A1 publication Critical patent/WO2014072130A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
    • H01B7/282—Preventing penetration of fluid, e.g. water or humidity, into conductor or cable
    • H01B7/285—Preventing penetration of fluid, e.g. water or humidity, into conductor or cable by completely or partially filling interstices in the cable
    • H01B7/288—Preventing penetration of fluid, e.g. water or humidity, into conductor or cable by completely or partially filling interstices in the cable using hygroscopic material or material swelling in the presence of liquid

Definitions

  • the present invention relates to water-absorbing polymer structures, a process for producing water-absorbing polymer structures, the water-absorbing polymer structures obtainable by this process, a composite, a process for producing a composite, the composite obtainable by this process, cables and the use of a water-absorbing composition or a composite Production of a coating layer in a cable.
  • Cables represent long-lived capital goods and must therefore meet increased operational safety requirements. Damage caused by ingress of water can be avoided by using cable insulation to seal the cables against water.
  • the "Wire World” (issue 5/1992) describes various methods for the longitudinally watertight insulation of power cables, communication cables and optical fibers, with a focus on the discussion of swelling powders or polyacrylate-based swellable webs (superabsorbents) that are incorporated into the cable construction the superabsorbents, for example, in the form of a swellable nonwoven cable bandage, onto which superabsorber particles are applied, as described, for example, in EP-A-0 269 778.
  • the superabsorbent particles in the cable bandage swell when water enters and thus prevent the spread of water Water along the cable longitudinal axis.
  • Superabsorbents are water-insoluble, crosslinked polymers which are capable of absorbing, and retaining under pressure, large quantities of water, aqueous liquids, in particular body fluids, preferably urine or blood, while swelling and forming hydrogels. Superabsorbents preferably absorb at least 100 times their own weight Water. Further details of superabsorbents are disclosed in Röder's Superabsorbent Polymer Technology, FL Buchholz, AT Graham, Wiley-VCH, 1998.
  • the present invention was based on the object of overcoming the disadvantages known from the prior art in connection with superabsorbers, which are used for the longitudinally watertight insulation of cables, in particular for the longitudinally watertight insulation of communications cables and optical waveguides.
  • the present invention has the object to provide superabsorbent, the property of insulating cable longitudinally watertight, even after a long time, for example, after days, weeks, months or years, if possible, not appreciably affected.
  • the object of the present invention was to specify a method by means of which such advantageous superabsorbers can be produced.
  • a contribution to achieving the abovementioned objects is afforded by a water-absorbing polymer structure based on partially neutralized, crosslinked polyacrylic acid, the water-absorbing polymer structure having the following properties: i) a content of soluble fractions of at least 10% by weight, determined in accordance with the test method described herein preferably at least 12.5% by weight, and most preferably at least 15% by weight; ii) a modulus of elasticity, determined according to the test method described herein, of at most 3 Pa, more preferably of at most 2.5 Pa, and most preferably of at most 2 Pa; iii) a gel viscosity drop determined by the test method described herein after 7 days at 80 ° C of the highest 25%, more preferably of at most 17.5% and most preferably of more than 10%.
  • Water-absorbing polymer structures which are preferred according to the invention are in the form of fibers, foams or particles, fibers and particles being preferred and particles being particularly preferred.
  • polymer fibers are dimensioned so that they can be incorporated into or as yarn for textiles and also directly in textiles. It is preferred according to the invention that the polymer fibers have a length in the range of 1 to 500 mm, preferably 2 to 500 mm and more preferably 5 to 100 mm and a diameter in the range of 1 to 200 denier, preferably 3 to 100 denier and more preferably 5 own up to 60 deniers.
  • the water-absorbing polymer structures according to the invention are based on partially neutralized, crosslinked polyacrylic acid.
  • the water-absorbing polymer structures according to the invention are crosslinked polyacrylates which contain at least 50% by weight, preferably at least 70% by weight and more preferably at least 90% by weight, based in each case on Weight of polymer structures based on polymerized acrylic acid.
  • the water-absorbing polymer structures of the invention to comprise at least 50% by weight, preferably at least 70% by weight, based in each case on the weight of the polymer structures, of polymerized acrylic acid which is preferably at least 20 mol%, more preferably at least 50 mol% and more preferably is neutralized in a range of 60 to 85 mol%.
  • the water-absorbing polymer structures according to the invention are obtainable, for example, by a process comprising the process steps:
  • an aqueous monomer solution comprising acrylic acid or a salt thereof and at least one crosslinker are first provided.
  • Crosslinkers used are preferably those compounds which are mentioned in WO 2004/037903 A2 as crosslinking agents (a3).
  • crosslinkers water-soluble crosslinkers are particularly preferred. Most preferred are N, N'-methylenebisacrylamide,
  • polyethylene glycol di (meth) acrylates triallylmethylammonium chloride, tetraallylammonium chloride, optionally ethoxylated trimethylolpropane triracylate or optionally ethoxylated allylnonaethylene glycol acrylate, with the use of trimethylolpropane triacrylate ethoxylated with 3 mol of ethylene oxide, which is available, for example, under the name "Sartomer 454" from the Sartomer Company, USA
  • the monomer solution may also contain acrylic acid-copolymerizable, monoethylenically unsaturated monomers, such as, for example, acrylamides, methacrylamides or vinylamides
  • Further preferred co-monomers are in particular those disclosed in WO 2004/037903 A2 Be called co-monomers ( ⁇ x2).
  • the monomer solution may also include water-soluble polymers.
  • Preferred water-soluble polymers include partially or fully saponified polyvinyl alcohol, polyvinylpyrrolidone, starch or starch derivatives, polyglycols or polyacrylic acid. The molecular weight of these polymers is not critical as long as they are water-soluble. Preferred water-soluble polymers are starch or starch derivatives or polyvinyl alcohol.
  • the water-soluble polymers, preferably synthetic, such as polyvinyl alcohol can not only serve as a grafting base for the monomers to be polymerized. It is also conceivable that these water-soluble polymers only after the polymerization with the Hydrogel or the already dried, water-absorbing polymer to mix.
  • the monomer solution may also contain auxiliaries, these aids in particular include the initiators optionally required for the polymerization.
  • Suitable solvents for the monomer solution are water, organic solvents or mixtures of water and organic solvents, wherein the choice of the solvent also depends in particular on the manner of the polymerization.
  • the relative amount of monomers, co-monomers and crosslinkers, water-soluble polymers and auxiliaries in the monomer solution is preferably selected so that the water-absorbing polymer structure obtained in step IV) after drying to 20 to 99.999 wt .-%, preferably to 55 bis 98.99 wt .-% and particularly preferably from 70 to 98.79 wt .-% of acrylic acid or its salts, to 0 to 80 wt .-%, preferably to 0 to 44.99 wt .-% and particularly preferably to 0.1 to 44.89% by weight on the co-monomers,
  • crosslinkers from 0 to 5% by weight, preferably from 0.001 to 3% by weight and more preferably from 0.01 to 2.5% by weight, of the crosslinkers,
  • Optimal values for the concentration, in particular of the monomers, the crosslinkers and water-soluble polymers in the monomer solution can be determined by simple preliminary tests or else in the prior art, in particular US Pat. Nos. 4,286,082, DE-A-2,706,135, US 4,076,663, DE-A DE-A-42 44 548, DE-A-43 33 056 and DE-A-44 18 818.
  • the acrylic acid is radically polymerized to give a polymer gel.
  • all polymerization processes known to the person skilled in the art can be considered for free radical polymerization of the monomer solution.
  • solution polymerization which is preferably carried out in kneading reactors such as extruders or continuously on a polymerization belt, spray polymerization, inverse emulsion polymerization and inverse suspension polymerization should be mentioned in this connection.
  • the solution polymerization is carried out in water as a solvent.
  • the solution polymerization can be continuous or discontinuous.
  • reaction conditions such as temperatures, type and amount of initiators and the reaction solution can be found.
  • Typical processes are described in the following patents: US Pat. No. 4,286,082, DE-A-27 06 135 A1, US Pat. No. 4,076,663, DE-A-35 03 458, DE 40 20 780 C1, DE-A-42 44 548, DE-A- 43 33 056, DE-A-44 18 818.
  • the disclosures are hereby incorporated by reference and thus are considered part of the disclosure.
  • the polymerization is initiated as usual by an initiator.
  • initiators for the initiation of the polymerization all of the Polymerization conditions Radical initiators are used, which are commonly used in the production of superabsorbents. It is also possible to initiate the polymerization by the action of electron beams on the polymerizable, aqueous mixture. However, the polymerization can also be initiated in the absence of initiators of the abovementioned type by the action of high-energy radiation in the presence of photoinitiators.
  • Polymerization initiators may be contained or dispersed in the monomer solution. Suitable initiators are all compounds which decompose into free radicals and which are known to the person skilled in the art.
  • a redox system consisting of hydrogen peroxide, sodium peroxodisulfate and ascorbic acid is used to prepare the water-absorbing polymer structures.
  • the inverse suspension and emulsion polymerization can also be used to prepare the water-absorbing polymer structures. According to these processes, an aqueous, partially neutralized solution of the acrylic acid and optionally containing the other co-monomers, the water-soluble polymers and auxiliaries, dispersed with the aid of protective colloids and / or emulsifiers in a hydrophobic organic solvent and initiated by radical initiators the polymerization.
  • crosslinkers are either dissolved in the monomer solution and are metered together with this or added separately and optionally during the polymerization.
  • a water-soluble polymer as a grafting base via the monomer solution or by direct submission to the oil phase. Subsequently, the water is removed azeotropically from the mixture and the polymer is filtered off.
  • the crosslinking by Polymerization of the polyfunctional crosslinker dissolved in the monomer solution and / or by reaction of suitable crosslinkers with functional groups of the polymer take place during the polymerization steps.
  • the methods are described, for example, in the publications US 4,340,706, DE-A-37 13 601, DE-A-28 40 010 and WO-A-96/05234, the corresponding disclosure of which is hereby incorporated by reference.
  • the hydrogel obtained in process step II) is optionally comminuted, this comminution taking place in particular when the polymerization is carried out by means of a solution polymerization.
  • the comminution can be done by comminution devices known to those skilled in the art, such as a meat grinder.
  • the optionally previously comminuted hydrogel is dried.
  • the drying of the hydrogel is preferably carried out in suitable dryers or ovens.
  • suitable dryers or ovens By way of example rotary kilns, fluidized bed dryers, plate dryers, paddle dryers or infrared dryers may be mentioned.
  • the drying of the hydrogel in process step c) takes place to a water content of 0.5 to 25 wt .-%, preferably from 1 to 10 wt .-%, wherein the drying temperatures usually in a range of 100 to 200 ° C lie.
  • the water-absorbing polymer structures obtained in process step IV) can in particular, if they were obtained by solution polymerization, still be ground and sieved to the desired grain size mentioned above.
  • the grinding of the dried, water-absorbing polymers is preferably carried out in suitable mechanical comminution devices, such as a ball mill, while the screening can be carried out, for example, by using sieves of suitable mesh size.
  • the process described above is characterized in that a) the aqueous monomer solution before process step II) or during process step II), preferably before process step II), b) the polymer gel after process step II) and before process step IV) or during process step IV), preferably before process step IV), or c) the water-absorbing polymer structure after process step IV) a chelating agent in an amount of more than 2,000 ppm, more preferably at least 2,500 ppm and most preferably at least 3,000 ppm, in each case based on the amount of acrylic acid in the monomer solution or on polymerized acrylic acid in the water-absorbing polymer structure is added.
  • Suitable chelating agents are all compounds which have a metal chelating ability. They are therefore compounds with a bidentate or multidentate ligand capable of binding to a metal ion to form a metal chelate.
  • a chelating agent are preferably water-soluble inorganic phosphoric acid compounds such as polyphosphoric acids, eg.
  • tripolyphosphoric acid for example, tripolyphosphoric acid, tetrapolyphosphoric acid, pentapolyphosphoric acid, pyrophosphoric acid, metaphosphoric acid and polyphosphoric acid and salts thereof (for example the Na salt or the K salt), aminocarboxylic acid compounds such as ethylenediaminetetraacetic acid, 1,3-propanediaminetetraacetic acid, diethylenetriaminepentaacetic acid , Triethylenetetraminehexaacetic acid, L-glutamic acid, N, N-bis (carboxymethyl) -L-glutamic acid and hydroxyethylethylenediaminetriacetic acid and the Salts thereof (for example the Na, K or ammonium salt), organic phosphorus compounds such as aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and 2-phosphono-but
  • particularly preferred chelating agent is diethylenetriaminepentaacetic acid, which is preferably used in form of its penta sodium salt available under the designation "VERSENEX ®".
  • the chelating agent can be used both in solid particulate form and in the form of aqueous solutions of the monomer solution, the polymer gel or the water-absorbent polymer structure are added, wherein the additive is in the form of aqueous solutions, for example in the form available under the designation "VERSENEX ®" aqueous solutions being most preferred.
  • these therefore comprise more than 2,000 ppm, more preferably at least 2,500 ppm and most preferably at least 3,000 ppm of a chelating agent, more preferably diethylenetriaminepentaacetic acid or a salt of diethylenetriaminepentaacetic acid, based in each case on the content of acrylic acid in the water-absorbing polymer structure.
  • a chelating agent more preferably diethylenetriaminepentaacetic acid or a salt of diethylenetriaminepentaacetic acid, based in each case on the content of acrylic acid in the water-absorbing polymer structure.
  • at least 90 wt .-% of the particles of the water-absorbing polymer structure have a particle size of less than 300 ⁇ .
  • the water-absorbing polymer structure has no core-shell structure.
  • a core-shell structure is formed when gel particles of the water-absorbing polymer structures or else the particles of the water-absorbing polymer obtained after drying Polymer structure in a further process step by means of chemical crosslinkers or polyvalent metal cations surface post-crosslinked, so that the crosslinking density in the outer region of the water-absorbing polymer structures is greater than in the core.
  • the water-absorbing polymer structures are not surface post-crosslinked.
  • Preferred chelating agents are in turn those chelating agents which have already been mentioned as preferred chelating agents in connection with the water-absorbing polymer structure according to the invention. Furthermore, it is preferred in connection with the process according to the invention that the water-absorbing polymer structures are screened off in process step V) in such a way that the proportion of polymer particles having a particle size of less than 300 ⁇ m at least 70% by weight, particularly preferably at least 80% by weight. %, and most preferably at least 90% by weight, based on the total weight of the water-absorbing polymer structures.
  • the water-absorbing polymer structure obtainable by the process according to the invention has the following properties: i) a soluble content of at least 10% by weight, more preferably at least 12.5% by weight and most preferably at least 15% by weight, determined according to the test method described herein; ii) a modulus of elasticity, determined according to the test method described herein, of at most 3 Pa, more preferably of at most 2.5 Pa, and most preferably of at most 2 Pa; iii) a gel viscosity drop determined by the test method described herein after 7 days at 80 ° C of the highest 25%, more preferably of at most 17.5% and most preferably of more than 10%.
  • a composite comprising a water-absorbing polymer structure according to the invention or a water-absorbing polymer structure obtainable by the process according to the invention and a substrate.
  • this composite is a swellable nonwoven fabric bandage known, for example, from EP-A-0 269 778, on which the particles of the water-absorbing polymer structure are applied.
  • nonwoven fabrics which represent, for example, a mixture of viscose fibers and polyvinyl alcohol fibers are suitable as the substrate.
  • Nonwoven fabrics comprising 75 to 95% by weight of viscose fibers and 5 to 25% by weight of polyvinyl alcohol fibers are particularly preferred, the basis weight of this nonwoven fabric preferably being at least 20 g / m 2 .
  • the amount of water-absorbing polymer structures in such a swellable non-woven fabric cable bandage is preferably 5 to 100 g / m 2 , more preferably 20 to 40 g / m 2 .
  • a contribution to achieving the abovementioned objects is also provided by a process for producing a composite, wherein the water-absorbing polymer structures according to the invention or the water-absorbing polymer structures obtainable by the process according to the invention are brought into contact with one another and optionally with an auxiliary.
  • the composite is the above-described swellable non-woven fabric bandage known from EP-A-0 269 778 on which the particles of the water-absorbing polymer structure are applied.
  • a substrate preferably a non-woven fabric of viscose fibers and polyvinyl alcohol fibers described above, coated on one side with the water-absorbing polymer structure or obtainable by the process according to the invention water-absorbing polymer structures and then this layer with another substrate, preferably with another Nonwoven fabric of viscose fibers and polyvinyl alcohol fibers, is covered, as described in EP-A-0 269 778.
  • the layer structure thus obtained can then be impregnated on both sides with a polyvinyl alcohol solution and then dried according to the teaching of EP-A-0 269 778.
  • a contribution to achieving the abovementioned objects is further provided by a cable comprising at least one coating layer which comprises the water-absorbing polymer structures according to the invention, the water-absorbing polymer structures obtainable by the process according to the invention, a composite according to the invention or a composite obtainable by the process according to the invention.
  • a contribution to the solution of the abovementioned objects is further made possible by the use of the water-absorbing polymer structures according to the invention, the water-absorbing polymer structures obtainable by the process according to the invention, a composite according to the invention or a composite obtainable by the process according to the invention for producing at least one coating layer in a cable.
  • a melting point tube 1 (inner diameter 2 mm, length 120 mm) closed on one side with cotton wool 2 is filled with water-absorbing polymer structures 3.
  • the water-absorbing polymer structure 3 is first filled into a Petri dish.
  • the melting point tube 1 is then pressed with the open end into the water-absorbing polymer structure 3 until the tube 1 is filled with the polymer structure 3 to a length of 5 mm.
  • the tube 1 is dropped three times from a height of 10 cm perpendicular to the cotton-sealed end on the table top to compact the water-absorbing polymer structure 3 inside the tube 1. This process is repeated until only about 10 mm of the tube 1 remain as a space not filled by the water-absorbing polymer structure 3.
  • the valves 9 and 10 are opened. After certain times (5 minutes, 10 minutes, 20 minutes, 1 hour, 2 hours, 8 hours, 1 day, 2 days, 3 days, 4 days, 5 days, 6 days and 7 days), the distance over which the Liquid penetrated into the tube 1 is determined (recognizable by the boundary line between the transparent gel and the white water-absorbing polymer structure).
  • the content of soluble fractions is determined in accordance with WSP 270.3 (11) after 16 hours.
  • the water-absorbing polymer structures are swollen with 50% of the amount of deionized water, which is able to absorb the water-absorbing polymer structures to a maximum.
  • the viscosity ⁇ of the gels by means of a Brookfield viscometer determined. Before determining the viscosity of the gels at time t 7 d, the gels are allowed to reach room temperature
  • the drop in gel viscosity is calculated as follows:
  • the polymerization by the subsequent addition of 0.85 g of sodium peroxodisulfate in 10 g of dist. Water, 0.7 g of 35% hydrogen peroxide solution in 10 g of dist. Water and 0.03 g of ascorbic acid in 2 g of dist. Water started. After the final temperature (about 100 ° C) was reached, the gel was minced with a meat grinder and sprayed with 3 g of Versenex ® 80, which in 50 mL dist. Water was dissolved. Then it was dried for 2 h at 150 ° C in a convection oven. The dried product was roughly crushed, ground and adjusted to the above particle size distribution.
  • Comparative examples are commercially available water-absorbing polymer structures, which are offered for use in cable sheathing.
  • Example 1 The polymer of Example 1 and the commercial reference products of Comparative Examples 1 and 2 were subjected to the above-described penetration test by means of the apparatus described in FIG.
  • the following table shows the distance over which deionized water has penetrated the melting point tube through the layer of the water-absorbing polymer structure at a temperature of 20 ° C. after 7 days:

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  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

La présente invention concerne des structures polymères absorbant l'eau à base d'acide polyacrylique réticulé partiellement neutralisé. Ces structures présentent les propriétés suivantes : i) une teneur en fractions solubles, déterminée par la méthode d'essai décrite ici, au moins égale à 10% en poids ; ii) un module d'élasticité, déterminé par la méthode d'essai décrite ici, au maximum égal à 3 Pa ; iii) une baisse de la viscosité du gel après 7 jours à 80°C, déterminée par la méthode d'essai décrite ici, au maximum égale à 25%. La présente invention concerne également un procédé de fabrication de structures polymères absorbant l'eau, les structures polymères absorbant l'eau qui peuvent être obtenues par ce procédé, un composite, un procédé de fabrication d'un composite, le composite qui peut être obtenu par ce procédé, un câble, ainsi que l'utilisation d'une composition ou d'un composite absorbant l'eau pour fabriquer une couche de gainage d'un câble.
PCT/EP2013/070509 2012-11-09 2013-10-02 Agent superabsorbant pour câbles Ceased WO2014072130A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012220400.8 2012-11-09
DE201210220400 DE102012220400A1 (de) 2012-11-09 2012-11-09 Superabsorber für Kabelanwendungen

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WO2014072130A1 true WO2014072130A1 (fr) 2014-05-15

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DE102021118114A1 (de) 2021-07-14 2023-01-19 Audi Aktiengesellschaft Hochvoltanordnung und Kraftfahrzeug
DE102022120726A1 (de) 2022-08-17 2024-02-22 Audi Aktiengesellschaft Energiespeicher für ein Kraftfahrzeug, Kraftfahrzeug und Verfahren zum Herstellen eines Energiespeichers

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DE2706135A1 (de) 1977-02-14 1978-08-17 Stockhausen & Cie Chem Fab Verdickungsmittel fuer ausgeschiedenen darminhalt und harn
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DE4020780C1 (fr) 1990-06-29 1991-08-29 Chemische Fabrik Stockhausen Gmbh, 4150 Krefeld, De
DE4244548A1 (de) 1992-12-30 1994-07-07 Stockhausen Chem Fab Gmbh Pulverförmige, unter Belastung wäßrige Flüssigkeiten sowie Blut absorbierende Polymere, Verfahren zu ihrer Herstellung und ihre Verwendung in textilen Konstruktionen für die Körperhygiene
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DE4333056A1 (de) 1993-09-29 1995-03-30 Stockhausen Chem Fab Gmbh Pulverförmige, wäßrige Flüssigkeiten absorbierende Polymere, Verfahren zu ihrer Herstellung und ihre Verwendung als Absorptionsmittel
WO1996005234A1 (fr) 1994-08-12 1996-02-22 Kao Corporation Procede d'elaboration d'un polymere super absorbant ameliore
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WO2004037903A2 (fr) 2002-10-25 2004-05-06 Stockhausen Gmbh Matiere polymere absorbante a capacite de retention et permeabilite ameliorees

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076663A (en) 1975-03-27 1978-02-28 Sanyo Chemical Industries, Ltd. Water absorbing starch resins
DE2706135A1 (de) 1977-02-14 1978-08-17 Stockhausen & Cie Chem Fab Verdickungsmittel fuer ausgeschiedenen darminhalt und harn
DE2840010A1 (de) 1977-12-15 1979-06-21 Nat Starch Chem Corp Pfropfmischpolymerisate und verfahren zu deren herstellung
US4286082A (en) 1979-04-06 1981-08-25 Nippon Shokubai Kagaku Kogyo & Co., Ltd. Absorbent resin composition and process for producing same
US4340706A (en) 1980-03-19 1982-07-20 Seitetsu Kagaku Co., Ltd. Alkali metal acrylate or ammonium acrylate polymer excellent in salt solution-absorbency and process for producing same
DE3503458A1 (de) 1984-02-04 1985-08-08 Arakawa Kagaku Kogyo K.K., Osaka Verfahren zur herstellung verbesserter wasser absorbierender harze
US4837077A (en) * 1984-12-21 1989-06-06 Intissel Hydroexpansible composite material, the preparation thereof and a composition for its implementation as well as the uses thereof
US4711022A (en) * 1986-03-26 1987-12-08 Freeman Clarence S Method for wire insulation
EP0269778A1 (fr) 1986-11-21 1988-06-08 Firma Carl Freudenberg Procédé pour la fabrication d'un bandage gonflant pour câble
DE3713601A1 (de) 1987-04-23 1988-11-10 Stockhausen Chem Fab Gmbh Verfahren zur herstellung eines stark wasserabsorbierenden polymerisats
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