EP1831312A2 - Hydrogels a point de congelation bas - Google Patents

Hydrogels a point de congelation bas

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Publication number
EP1831312A2
EP1831312A2 EP05818769A EP05818769A EP1831312A2 EP 1831312 A2 EP1831312 A2 EP 1831312A2 EP 05818769 A EP05818769 A EP 05818769A EP 05818769 A EP05818769 A EP 05818769A EP 1831312 A2 EP1831312 A2 EP 1831312A2
Authority
EP
European Patent Office
Prior art keywords
hydrogel
water
solvent
weight
polymer
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.)
Withdrawn
Application number
EP05818769A
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German (de)
English (en)
Inventor
Dieter Hermeling
Bernhard Steinmetz
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.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1831312A2 publication Critical patent/EP1831312A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C08F291/06—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to oxygen-containing macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D2303/00—Details of devices using other cold materials; Details of devices using cold-storage bodies
    • F25D2303/08—Devices using cold storage material, i.e. ice or other freezable liquid
    • F25D2303/085—Compositions of cold storage materials

Definitions

  • the present invention relates to low freezing hydrogels, processes for their preparation and the use of the hydrogels in coolants.
  • Water-absorbing polymers are in particular polymers of (co) polymerized hydrophilic monomers, graft (co) polymers of one or more hydrophilic monomers on a suitable graft base, crosslinked cellulose or starch ethers, crosslinked carboxymethyl cellulose, partially crosslinked polyalkylene oxide or swellable in aqueous liquids Natural products, such as guar derivatives. Such polymers are used as aqueous solution-absorbing products for the production of diapers, tampons, sanitary napkins and other sanitary articles, as water-retaining agents in agricultural horticulture, but also as thickeners for aqueous liquids.
  • WO-A-03/002623 describes postcrosslinked water-absorbing polymers based on acid group-carrying monomers which have been neutralized to 5 to 60 mol%.
  • WO 98/10032 discloses deicing compositions comprising a thickener and a hygroscopic substance and / or a short-chain aliphatic monohydric alcohol.
  • the thickening agent prevents the active substance (glycols, such as ethylene glycol and propylene glycol) from flowing off an inclined plane, for example a windscreen, and thus the formation of a water ice layer.
  • water-absorbing polymers are their use in coolant compositions, for example in cooling elements. It would be advantageous if the coolant is still deformable even at low temperatures. As a result, the cooling elements can optimally adapt to corresponding cavities. At the same time, the coolant should not leak if the sleeve is damaged.
  • the disadvantage here is that the additives tend to segregation, ie, that the additive separates from the hydrogel already during mixing of the water-absorbing polymer with the aqueous solution from the solution or during storage of the hydrogel in the cold.
  • the object of the present invention was to provide coolant compositions based on crosslinked water-absorbing polymers which do not have the abovementioned disadvantages.
  • At least one water-absorbing polymer comprising at least one polymerized ethylenically unsaturated, acid group-carrying monomer, wherein the acid groups are neutralized to 10 to 50 mol% and have sodium and / or potassium ions as counterion, and at least one polymerized crosslinker, b) at least one non-aqueous solvent and c) water,
  • the nonaqueous solvent is indefinitely miscible with water at 23 ° C, has a melting point below -2O 0 C, the solubility of common salt in a 50gew.-% aqueous solution of the solvent is at least 10g / 100g and the hydrogel at least 5 wt .-% of the solvent, based on the hydrogel contains.
  • the acid groups of the at least one polymerized ethylenically unsaturated, acid group-carrying monomer are preferably from 15 to 45 mol%, particularly preferably from 20 to 40 mol%, neutralized.
  • the neutralized acid groups preferably have at least 50 mol%, particularly preferably at least 75 mol%, very particularly preferably 100 mol%, of sodium and / or potassium ions as the counterion.
  • Sodium ions as the counterion are particularly preferred.
  • the melting point of the non-aqueous solvent is preferably below -30 0 C, more preferably below -4O 0 C, most preferably below -50 ° C.
  • the solubility of common salt in a 50% strength by weight aqueous solution of the solvent at 23 ° C. is preferably at least 11 g, more preferably at least 12 g, in each case based on 100 g of the 50% strength by weight aqueous solution used.
  • the solubility can only be determined if no segregation of water and non-aqueous solvent occurs (no salting out). Otherwise, a nonaqueous solvent-depleted liquid phase is formed, which naturally can dissolve more saline. This value does not therefore correspond to the solubility in a 50% by weight aqueous solution of the solvent tested.
  • the water-absorbing polymers are preferably used from 0.01 to 5 wt .-%, particularly preferably 0.05 to 4 wt .-%, most preferably 0.1 to 3 wt .-%, based on the hydrogel.
  • the hydrogel according to the invention preferably contains at least 10% by weight, preferably from 10 to 85% by weight, particularly preferably from 30 to 65% by weight, very particularly preferably from 40 to 55% by weight, based on the hydrogel, of the nonaqueous solvent.
  • Preferred non-aqueous solvents are methanol, 2-methoxyethanol, dimethylformamide and 1, 2-propylene glycol.
  • the solvents may be used alone or as a mixture, for example methanol, 1, 2-propylene glycol or methanol / 1, 2-propylene glycol.
  • the hydrogel according to the invention preferably contains at least 10% by weight, preferably from 10 to 85% by weight, particularly preferably from 30 to 65% by weight, very particularly preferably from 40 to 55% by weight, based on the hydrogel , Water.
  • the sum of components a) to c) amounts to a maximum of 100% by weight.
  • the hydrogels according to the invention are obtained by mixing components a) to c), it being possible if appropriate to add further components.
  • the order of mixing is arbitrary, preferably the components b) and c) are premixed.
  • Another object of the present invention are hydrogels having a freezing point of below -10 ° C, preferably below -20 0 C, most preferably below -30 0 C.
  • hydrogels according to the invention are suitable as coolants in cooling elements.
  • Another object of the present invention are cooling elements comprising
  • the freezing point of the hydrogels used is preferably below -20 0 C, most preferably below -30 0 C.
  • Suitable materials for the outer shell are, for example, polyethylene, polypropylene and polyvinyl chloride.
  • the water-absorbing polymers to be used in the process according to the invention are subject to no restriction.
  • the preparation of water-absorbing polymers is described, for example, in the monograph "Modern Superabsorbent Polymer Technology", F.L. Buchholz and AT. Graham, Wiley-VCH, 1998, or in Ullmann's Encyclopedia of Industrial Chemistry, 6th ed., Vol. 35, pages 73-93.
  • ethylenically unsaturated, acid group-carrying monomers are reacted in the presence of crosslinking agents to form a base polymer.
  • the reaction is preferably carried out in a kneader, for example as described in WO-A-01/38402, or on a belt reactor, as described, for example, in EP-A-0 955 086. Subsequently, the base polymers can still be post-crosslinked.
  • the water-absorbing polymers to be used in the process according to the invention are, in particular, polymers of crosslinked (co) polymerized hydrophilic monomers, polyaspartic acid, graft (co) polymers of one or more hydrophilic monomers onto a suitable graft base, crosslinked cellulose or starch ethers.
  • the polymer to be crosslinked is a polymer containing structural units derived from acrylic acid or its esters, or obtained by graft copolymerization of acrylic acid or acrylic acid esters onto a water-soluble polymer matrix.
  • These hydrogels are known to the person skilled in the art and are described, for example, in US Pat. Nos.
  • Hydrophilic monomers suitable for preparing these water-absorbing polymers include, for example, polymerizable acids such as acrylic acid, methacrylic acid, vinylsulfonic acid, vinylphosphonic acid, maleic acid including its anhydride, fumaric acid, itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido 2-methylpropanephosphonic acid and its amides, hydroxyalkyl esters and aminogroup or ammonium group-containing esters and amides, and also the alkali metal and / or ammonium salts of the monomers containing acid groups.
  • water-soluble N-vinyl amides such as N-vinylformamide or diallyldimethylammonium chloride are suitable.
  • Preferred hydrophilic monomers are compounds of general formula I.
  • R 1 is hydrogen, methyl, ethyl or carboxyl
  • R 2 -COOR 4 hydroxysulfonyl or phosphonyl, one with a C 1 -C 4 -AlOnOl esterified phosphonyl group or a group of formula II
  • R 3 is hydrogen, methyl or ethyl
  • R 4 is hydrogen, Ci-d-aminoalkyl, dd-hydroxyalkyl, alkali metal or ammonium ammonium ion and
  • R 5 is a sulfonyl group, a phosphonyl group or a carboxyl group or in each case their alkali metal or ammonium salts.
  • C 1 -C 4 -alkanols are methanol, ethanol, n-propanol, isopropanol or n-butanol.
  • hydrophilic monomers are acrylic acid and methacrylic acid, as well as their sodium and potassium salts.
  • Suitable graft bases for water-absorbing polymers obtained by graft copolymerization of olefinically unsaturated acids or their alkali metal or ammonium Salts are available, may be natural or synthetic origin. Examples are starch, cellulose or cellulose derivatives and other polysaccharides and oligosaccharides, polyalkylene oxides, in particular polyethylene oxides and polypropylene oxides, and also hydrophilic polyesters.
  • Suitable polyalkylene oxides have, for example, the formula III
  • R 6 , R 7 independently of one another are hydrogen, alkyl, alkenyl or aryl,
  • R 8 is hydrogen or methyl
  • p is an integer from 1 to 500.
  • R 6 and R 7 are preferably hydrogen, C 1 -C 4 -alkyl, C 2 -C 6 -alkenyl or phenyl.
  • Preferred water-absorbing polymers are, in particular, polyacrylates, polymethacrylates and also the graft polymers described in US Pat. Nos. 4,931,497, 5,011, 892 and 5,041,496.
  • the water-absorbing polymers are crosslinked, ie they contain compounds having at least two double bonds, which are polymerized into the polymer network.
  • Suitable crosslinking agents are, in particular N, N'-methylenebisacrylamide and N 1 N'-methylenebismethacrylamide, esters of unsaturated mono- or polycarboxylic acids of polyols, such as diacrylate or triacrylate, for example butanediol or ethylene diacrylate or trimethylolpropane triacrylate and allyl compounds such as methacrylate and Al lyl ( meth) acrylate, triallyl cyanurate, maleic acid diallyl esters, polyallyl esters, tetraallyloxyethane, triallylamine, tetraallylethylenediamine, allyl esters of phosphoric acid and vinylphosphonic acid derivatives, as described, for example, in EP-A 343 427.
  • di (meth) acrylates of polyethylene glycols in the process according to the invention, the polyethylene glycol used having a molecular weight between 300 and 1000.
  • di- and / or tri (meth) acrylates of polyethoxylated trimethylolpropane or trimethylolethane Particularly suitable are tri (meth) acrylates of 5-fold to 30-fold ethoxylated trimethylolpropane or trimethylolethane.
  • Most suitable are the triacrylates of 13-fold to 18-fold ethoxylated trimethylolpropane or trimethylolethane.
  • hydrogels which are prepared by using polyallyl ethers as crosslinkers and by acidic homopolymerization of acrylic acid.
  • Suitable crosslinkers are pentaerythritol tri- and tetraallyl ethers, polyethylene glycol diallyl ether, monoethylene glycol diallyl ether, glycerol di- and triallyl ethers, polyallyl ethers based on sorbitol, and ethoxylated variants thereof.
  • Very particularly preferred crosslinking agents are the polyethyleneglyoxylated and / or propoxylated glycerols esterified with acrylic acid or methacrylic acid to form di- or triacrylates, as described, for example, in the earlier German patent application with the file reference 103 19 462.2.
  • Particularly advantageous are di- and / or triacrylates of 3- to 10-fold ethoxylated glycerol.
  • diacrylates or triacrylates of 1 to 5 times ethoxylated and / or propoxylated glycerol.
  • Most preferred are the triacrylates of 3 to 5 times ethoxylated or propoxylated glycerol.
  • base polymer which can be used in the process according to the invention are described in "Modern Superabsorbent Polymer Technology", F.L. Buchholz and AT. Graham, Wiley-VCH, 1998, pages 77-84. Particular preference is given to base polymers which are prepared in the kneader, as described, for example, in WO 01/38402, or on a belt reactor, as described, for example, in EP-A 955 086.
  • the water-absorbing polymer is preferably a polymeric acrylic acid or a polyacrylate.
  • the preparation of this water-absorbing polymer can be carried out by a method known from the literature. Preference is given to polymers which contain crosslinking comonomers in amounts of from 0.01 to 10 mol%, preferably from 0.2 to 1 mol%, but very particular preference is given to polymers obtained by free-radical polymerization in which a polyfunctional ethylenically unsaturated Radical crosslinker was used, which additionally carries at least one free hydroxyl group (such as pentaerythritol triallyl ether or trimethylolpropandiallylether).
  • the water-absorbing polymers can be prepared by per se known polymerization.
  • the polymerization in aqueous solution by the method of so-called gel polymerization.
  • gel polymerization for example, 15 to 50% strength by weight aqueous solutions of one or more hydrophilic monomers and, if appropriate, a suitable grafting base in the presence of a free-radical initiator, preferably without mechanical mixing, utilizing the Tromms-Dorff-Norrish effect (Makromol Chem 1, 169 (1947)), polymerized.
  • the polymer tion reaction can be carried out in the temperature range between 0 and 15O 0 C, preferably between 10 and 100 0 C, both at atmospheric pressure and under elevated or reduced pressure.
  • the polymerization can also be carried out in a protective gas atmosphere, preferably under nitrogen, high-energy electromagnetic radiation or the usual chemical polymerization initiators can be used to initiate the polymerization, for example organic peroxides, such as benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone oxide , Cumene hydroperoxide, azo compounds such as azodiisobutyronitrile and inorganic peroxo compounds such as (NH 4 ) 2 S 2 O 8 , K 2 S 2 O 8 , Na 2 S 2 O 8 or H 2 O 2 .
  • organic peroxides such as benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone oxide , Cumene hydroperoxide, azo compounds such as azodiisobutyronitrile and inorganic peroxo compounds such as (NH 4 ) 2 S 2 O 8 , K 2 S 2 O 8 , Na 2 S
  • reducing agents such as sodium bisulfite and iron (II) sulfate or redox systems containing as reducing component an aliphatic and aromatic sulfinic acid such as benzenesulfinic acid and toluenesulfinic acid or derivatives of these acids, such as Mannich adducts of sulfinic acids, aldehydes and amino compounds, be used.
  • reducing agents such as sodium bisulfite and iron (II) sulfate or redox systems containing as reducing component an aliphatic and aromatic sulfinic acid such as benzenesulfinic acid and toluenesulfinic acid or derivatives of these acids, such as Mannich adducts of sulfinic acids, aldehydes and amino compounds, be used.
  • the gels obtained are neutralized to from 10 to 60 mol%, preferably from 20 to 55 mol% and particularly preferably from 25 to 50 mol%, based on the monomer used, it being possible to use the customary neutralizing agents, preferably alkali metal hydroxides or oxides, but particularly preferably sodium hydroxide, sodium carbonate and sodium bicarbonate.
  • the customary neutralizing agents preferably alkali metal hydroxides or oxides, but particularly preferably sodium hydroxide, sodium carbonate and sodium bicarbonate.
  • the hydrogels containing at least one non-aqueous solvent and water are at low temperatures. With a lower degree of neutralization of the water-absorbing polymer, its swelling capacity decreases.
  • the neutralization is achieved by mixing the neutralizing agent as an aqueous solution or preferably as a solid.
  • the gel is mechanically comminuted for this purpose, for example by means of a meat grinder and the neutralizing agent is sprayed on, sprinkled or poured over, and then carefully mixed.
  • the gel mass obtained can be further gewolfft for homogenization.
  • the neutralized gel mass is then dried with a belt or roller dryer until the residual moisture content is preferably below 10% by weight, in particular below 5% by weight.
  • the dried hydrogel is then milled and sieved, with mill stands, pin mills or vibratory mills usually being used for grinding.
  • the particle size of the sieved hydrogel is usually below 1000 .mu.m, often below 700 .mu.m, preferably below 500 .mu.m.
  • the postcrosslinking is usually carried out such that a solution of the surface postcrosslinker to the hydrogel or the dry base polymer powder is sprayed on. Following the spraying, the polymer powder is thermally dried, whereby the crosslinking reaction can take place both before and during drying.
  • reaction mixers or mixing and drying plants such as, for example, Lödige® mixers, BEPEX® mixers, NAUTA® mixers, SCHUGGI® mixers, NARA® dryers and PROCESSALL®.
  • fluidized bed dryers can also be used.
  • the drying can take place in the mixer itself, by heating the jacket or blowing hot air. Also suitable is a downstream dryer, such as a hopper dryer, a rotary kiln or a heatable screw. However, it is also possible, for example, to use an azeotropic distillation as the drying process.
  • Preferred drying temperatures are in the range 50 to 250 0 C, preferably at 50 to 200 0 C, and more preferably at 50 to 150 0 C.
  • the preferred residence time at this temperature in the reaction mixer or dryer is less than 30 minutes, more preferably less than 10 minutes.
  • the crosslinker is preferably dissolved in non-reactive solvents, preferably in lower alcohols, such as, for example, methanol, ethanol, propanediol, ethylene glycol, very particularly preferably in aqueous solutions of such suitable alcohols, the alcohol content of the solution being from 10 to 90% by weight, particularly preferably from 40 to 60% by weight.
  • lower alcohols such as, for example, methanol, ethanol, propanediol, ethylene glycol
  • the crosslinker is used in an amount of 0.01 to 1 wt .-%, based on the polymer used, and the crosslinker solution itself in an amount of 1 to 20 wt .-%, preferably 5 to 15 wt .-% , based on the polymer used, used.
  • the hydrogels of the invention have a low freezing point and do not segregate even after prolonged storage. This is achieved by the optimal coordination of ionic strength of the counterions and degree of neutralization. If the water-absorbing polymer is too hydrophobic, water precipitates as a liquid, slowly solidifying phase at low temperatures; if the water-absorbing polymer is too hydrophilic, the diol separates out at low temperatures as a liquid phase.
  • water-absorbing polymers can also be used for the hydrogels according to the invention, as used, for example, for adult incontinence.
  • water-absorbing polymers for the hydrogels of the invention are available at low cost.
  • the measurements should be carried out at an ambient temperature of 23 ⁇ 2 0 C and a relative humidity of 50 ⁇ 10%.
  • the swellable hydrogel-forming polymer is thoroughly mixed before the measurement.
  • the swelling capacity is determined according to the test method No. 440.2-02 "Free swell capacity" recommended by the EDANA (European Disposables and Nonwovens Association).
  • centrifuge retention capacity is determined according to the test method No. 441.2-02 "Centrifuge retention capacity" recommended by the EDANA (European Disposables and Nonwovens Association).
  • a Dewar vessel was charged with 248 g of water, 91 g of acrylic acid, 0.5 g of pentaerythritol triallyl ether and 0.036 g of Kymene® 736 (aqueous reaction product of a polymeric amine with epichlorohydrin). Nitrogen was sparged for 30 minutes while sparging with nitrogen. Then, by addition of 0.01 g of 35% strength by weight hydrogen peroxide, 1.0 g of 1% strength by weight aqueous ascorbic acid and 9.1 g of 10% strength by weight aqueous sodium hydrogensulfite were started at about 23 ° C. The gel ultimately obtained was neutralized in a meat grinder with 73.8 g of 50% strength by weight sodium hydroxide solution. Then it was dried at 180 0 C for about 3 hours in a convection oven. It was then ground and sieved to 100 to 850 microns.
  • the postcrosslinking solution had the following composition: 4.8% by weight of ethylene glycol diglycidyl ether, 47.6% by weight of propylene glycol and 47.6% by weight of water.
  • the postcrosslinked, water-absorbing polymer A had the following properties: FSC: 47.7 g / g
  • the postcrosslinking solution had the following composition: 2% by weight of ethylene glycol diglycidyl ether, 30% by weight of propylene glycol and 68% by weight of water.
  • the postcrosslinked, water-absorbing polymer B had the following properties:
  • hydrogel A portion of the hydrogel was placed in a large test tube and cooled externally with acetone / dry ice. The hydrogel completely solidified at -39 ° C. The remainder of the hydrogel was placed in a sealable bottle and stored at 23 ° C. After a week, no phase separation was seen.
  • hydrogel A portion of the hydrogel was placed in a large test tube and cooled externally with acetone / dry ice. The hydrogel completely solidified at -39 ° C.
  • the remainder of the hydrogel was placed in a sealable bottle and stored at 23 ° C. After a week, a phase separation was seen. The hydrogel had settled. Above the hydrogel, a liquid phase (1,2-propanediol) was detected.
  • a portion of the hydrogel was placed in a large test tube and cooled externally with acetone / dry ice.
  • the freezing point of the hydrogel was below -50 ° C.
  • the remainder of the hydrogel was placed in a sealable bottle and stored at 23 ° C. After a week, no phase separation was seen.
  • hydrogel A portion of the hydrogel was placed in a large test tube and cooled externally with acetone / dry ice. The hydrogel completely solidified at -42 ° C.
  • hydrogel A portion of the hydrogel was placed in a large test tube and cooled externally with acetone / dry ice. The hydrogel completely solidified at -51 0C.
  • the remainder of the hydrogel was placed in a sealable bottle and stored at 23 ° C. After a week, no phase separation was seen.
  • hydrogel A portion of the hydrogel was placed in a large test tube and cooled externally with acetone / dry ice. The hydrogel solidified completely at -15 ° C.
  • the remainder of the hydrogel was placed in a sealable bottle and stored at 23 ° C. After three hours, a phase separation was seen. The hydrogel had settled. Above the hydrogel, a liquid phase (1-propanol) was detected.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Colloid Chemistry (AREA)

Abstract

L'invention concerne des hydrogels à point de congélation bas, qui contiennent au moins un polymère absorbant l'eau, au moins un solvant non aqueux, ainsi que de l'eau. L'invention concerne également un procédé pour la production de tels hydrogels et leur utilisation dans des éléments réfrigérants.
EP05818769A 2004-12-20 2005-12-16 Hydrogels a point de congelation bas Withdrawn EP1831312A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004062458A DE102004062458A1 (de) 2004-12-20 2004-12-20 Hydrogele mit niedrigem Gefrierpunkt
PCT/EP2005/013554 WO2006066811A2 (fr) 2004-12-20 2005-12-16 Hydrogels a point de congelation bas

Publications (1)

Publication Number Publication Date
EP1831312A2 true EP1831312A2 (fr) 2007-09-12

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EP05818769A Withdrawn EP1831312A2 (fr) 2004-12-20 2005-12-16 Hydrogels a point de congelation bas

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US (1) US20080221260A1 (fr)
EP (1) EP1831312A2 (fr)
JP (1) JP2008524411A (fr)
CN (1) CN101084278A (fr)
DE (1) DE102004062458A1 (fr)
WO (1) WO2006066811A2 (fr)

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WO2010113276A1 (fr) * 2009-03-31 2010-10-07 本田技研工業株式会社 Composition de liquide de refroidissement
KR102411151B1 (ko) * 2015-09-15 2022-06-22 한국전자통신연구원 냉각장치 및 그 제조 방법
AU2018387123B2 (en) 2017-12-22 2024-03-14 Cronin Group Pty Ltd A cooling device and methods of forming and regenerating same
CN109459462B (zh) * 2018-10-31 2021-03-19 泉州市全通光电科技有限公司 一种自动冰点测定仪及其测试方法

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EP1425320B1 (fr) * 2001-06-28 2006-09-20 Basf Aktiengesellschaft Hydrogels acides a forte capacite de gonflement

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CN101084278A (zh) 2007-12-05
WO2006066811A3 (fr) 2006-10-12
WO2006066811A2 (fr) 2006-06-29
DE102004062458A1 (de) 2006-07-06
US20080221260A1 (en) 2008-09-11
JP2008524411A (ja) 2008-07-10

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