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WO1998016308A1 - Materiaux composites - Google Patents

Materiaux composites Download PDF

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Publication number
WO1998016308A1
WO1998016308A1 PCT/EP1997/005664 EP9705664W WO9816308A1 WO 1998016308 A1 WO1998016308 A1 WO 1998016308A1 EP 9705664 W EP9705664 W EP 9705664W WO 9816308 A1 WO9816308 A1 WO 9816308A1
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Prior art keywords
acid
composite materials
water
materials according
foam
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PCT/EP1997/005664
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German (de)
English (en)
Inventor
Matthias Kroner
Hans-Joachim HÄHNLE
Martin Rübenacker
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Basf Aktiengesellschaft
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Publication of WO1998016308A1 publication Critical patent/WO1998016308A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function

Definitions

  • the present invention relates to composite materials made of inorganic minerals and polymer gels and their use.
  • Composite materials made from inorganic minerals and naturally occurring organic polymers are known and widely used in nature. They include e.g. Shellfish shells, coral reefs, snail shells, egg shells, bones, teeth and antlers. Shellfish and mother-of-pearl e.g. are natural composite materials that consist of 95 to 99% by weight of calcium carbonate and 1 to 5% by weight of proteins and chitin. These composites, also known as bio-minerals, are notable for their hardness and strength, but are not brittle, while synthetic inorganic solids generally also have an undesirable brittleness in addition to their hardness, which leads to breakage of the materials when impacted.
  • JP-A-55124-651 describes the production of composites from CaC0 3 and plastic films or synthetic papers by carbonizing Ca (OH) 2 with C0 2 in the presence of polymers of isobutene and maleic anhydride.
  • JP-A-54149-399 describes the production of cubic CaC0 3 by crystallization from Ca (OH) 2 and C0 2 in the presence of polyacrylic acids and other additives, such as, for example, alkali metal chlorides. -carbonates, -hydrogencarbonates and glycerol and a water-soluble saccharide.
  • JP-A-53002-557 describes the preparation of an aqueous 5 CaC0 3 dispersion with a solids content of 40 to 70% by weight by reaction of Ca (OH) 2 and C0 2 in a solution of polyacrylic acid with a molecular weight of about 9000 or an alkali salt thereof.
  • control agents such as e.g. 20 sodium hexamethaphosphate or various polymers, such as polyacrylic acid with a molecular weight of 800 to 20,000, sulfo-containing polymers, polymaleic acids and polyacrylamides.
  • the object is achieved if the composite materials comprise a polymer gel and an inorganic salt or mineral.
  • the invention therefore relates to composite materials comprising A) at least one water-swellable polymer gel, B) at least one electroneutral compound which comprises one or more cations (s) and one or more anion (s) (the charges of the cations and anions being different compensate each other so that the connection is electroneutral), as well as other components if necessary.
  • the composite materials according to the invention contain at least one water-swellable polymer gel A).
  • Suitable polymer gels A) are gels with limited swellability. It can be natural polymer gels, especially based on carbohydrates or proteins.
  • Suitable carbohydrates are e.g. cross-linked starch and cellulose and derivatives thereof.
  • Suitable crosslinking agents are diols, such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, etc., dialdehydes, such as glutaraldehyde, epichlorohydrin, etc.
  • the carbohydrates can also be chemically modified, e.g. by alkylation, hydroxyalkylation, carboxyalkylation.
  • Examples of chemically modified carbohydrates are methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl methyl cellulose etc., all of which are commercially available.
  • Suitable polymer gels are e.g. So-called superabsorbers, which have a absorption capacity of up to 200 times their weight when swollen in liquids, such as water, without losing their geometric shape.
  • the polymer gels can have any regular or irregular shapes or can be applied to carrier materials. According to a special embodiment, these gels can be foam-shaped.
  • highly swellable gels are also suitable as polymer gels A), which lose their shape when swollen in liquids and change into a colloidal state.
  • Such gels are e.g. in EP-B-0 412 388 and are described inter alia in used as a thickener in textile printing, for thickening paper coating slips or for thickening aqueous paint dispersions.
  • Polymer gels A are preferably prepared by polymerizing a mixture (Ml) which a) contains at least one monomer with a hydrophilic group, in particular a water-soluble, monoethylenically unsaturated monomer, b) optionally contains a crosslinker with at least one two non-conjugated, ethylenically unsaturated double bonds, c) optionally at least one additional, copolymerizable, water-insoluble monoethylenically unsaturated monomer, d) at least one polymerization initiator, e) optionally at least one polymerization regulator and, if appropriate, further constituents, in water or a water-containing solvent mixture.
  • Ml a mixture
  • Ml a) contains at least one monomer with a hydrophilic group, in particular a water-soluble, monoethylenically unsaturated monomer
  • b) optionally contains a crosslinker with at least one two non-conjugated, ethylenically
  • Suitable monomers a) are, for example, monoethylenically unsaturated C 3 -C 25 -carboxylic acids or anhydrides, preferably C 3 - to C ⁇ -carboxylic acids and their amides and esters with amino alcohols of the formula
  • A is an alkylene radical with 2 to 5 carbon atoms
  • R 1 , R 2 and R 3 independently of one another are hydrogen, methyl, ethyl and propyl and X® is an anion.
  • Suitable monomers a) are amides of the aforementioned carboxylic acids, which are derived from amines of the formula
  • the monomers a) are then, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, acrylamide, methacrylamide, crotonic acid amide, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylamino neopentylacrylate and dimethylaminoethyl methacrylate, dimethyl aminophenyl methacrylate, dimethyl methacrylate .
  • the basic acrylates and methacrylates or basic amides which are derived from the compounds of the formula II, are used in the form of their salts with strong mineral acids, sulfonic acids or carboxylic acids or in quaternized form.
  • the Anion X® then stands for the acid residue of the mineral acids or carboxylic acids or for a methosulfate, ethosulfate or halide from a quaternizing agent.
  • Suitable water-soluble monomers (a) are N-vinylpyrrolidone, N-vinylformamide, monoethylenically unsaturated sulfonic acids, such as, for example, vinylsulfonic acid, allylsulfonic acid, vinylphosphonic acid, vinyl lactic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate 3, 2-hydroxyl methacrylate, 2 acryloxy propylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylphosphonic acid, vinylphosphoric acid and allylphosphonic acid.
  • sulfonic acids such as, for example, vinylsulfonic acid, allylsulfonic acid, vinylphosphonic acid, vinyl lactic acid, sulfoethyl acrylate
  • Suitable organic peroxides are, for example, acetyl acetone peroxide, methyl ethyl ketone peroxide, tert. -Butyl hydroperoxide, cumene hydroperoxide, tert. -Amyl perpivalate, tert. Butyl perpivalate, tert. Butyl perneohexanoate, tert. Butyl perisobutyrate, tert. -Butyl- per-2-ethylhexanoate, tert. Butyl perisononanoate, tert. Butyl per maleate, tert. Butyl perbenzoate, tert.
  • the reaction mixture heats up depending on the starting conditions chosen, such as the concentration of the monomers in the aqueous solution and the type of monomers. Due to the heat of polymerization released, the temperature of the reaction mixture rises to, for example, 30 to 180, preferably 40 to 130 ° C.
  • the polymerization can be carried out under normal pressure, under reduced pressure or under increased pressure. Working under increased pressure can be advantageous in such cases if the temperature maximum to be expected during the polymerization is above the boiling point of the solvent mixture used. On the other hand, it can be advantageous to lower the maximum temperature with the help of evaporative cooling by polymerizing under reduced pressure or by external cooling, especially in the production of very high molecular weight products.
  • the foaming being carried out by dispersing fine bubbles of a gas which is inert to free radicals, and
  • Preferred monomers a) for producing foam-like superabsorbers are acrylic acid, methacrylic acid, vinylsulfonic acid, acrylamidopropanesulfonic acid, or mixtures thereof.
  • the monomers a) are neutralized to at least 50 mol%, preferably to 65 mol%.
  • the bases mentioned above are used for neutralization, preferably sodium hydroxide solution or potassium hydroxide solution.
  • the above-mentioned components b) are suitable crosslinkers b) for the production of foam-like polymers A).
  • two different crosslinkers are used, one of which is water-soluble and the other of which is water-insoluble.
  • the hydrophilic crosslinker which is soluble in the aqueous phase of the reaction mixture, conventionally brings about a relatively uniform crosslinking of the resulting polymer, as is customary in the production of a superabsorbent.
  • the hydrophobic crosslinking agent which is insoluble or only sparingly soluble in the polymerizable aqueous mixture, accumulates in the surfactant boundary layer between the gas phase and the polymerizable aqueous phase. As a result, the surface of the foam is crosslinked more than the inner part of the superabsorbent hydrogel in the subsequent polymerization.
  • Products according to the invention with a core-shell structure show significantly improved properties compared to homogeneously cross-linked samples with regard to the uptake rate, distribution effect and gel stability.
  • polyvalent metal ions all of the water-insoluble crosslinkers described above, which can be assigned to the different groups, are suitable for producing foams with a core-shell structure, that is to say foams in which the entire surface is more strongly crosslinked than the underlying layer was referred to above as the core layer.
  • hydrophobic crosslinkers are diacrylates or dimethacrylates or divinyl ethers of alkanediols with 2 to 25 C atoms (branched, linear, with any arrangement of the OH groups), such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentylglycol, 1, 9-nonanediol or 1,2-dodecanediol, di-, tri- or polypropylene glycol diacrlyate or dimethacrylate, allyl acrylate, allyl methacryla, divinylbenzene, glycidyl acrylate or glycidyl methacrylate, allyl glycidyl ether and bisglycidyl ether of the alkane listed above.
  • photoinitiators are usually used as initiators. These can be, for example, so-called ⁇ -splitters, H-abstracting systems or also azides.
  • initiators are benzophenone derivatives such as Michlers ketone, phenanthrene derivatives, fluorene derivatives, anthraquinone derivatives, thioxanone derivatives, coumarin derivatives, benzoin ethers and their derivatives, substituted azo compounds such as the radical formers mentioned above Hexaarylbisimidazole or acylphosphine oxides.
  • azides examples include 2- (N, N-dimethylamino) ethyl 4-azidocinnamate, 2- (N, N-dimethylamino) ethyl-4-azidonaphthyl ketone, 2- (N, N-dimethylamino) -ethyl-4-azidobenzoate, 5-azido-l-naphthyl-2 '- (N, N-dimethylamino) ethylsulfone, N- (4-sulfonyl azidophenyl) maleimide, N-acetyl-4-sulfonyl azidoaniline, 4-sul- fonylazidoaniline, 4-azidoaniline, 4-azidophenacyl bromide, p-azide-topzoic acid, 2,6-bis (p-azidobenzylidene) cyclohexanone and 2,6-bis (p-
  • polymerization regulator e a polymerization regulator e
  • a mixture of several polymerization regulators Suitable polymerization regulators are those mentioned above.
  • the amounts of polymerization regulator e) can be up to 10% by weight, preferably 0.1 to 5% by weight, based on the monomers used.
  • the polymerizable aqueous mixtures (M2) contain as component f) 0.1 to 20% by weight of at least one surfactant.
  • the tensides are of crucial importance for the production and stabilization of the foam.
  • Anionic, cationic or nonionic surfactants or surfactant mixtures which are compatible with one another can be used.
  • Low-molecular or polymeric surfactants f) can be used, combinations of different or similar types of surfactants having proven to be advantageous.
  • Suitable nonionic surfactants f) are, for example, addition products of alkylene oxides, in particular ethylene oxide, propylene oxide and / or butylene oxide with alcohols, amines, phenols, naphthols or carboxylic acids. Addition products of ethylene oxide and / or propylene oxide with alcohols containing at least 10 carbon atoms are advantageously used as surfactants, the addition products containing 3 to 200 moles of ethylene oxide and / or propylene oxide per mole of alcohol. The addition products contain the alkylene oxide units in the form of blocks or in a statistical distribution.
  • nonionic surfactants f) are, for example, addition products of 7 mol of ethylene oxide with 1 mol of tallow fatty alcohol, Additions of 9 moles of ethylene oxide to 1 mole of tallow fatty alcohol and addition products of 80 moles of ethylene oxide to 1 mole of tallow fatty alcohol are used.
  • nonionic surfactants include reaction products of oxo alcohols (isomer mixture of higher alcohols obtained by oxo synthesis) or Ziegler alcohols (primary, linear C ⁇ o to C 22 alcohols, obtained by oligomerization of ethylene and subsequent oxidation after the Ziegler-Alfol process) with 5 to 12 moles of ethylene oxide per mole of alcohol, in particular with 7 moles of ethylene oxide.
  • oxo alcohols is mixture of higher alcohols obtained by oxo synthesis
  • Ziegler alcohols primary, linear C ⁇ o to C 22 alcohols, obtained by oligomerization of ethylene and subsequent oxidation after the Ziegler-Alfol process
  • f are produced by ethoxylating castor oil. For example, 12 to 80 moles of ethylene oxide are added per mole of castor oil.
  • Preferred nonionic surfactants f) are, for example, the reaction products of 18 moles of ethylene oxide with 1 mole of tallow fatty alcohol, the addition products of 10 moles of ethylene oxide with 1 mole of a C 3 / Ci 5 oxo alcohol, or the reaction products of 7 to 8 moles of ethylene oxide with 1 mole a C ⁇ 3 / Ci 5 oxo alcohol.
  • Other suitable nonionic surfactants f) are phenol alkoxylates such as p-tert. -Butylphenol with 9 moles of ethylene oxide or methyl ether of reaction products from 1 mole of a -C 2 - to cig alcohol and 7.5 moles of ethylene oxide.
  • Suitable anionic surfactants f) are, for example, alkali metal or ammonium salts of sulfuric acid semiesters of addition products of ethylene oxide and / or propylene oxide with fatty alcohols, alkali metal or ammonium salts of alkylbenzenesulfonic acid or of alkylphenol ether sulfates.
  • the nonionic surfactants f) described above can be converted into the corresponding sulfuric acid semiesters, for example by esterification with sulfuric acid.
  • Suitable anionic surfactants f) are commercially available.
  • the surfactant content of the polymerizable aqueous mixture (M2) is 0.1 to 20% by weight, preferably 0.5 to 10% by weight, in particular 1.5 to 6% by weight.
  • the polymerizable aqueous mixtures can optionally contain at least one solubilizer as component g).
  • Suitable solubilizers g) are water-miscible organic solvents, such as e.g. Alcohols, glycols, polyethylene glycols and monoethers derived therefrom, the monoethers, e.g. Methyl glycol, butyl glycol, butyl diglycol, methyl diglycol, butyl triglycol, 3-ethoxy-l-propanol and glycerol monomethyl ether.
  • the polymerizable aqueous mixtures (M2) contain 0 to 50% by weight, preferably 0 to 25% by weight, of at least one solubilizer g).
  • Suitable thickeners h) are, for example, high molecular weight polymers of the monoethylenically unsaturated monomers containing acid groups described above under a), such as homopolymers of acrylic acid and / or methacrylic acid or slightly crosslinked copolymers of acrylic acid and / or methacrylic acid and a crosslinking agent which contains at least 2 ethylenically unsaturated Contains double bonds, such as butanediol diacrylate.
  • High molecular weight polymers of acrylamide and methacrylamide or copolymers of acrylic acid and acrylamide with molecular weights of more than 1,000,000 are also suitable.
  • High molecular weight are also suitable Polyethylene glycols or copolymers of ethylene glycol and propylene glycol, as well as high molecular polysaccharides such as starch, guar gum, locust bean gum or derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose and mixed cellulose ether.
  • Other suitable thickeners h) are water-insoluble products, such as, for example, finely divided silicon dioxide, pyrogenic silicas, precipitated silicas in hydrophilic or hydrophobic modifications, zeolites, titanium dioxide, cellulose powder, or other finely divided powders of crosslinked polymers other than superabsorbents.
  • the polymerizable aqueous mixtures (M2) can contain the thickeners in amounts of 0 to 30% by weight, preferably 0.5 to 20% by weight.
  • the polymerizable aqueous mixture (M2) may further contain foam stabilizers h) in order to optimize the foam structure.
  • foam stabilizers g) are e.g. Hydrocarbons with at least 5 carbon atoms in the molecule, e.g. Pentane, hexane, cyclohexane, heptane, octane, isooctane, decane and dodecane.
  • Suitable aliphatic hydrocarbons can be straight-chain, branched or cyclic and have a boiling temperature which is above the temperature of the aqueous mixture (M2) during foaming.
  • the aliphatic hydrocarbons increase the service life of the as yet unpolymerized, foamed aqueous reaction mixture.
  • the hydrocarbons are used in an amount of 0 to 10% by weight, preferably 0.1 to 5% by weight, based on the weight of the polymerizable aqueous mixture (M2).
  • the foamed polymerizable aqueous mixture (M2) obtainable in the first process step can also be shaped and polymerized into large blocks. After the polymerization, the blocks can be cut or sawn into smaller shaped bodies. Sandwich-like structures can also be produced by applying a foamed polymerizable aqueous mixture (M2) in layers which are interrupted by the aforementioned carrier materials.
  • the foamed polymerizable aqueous mixture (M2) is polymerized.
  • the polymerization can be carried out by increasing the temperature, by exposure to light, by irradiation with electron beams or by increasing the temperature and exposure to light.
  • all methods customary in the art can be used, for example bringing the foam into contact with heatable plates, exposure to infrared radiation on the polymerizable foam or heating with the aid of microwaves. If thicker layers of foam are to be produced, e.g. Foams with a thickness of several centimeters, the heating of the polymerizable foamed material with the aid of a microwave is particularly advantageous, because in this way a relatively uniform heating can be achieved.
  • the polymerization then takes place, for example, at a temperature of 20 to 180 ° C., preferably 20 to 100 ° C.
  • all conventional imagesetter systems can be used, provided their emission spectrum is adapted to the photoinitiator used.
  • the polymerization is started by exposure, it is advantageous to use a combination of a photoinitiator of a thermal initiator and / or a photoinitator which can also act as a thermal initiator, for example azo initiators. Since the foam heats up strongly during the polymerization due to the high heat of polymerization, a particularly rapid and effective course of the polymerization reaction is achieved in this way.
  • the polymerization temperature is in the range from 0 to 150, preferably 10 to 100 ° C.
  • the polymerization proceeds with largely maintaining the structure of the foamed polymerizable aqueous mixture, i.e. the polymerizable foam changes its volume only slightly during the polymerization.
  • the polymerization reaction is influenced by the start temperature, the initiation technology or the heat dissipation.
  • the polymerization temperature is chosen so that boiling of the polymerizable aqueous mixture is avoided.
  • the foam solidifies due to increasing gel formation.
  • there is a foam-like hydrogel which has a water content of 30 to 80% by weight.
  • the foam has, at least in part, an open-cell structure.
  • a residual moisture content of 1 to 45, preferably 15 to 35% by weight is desirable.
  • the foam-like hydrogel obtained in the polymerization is therefore generally dried.
  • the foam In order to obtain a flexible foam, the foam must have a certain residual moisture. The water content strongly depends on the density of the foam produced. The higher the density, the more residual moisture has to be set.
  • Methods for drying the foam include e.g. Heating with a hot gas stream, applying vacuum, infrared radiation or heating with microwave radiation. Microwave radiation is advantageous for drying large-volume molds.
  • the relatively hard and brittle foam initially obtained can, if desired, be made more flexible with the aid of external plasticizers or by means of internal flexibilization.
  • External plasticizers are, for example, hydrophilic and hygroscopic substances for the targeted adjustment of a certain residual water content.
  • the flexibility can be improved, for example, by using polyols, such as glycerol, polyalkylene glycols, such as polyethylene glycols or polypropylene glycols, or cationic surfactants. Suitable cationic surfactants are described above as component f).
  • Suitable substances are those which themselves bear unsaturated groups, such as the aforementioned monomers c) and which are incorporated into the gel structure or react with the gel-forming material.
  • the internal plasticizer is said to lower the glass temperature of the super absorber.
  • Suitable internal plasticizers are, for example, olefins, esters of ethylenically unsaturated C 3 to Cs carboxylic acids and monohydric C to C 3 o alcohols or polyethylene glycol or polypropylene glycol monoesters of monoethylenically unsaturated C 3 to Cs carboxylic acids.
  • Suitable monomers c) for internal flexibilization are those which reduce the glass transition temperature of the copolymers formed with the monomers (a), for example vinyl esters of saturated carboxylic acids with 4 or more carbon atoms, alkyl vinyl ethers with at least 2 carbon atoms in the alkyl group, vinyl lactams and alkyl-substituted styrenes .
  • an inhomogeneous crosslinking density can be generated in the superabsorbent foams according to the invention during production. This is particularly advantageous when used as monomers of the components described above
  • b) uses a mixture of at least one water-soluble and at least one water-insoluble crosslinker.
  • Such monomers are, for example, hydroxyl group-containing monomers which are capable of reacting with carboxyl groups in the foam structure at a higher temperature, for example at temperatures above 150 ° C.
  • Suitable monomers that contain latent have crosslinking sites, for example the crosslinkers b) described above, which contain at least one polymerizable ethylenically unsaturated double bond and at least one further functional group which, for reaction with further functional groups, such as, for example, the carboxyl groups or sulfonic acid groups of the monomers a) described above or the like, or are capable of different crosslinkers b).
  • Suitable postcrosslinkers form covalent or ionic bonds with the functional groups of the polymer matrix.
  • Suitable crosslinking agents are e.g. Compounds which have at least two identical or different functional groups, e.g. selected from hydroxyl, amino, quaternary ammonium, isocyanato, epoxy, aziridino, ester or amide groups.
  • Preferred post-crosslinking agents are polyalcohols such as glycerol or bisepoxides.
  • the crosslinking agents can be applied to the foamed material, for example by spraying, dipping or by vapor deposition.
  • the foam-like superabsorbers A) have a gravimetrically determined density of 10 -3 to 0.9 g / cm 3 , preferably 0.05 to 0.7 g / cm 3 .
  • Suitable polymer gels A) contained in the composite materials according to the invention are also highly swellable gels which lose their shape when swollen in liquids, in particular in water, and change into a colloidal state.
  • such polymers are e.g. in EP-B-0 412 388.
  • EP-B-0 412 388 are finely divided polymer powders which are prepared by polymerizing water-soluble polymers in the aqueous phase of a water-in-oil emulsion in the presence of free radical initiators and corresponding emulsifiers.
  • the polymerization is carried out in the presence of protective colloids or these protective colloids are added to the resulting water-in-oil polymer suspension after the polymerization has ended.
  • strongly swellable polymer gels A which comprise agglomerated polymer particles which disintegrate into the primary particles when introduced into an aqueous medium.
  • Agglomerated polymer particles of water-swellable polymers with an average particle diameter of 20 to 5000 ⁇ m are preferably used, the agglomerated polymer particles consisting of primary particles with an average particle diameter of 0.1 to 15 ⁇ m and by polymerizing water-soluble monomers in the presence of Regulators and crosslinking agents like a water-in-oil
  • (a) can be obtained by addition of C 2 - to C 4 -alkylene oxides onto alcohols, phenols, amines or carboxylic acids, and
  • the preferred water-soluble ethylenically unsaturated monomers are acrylic acid, methacrylic acid, acrylamide, methacrylamide,
  • 2-Acrylamido-2-methylpropanesulfonic acid N-vinylimidazole, N-vinyl ⁇ formamide, hydroxyethyl acrylate, hydroxypropyl acrylate, N-methylol acrylamide or mixtures thereof.
  • the monomers can either be polymerized alone to give homopolymers or polymerized as a mixture with one another to give copolymers.
  • copolymers of acrylamide and acrylic acid for example, copolymers of acrylamide and acrylic acid, copolymers of acrylamide and methacrylic acid, copolymers of methacrylamide and acrylic acid, copolymers of methacrylamide and methacrylic acid, copolymers of acrylamide, acrylic acid and acrylamide-2-methylpropanesulfonic acid, copolymers of acrylamide and dimethylaminoethyl acrylate, copolymers of acrylamide and diethylaminoethyl methacrylate and copolymers of methacrylamide and dimethylaminoethyl acrylate.
  • carboxylic acids and the other ethylenically unsaturated acids can be used in the polymerization either in the form of the free acid, in partially neutralized or else in completely neutralized form.
  • Bases for neutralizing these monomers are, for example, sodium hydroxide solution, potassium hydroxide solution, ammonia, amines, such as triethylamine, butylamine, triethylamine, morpholine and ethanolamine.
  • the basic acrylates and methacrylates are preferably used as a salt or in quaternized form in the homo- or copolymerization.
  • the basic acrylates and methacrylates are neutralized, for example, with the aid of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid and carboxylic acid. such as formic acid, acetic acid and propionic acid.
  • the basic acrylates and methacrylates are also used in quaternized form.
  • the quaternization products are obtained by quaternizing these compounds with customary quaternizing agents, such as methyl chloride, ethyl chloride, benzyl chloride, lauryl chloride, dimethyl sulfate, diethyl sulfate or epichlorohydrin.
  • customary quaternizing agents such as methyl chloride, ethyl chloride, benzyl chloride, lauryl chloride, dimethyl sulfate, diethyl sulfate or epichlorohydrin.
  • the water-soluble monomers can also be polymerized in the presence of crosslinking agents.
  • Suitable crosslinkers are the components b) mentioned above with at least two non-conjugated, ethylenically unsaturated double bonds.
  • water-soluble crosslinking agents are used, e.g. N, N '-methylene-bis-acrylamide, polyethylene glycol diacrylates, polyethylene glycol dimethacrylates, pentaerythritol triallyl ether and / or divinyl urea.
  • the crosslinking agents are used in an amount of 50 to 5000 ppm, corresponding to approximately 0.003 to 0.3 mol%, based on the monomers used in the polymerization.
  • the crosslinking agents are used in an amount of at least 1000 ppm, in particular at least 2000 ppm, preferably 0.20% to 10% by weight, based on the monomers used overall in the polymerization.
  • the amount of crosslinking agents is particularly preferably 0.2 to 0.5% by weight, based on the total monomers used.
  • the water-soluble monomers are polymerized in the presence of at least 1000 ppm of at least one crosslinking agent and at least 1% by weight of at least one regulator, the amounts based in each case on the monomers used.
  • Suitable crosslinkers and regulators are described above.
  • Polymerization regulators used with particular preference are isopropanol, formic acid and their alkali metal and ammonium salts, thioglycolic acid and their alkali metal and ammonium salts, and all regulators which have a similarly high transmission constant to thioglycolic acid.
  • the polymerization regulators are preferably used in amounts of 0.25 to 10% by weight, based on the monomers used in the polymerization. Mixtures of the polymerization regulators can also be used in the polymerization.
  • the monomers are first dissolved in water.
  • the concentration of the monomers in the aqueous solution is 20 to 80, preferably 30 to 60% by weight.
  • the aqueous solution is then emulsified to form a water-in-oil emulsion in an inert hydrophobic liquid (oil phase) in the presence of at least one water-in-oil emulsifier. Virtually all of them cannot be used as inert hydrophobic liquids with water miscible liquids are used that do not interfere with the polymerization.
  • Aliphatic and aromatic hydrocarbons or mixtures of aliphatic and aromatic hydrocarbons are preferably used for this. Suitable aliphatic hydrocarbons are, for example, pentane,
  • Aromatic hydrocarbons which are used as the hydrophobic liquid in reverse suspension polymerization are, for example, benzene, toluene, xylene and isopropylbenzene.
  • halogenated hydrocarbons such as tetrachloroethane, hexachloroethane, trichloroethane and chlorobenzene.
  • Cyclohexane or hydrocarbons with a boiling range from 60 to 170 ° C. are preferably used.
  • the proportion of the oil phase in the structure of the water-in-oil polymer emulsion is 15 to 70, preferably 20 to 60% by weight.
  • the known water-in-oil emulsifiers are used to disperse the aqueous monomer solution in the oil phase.
  • These are, for example, sorbitan esters, such as sorbitan monostearate, sorbitan monooleate, sorbitan palmitate and sorbitan laurate, and glycerol esters, the acid component of which is derived from C 14 to C 2 o-carboxylic acids.
  • Further suitable emulsifiers are the water-in-oil emulsifiers known from DE-A-25 57 324, which are obtainable by reacting
  • emulsifiers are made up of at least one hydrophilic and at least one hydrophobic block, the blocks each having molar masses of more than 500 to 100,000, preferably 550 to 50,000 and very particularly preferably 600 to 20,000.
  • the emulsifiers can have a comb-like or linear structure.
  • Linear block copolymers of the AB or ABA type, where A is a hydrophobic and B is a hydrophilic polymer block, are known, cf. EP-A-0 000 424 and EP-A-0 623 630.
  • the emulsifiers to be used are preferred soluble in the used water-immiscible solvent.
  • the hydrophilic blocks themselves are more than 1%, preferably 5% by weight, soluble in water at 25 ° C.
  • Examples are blocks which are built up from ethylene oxide, propylene oxide or butylene oxide units, optionally in a mixture with one another.
  • the hydroxyl groups of the alkylene oxide blocks can be additionally modified by sulfate or phosphate ester groups.
  • Suitable other blocks are derived from polytetrahydrofuran,
  • the hydrophobic parts of the emulsifiers consist for example of blocks of polystyrene, polyalkyl (meth) acrylates, polysiloxanes, poly (hydroxyalkanoic acids) such as e.g. Polycondensates from 2-hydroxypropanoic acid, 2-hydroxybutanoic acid, 2-hydroxyisobutanoic acid,
  • 2-hydroxyheptanoic acid 10-hydroxydecanoic acid, 12-hydroxydodecanoic acid, 12-hydroxystearic acid, 16-hydroxyhexadecanoic acid, 2-hydroxystearic acid, 2-hydroxyvaleric acid or the corresponding condensates obtained from lactones, condensates from diols and dicarboxylic acids such as polyethylene adipate, polylactamates such as poly-caprolactams , Polyisobutylene or polyurethane.
  • Blocks of polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyhydroxyalkanoic acids with more than 10 carbon atoms in the alkane unit, polydimethylsiloxanes or polyisobutylenes are preferred.
  • Blocks of polystyrene, polyhydroxy fatty acids such as poly (12-hydroxystearic acid) or polydimethylsiloxanes are very particularly preferred.
  • block copolymers are preferably used as emulsifiers, where
  • A is a hydrophobic polymer block from the group consisting of polystyrene, poly (hydroxycarboxylic acids), polydimethylsiloxanes or polyisobutylene and
  • B is a hydrophilic polymer block from the group of the C - to C 4 -polyalkylene glycols
  • the water-in-oil emulsifiers in question have an HLB value of at most 8.
  • the HLB value is the hydrophilic-lipophilic balance of the emulsifier, cf. WC Griffin, J. Soc. Cosmet. Chem. Volume 1, 311 (1949).
  • the water-in-oil emulsifiers are, based on the monomers used, in one
  • Those water-in-oil emulsifiers which are described in the aforementioned DE-A-25 57 324 are preferably used.
  • Suitable radical initiators are all polymerization initiators commonly used, such as the above-mentioned compounds of component d). Water-soluble initiators are preferred, with either a single initiator or mixtures of several initiators being used. The choice of initiators depends primarily on the temperature at which the polymerization is carried out. Additional salts of heavy metals, e.g. Use copper, cobalt, manganese, iron, nickel and chromium salts and / or organic compounds, such as benzoin, dirnethylaniline, ascorbic acid and reducing agents, such as, for example, alkali disulfite or formaldehyde sodium sulfoxylate, together with at least one of the radical initiating polymerization initiators.
  • Additional salts of heavy metals e.g. Use copper, cobalt, manganese, iron, nickel and chromium salts and / or organic compounds, such as benzoin, dirnethylaniline, ascorbic acid and reducing agents, such as, for example,
  • Polyhydric alcohols can also be used as alcohols, for example, as already mentioned above, ethylene glycols or propylene glycols and also glycerol, pentaerythritol and hexanediol-1, 6.
  • the alkylene oxides can also be phenol, and substituted phenols, such as C 1 -C 4 -alkylphenols be added.
  • Amines are also suitable as end group closures, for example C 1 -C 8 -alkyl- or dialkylamines and diamines, preferably ethylenediamine.
  • Of particular interest here are commercially available products which can be obtained, for example, by sequential addition of ethylene oxide and propylene oxide onto ethylenediamine.
  • the composite materials according to the invention contain at least one salt or mineral A) which is sparingly soluble in water.
  • these include, for example, magnesium chloride, magnesium dihydrogen diphosphate, magnesium diphosphate, magnesium polyphosphate, calcium carbonate, calcium phosphate, apatite Ca 5 [(F, C1.0H, 1 / 2C0 3 ) (P0 4 ) 3 , especially fluorapatite Ca 5 F (P0 4 ) 3 and Hydroxyapatite Cas (OH) (P0 4 ) 3 , calcium silicate, strontium carbonate, strontium sulfate, barium carbonate, barium sulfate, aluminum carbonate, basic aluminum carbonate, aluminum hydroxide, aluminum phosphate, basic aluminum phosphate, spinels, inverse spinels, iron oxides, cobalt oxides, vanadium sulfide, molybdenum sulfide, etc.
  • the composite materials according to the invention contain the inorganic salts and / or
  • Example 1 was repeated with the only exception that the polymerization was carried out under a pressure of 8 bar.
  • the maximum temperature of the reaction mixture reached was at 95 ° C.
  • the consistency of the gel obtained was firm, viscous and hardly sticky.
  • Example 2 the mixture was polymerized as described in Example 1. The maximum temperature reached was 97 ° C. The consistency of the gel obtained was firm, viscoplastic and only slightly sticky.
  • the homogeneous mixture obtained is poured into a 2 liter flask into which argon is introduced from below. Two whisks are inserted into the flask, each of which is connected to a Janke & Kunkel type RW 20 DZM stirrer. The argon flow is adjusted so that it bubbles through the reaction mixture at a rate of 2.5 l / h.
  • the two stirrers are first set to a speed of 60 rpm. 45.00 g of finely ground superabsorbent (particle size ⁇ 100 ⁇ m) are added to the reaction mixture and mixed in homogeneously. The free opening of the piston is almost completely sealed with parafilm and the stirrer speed is increased to 1000 rpm.
  • the mixture is whipped at this speed for 20 min at room temperature. 5 minutes before the end of the whipping process, 11.9 g of a 3% solution of 2, 2 '-azobis (2-amidinopropane dihydrochloride) are added to the flask. After the whipping period, a finely divided, free-flowing whipping foam is obtained.
  • the foam is filled in a layer thickness of 3 mm into a box made of polypropylene (dimensions: width 20 cm, depth 20 cm, height 15 cm), which was previously flushed with argon.
  • the foam is irradiated with an imagesetter for 60 seconds.
  • the result is an evenly 3 mm thick, slightly flexible foam layer that can be easily removed from the box. It is dried in a vacuum drying cabinet at 70 ° C and a vacuum of 20 mbar to a residual water content of 25%. For equilibration, the dried foam layer is stored overnight in a tightly closed polyethylene bag. After that, the foam layer obtained is still soft and flexible. For test purposes, a small part of the sample is dried completely in vacuo.
  • TMPTA trimethylpropane triacrylate
  • 2,2'-azobis N, N'-dimethyleneisobutyramidine dihydrochloride (3% aqueous solution)
  • the foam is poured into a 15.5x19.0x18.0 cm mold made of polypropylene and polymerized in the microwave for 10 minutes.
  • a 7 cm thick foam block is obtained.
  • TMPTA trimethylpropane triacrylate
  • the foam is transferred to a 15.5 * 19.0 * 18.0 cm polypropylene mold and polymerized in the microwave for 10 minutes. An 8 cm thick foam block is obtained.
  • the crosslinker (TMPTA) is first dissolved in the acrylic acid in a screw cap vessel.
  • the Na acrylate, the emulsifier and the precipitated silica are added with stirring.
  • the approach is in a commercially available Bosch kitchen machine with cover whipped to a foam at the highest stirring level. During this process, the air space above the foam is constantly filled with carbon dioxide. After 15 minutes, the starter solution is added and the mixture is beaten for a further 5 minutes. A fine, rigid whipped foam with a volume of approx. 2 liters is created.
  • the foam is transferred to a 15.5x19.0x18.0 cm polypropylene mold and polymerized in the microwave for 10 minutes. A 7 cm thick foam block is obtained.
  • the crosslinker is first dissolved in acrylic acid in a screw cap vessel.
  • the Na acrylate, the emulsifier and the hydroxyethyl cellulose are added with stirring.
  • the mixture is then stirred overnight.
  • the mixture is whipped into a foam for 20 minutes in a commercially available Bosch kitchen machine with a lid. During this process, the air space above the foam is constantly filled with carbon dioxide.
  • the starter solution is then added and the polymerizable mixture is beaten for a further 5 minutes.
  • the result is a fine, rigid foam with a volume of approx. 2.5 1.
  • the foam is filled into a 15.5x19.0x18.0 cm mold made of polypropylene and polymerized in the microwave oven.
  • Extractable proportions 10.3% 5 Water absorption: 55.3 g / g retention: 42.1 g / g
  • Input materials 400.00 g 37% aqueous Na-acrylate solution
  • the starting materials specified above are foamed and polymerized according to the instructions given in Example 4. First of all, a fine, rigid foam with a volume of 3 l is formed. After polymerizing, a 6 cm thick foam block is obtained.
  • Examples 1 to 62 of EP-B-0 412 388 are examples of the production of highly swellable polymer gels by polymerizing water-soluble monomers in the presence of water-in-oil emulsifiers and protective colloids.
  • the monomer emulsions described below are initially introduced in a 2 l capacity polymerization vessel which is provided with anchor stirrer, thermometer, nitrogen inlet and nitrogen outlet.
  • the polymerizable mixture is then emulsified by adding half the amount of starter for 30 minutes at room temperature under a nitrogen atmosphere at a stirring speed of 200 rpm.
  • the reaction mixture is then heated to a temperature in the range from 55 to 70 ° C. and polymerized in this temperature range for 1.5 h. Then the remaining amount of the starter is added and the reaction mixture is heated for a further 2 hours at 65 ° C. with stirring.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

L'invention concerne des matériaux composites formés de minéraux inorganiques et de gels polymères, ainsi que leur utilisation.
PCT/EP1997/005664 1996-10-16 1997-10-15 Materiaux composites WO1998016308A1 (fr)

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DE19642761A DE19642761A1 (de) 1996-10-16 1996-10-16 Kompositmaterialien

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
CN102176925A (zh) * 2008-10-07 2011-09-07 赢创施托克豪森有限责任公司 超吸聚合物的制备方法
US8048942B2 (en) 2008-10-08 2011-11-01 Evonik Stockhausen Gmbh Process for the production of a superabsorbent polymer
US8063121B2 (en) 2008-10-08 2011-11-22 Evonik Stockhausen Gmbh Process for the production of a superabsorbent polymer
US8357766B2 (en) 2008-10-08 2013-01-22 Evonik Stockhausen Gmbh Continuous process for the production of a superabsorbent polymer
WO2017178302A1 (fr) 2016-04-14 2017-10-19 Basf Se Particules polymères recouvertes comprenant un noyau polymère gonflant dans l'eau et un revêtement sol-gel
CN114957955A (zh) * 2022-05-17 2022-08-30 东莞市旺品实业有限公司 一种高散热聚碳酸酯材料及高散热性pc灯芯
CN115282948A (zh) * 2022-07-07 2022-11-04 江苏大学 一种离子液体介导低聚壳聚糖衍生IL-Cu/Al@NC微球的制备方法及应用

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DE10037629A1 (de) * 2000-08-02 2002-02-14 Skw Bauwerkstoffe Deutschland Wasserlösliche oder wasserquellbare sulfogruppenhaltige assoziativverdickende Copolymere, Verfahren zu deren Herstellung und deren Verwendung
DE102004022766A1 (de) * 2004-05-05 2005-12-01 Bayer Chemicals Ag Schäume zur Entfernung von Schadstoffen und/oder Schwermetallen aus strömbaren Medien
DE102015122070A1 (de) * 2015-12-17 2017-06-22 Thyssenkrupp Ag Harnstoffhaltige Düngemittel und Verfahren zu ihrer Herstellung

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WO1989009066A1 (fr) * 1988-03-24 1989-10-05 Bukh Meditec A/S Composition a diffusion regulee
WO1994025519A1 (fr) * 1992-03-05 1994-11-10 Chemische Fabrik Stockhausen Gmbh Composition polymere, composition de materiau absorbant, leur production et leur utilisation
WO1996025959A2 (fr) * 1995-02-20 1996-08-29 Chemische Fabrik Stockhausen Gmbh Structures super-absorbantes en forme de feuilles

Patent Citations (3)

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WO1989009066A1 (fr) * 1988-03-24 1989-10-05 Bukh Meditec A/S Composition a diffusion regulee
WO1994025519A1 (fr) * 1992-03-05 1994-11-10 Chemische Fabrik Stockhausen Gmbh Composition polymere, composition de materiau absorbant, leur production et leur utilisation
WO1996025959A2 (fr) * 1995-02-20 1996-08-29 Chemische Fabrik Stockhausen Gmbh Structures super-absorbantes en forme de feuilles

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102176925A (zh) * 2008-10-07 2011-09-07 赢创施托克豪森有限责任公司 超吸聚合物的制备方法
TWI500636B (zh) * 2008-10-07 2015-09-21 Evonik Degussa Gmbh 用於製造超吸性聚合物的方法
US8048942B2 (en) 2008-10-08 2011-11-01 Evonik Stockhausen Gmbh Process for the production of a superabsorbent polymer
US8063121B2 (en) 2008-10-08 2011-11-22 Evonik Stockhausen Gmbh Process for the production of a superabsorbent polymer
US8357766B2 (en) 2008-10-08 2013-01-22 Evonik Stockhausen Gmbh Continuous process for the production of a superabsorbent polymer
US8653210B2 (en) 2008-10-08 2014-02-18 Evonik Degussa Gmbh Continuous process for the production of a superabsorbent polymer
US9085648B2 (en) 2008-10-08 2015-07-21 Evonik Degussa Gmbh Superabsorbent polymer process
WO2017178302A1 (fr) 2016-04-14 2017-10-19 Basf Se Particules polymères recouvertes comprenant un noyau polymère gonflant dans l'eau et un revêtement sol-gel
US11015006B2 (en) 2016-04-14 2021-05-25 Basf Se Coated polymer particles comprising a water-swellable polymer core and a sol-gel coating
CN114957955A (zh) * 2022-05-17 2022-08-30 东莞市旺品实业有限公司 一种高散热聚碳酸酯材料及高散热性pc灯芯
CN115282948A (zh) * 2022-07-07 2022-11-04 江苏大学 一种离子液体介导低聚壳聚糖衍生IL-Cu/Al@NC微球的制备方法及应用
CN115282948B (zh) * 2022-07-07 2023-12-15 江苏大学 一种离子液体介导低聚壳聚糖衍生IL-Cu/Al@NC微球的制备方法及应用

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