EP1644432A1 - Support pour milieux aqueux - Google Patents

Support pour milieux aqueux

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Publication number
EP1644432A1
EP1644432A1 EP04740186A EP04740186A EP1644432A1 EP 1644432 A1 EP1644432 A1 EP 1644432A1 EP 04740186 A EP04740186 A EP 04740186A EP 04740186 A EP04740186 A EP 04740186A EP 1644432 A1 EP1644432 A1 EP 1644432A1
Authority
EP
European Patent Office
Prior art keywords
polymer substrate
carrier
loaded
surfactant
water
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Withdrawn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
EP04740186A
Other languages
German (de)
English (en)
Inventor
Hartmut Stenzel
Erich Kessler
Quan Huang
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.)
Membrana GmbH
Original Assignee
Membrana GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Membrana GmbH filed Critical Membrana GmbH
Publication of EP1644432A1 publication Critical patent/EP1644432A1/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Withdrawn legal-status Critical Current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
    • 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
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • 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
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • 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
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C08J9/42—Impregnation with macromolecular compounds
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • 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
    • C08J2425/00—Characterised by the use of homopolymers or 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 an aromatic carbocyclic ring; Derivatives of such polymers
    • 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
    • C08J2427/00—Characterised by the use of homopolymers or 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 halogen; Derivatives of such polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2984—Microcapsule with fluid core [includes liposome]

Definitions

  • the invention relates to a carrier for aqueous media and a method for producing such a carrier for aqueous media.
  • particulate carriers which are able to absorb water or generally aqueous media and, depending on the application, also to store them.
  • additives can e.g. Antioxidants, plasticizers, fragrances, lubricants, antistatic agents, surface-active substances u. the like.
  • a masterbatch process is often used for this, in which a concentrate of the additive to be incorporated is first prepared in a suitable polymer and this concentrate is then e.g. is incorporated into a polymer melt by means of an extrusion process with homogeneous distribution of the additive.
  • Porous particulate polymer structures are often used to produce such masterbatches, in the pores of which the respective additive is introduced.
  • DE 2737 745 C2 describes microporous polymer structures which are produced by a process with thermally induced phase separation from a homogeneous melt of the polymer and an organic liquid which is compatible with the polymer.
  • the functional active fluids at the same time being the compatible organic liquid used in the production of the polymer structures, which at least partially remains in the pore system after formation of the porous polymer structure.
  • unfilled microporous structures can be produced, in the pore system of which additives can subsequently be introduced in organic solution via absorption mechanisms. Similar structures which can be loaded with additives can also be produced by the process described in DE 32 05289 C2.
  • WO 98/55540 describes porous polymer particles based on polyolefins. These polymer particles can be absorbed e.g. be loaded with liquid additives. For the loading of hydrophobic polymer particles, as disclosed in WO 98/55540, however, it is a prerequisite that the additives are hydrophobic additives. For absorption, i.e. the hydrophobic porous polymer particles of WO 98/55540 are not able to absorb aqueous media.
  • hydrophobic polymers are required as carriers for additives or active liquids, ie, for example, polyolefins such as polyethylene, polypropylene or poly (4-methyl-1-pentene) or fluoropolymers such as polyvinylidene fluoride or polyvinyl fluoride.
  • polyolefins such as polyethylene, polypropylene or poly (4-methyl-1-pentene)
  • fluoropolymers such as polyvinylidene fluoride or polyvinyl fluoride.
  • such polymers are distinguished as such by properties such as high chemical resistance and / or physiological safety, high mechanical stability or temperature stability.
  • additive concentrates based on the aforementioned hydrophobic polymers.
  • Porous polymer structures made from these polymers are good with their hydrophobic properties hydrophobic active liquids or hydrophobic liquids containing additives can be loaded.
  • active fluids or additives are aqueous in nature.
  • numerous additives first in the form of an aqueous dispersion or emulsion, e.g. Dispersions of latex particles, color pigments, kaolin, nanoparticles, etc.
  • active liquids or additive dispersions cannot be absorbed by the known hydrophobic porous polymer particles, or at most to a very small extent, i.e. be included.
  • a number of products are known as so-called superabsorbers which are capable of being carriers for aqueous media and which can absorb many times their own weight in liquid and can even retain it under the highest pressure.
  • Products of this type are based, for example, on cellulosic polymers or on modified polyacrylates, polyacrylonitriles or polyvinyl alcohols, ie on hydrophilic polymers.
  • a disadvantage of such products it is often the case that they do not have sufficient mechanical stability and are not free-flowing.
  • they are also unsuitable for absorbing, for example, aqueous dispersions, and compatibility problems arise when such products are incorporated into hydrophobic thermoplastic polymers such as, for example, polyolefins.
  • a carrier in the form of particles which can be loaded with aqueous media, the particles being formed from a porous hydrophobic polymer substrate, having an average particle size between 50 ⁇ m and 5000 ⁇ m and an at least partially open-pore structure with an average pore diameter between 1 ⁇ m and have 200 ⁇ m and wherein the particulate carrier has a loadability with water, determined by contacting with water, from 10% by weight to 95% by weight, based on the total weight of the loaded carrier.
  • the carrier according to the invention is therefore a porous polymer particle that can be loaded with aqueous media and is based on a hydrophobic polymer substrate. Since the carrier according to the invention is in the form of particles, it is capable of blowing or pouring, which is particularly advantageous for further processing.
  • the porous polymer substrate is strat hydrophilized on at least a portion of its entire surface including the outer surface and the surface of its pores. It is particularly advantageous if the porous polymer substrate is hydrophilized on essentially its entire surface, which comprises the outer surface and the surface of its pores. This can be achieved with porous polymer substrates, the pore volume of which has a high proportion of accessible pores.
  • the object is further achieved by a method for producing a carrier which can be loaded with aqueous media in the form of particles based on a hydrophobic polymer, the carrier having a loadability with water, determined by bringing it into contact with water, from 10 to 95% by weight.
  • a porous hydrophobic polymer substrate in the form of particles, the polymer substrate having an average particle size between 50 and 5000 ⁇ m and an at least partially open-pore structure with an average pore diameter between 1 ⁇ m and 200 ⁇ m, - hydrophilizing the polymer substrate present in particles on at least part of its entire surface, which comprises the outer surface and the surface of its pores, in order to obtain the carrier which can be loaded with aqueous media.
  • the method according to the invention is particularly suitable for producing the carriers according to the invention. Furthermore, the method according to the invention for producing a carrier that can be loaded with aqueous media can be further developed into a method for producing a memory loaded with aqueous media. Another object of the invention is therefore achieved by a method for producing a storage medium loaded with an aqueous medium based on a hydrophobic polymer, comprising at least the steps of selecting a porous hydrophobic polymer substrate in the form of particles, the polymer substrate having an average particle size between 50 and 5000 ⁇ m and an at least partially open-pore structure with an average pore diameter between 1 and 200 ⁇ m, hydrophilizing the polymer substrate present in particles on at least a part of its total surface, comprising the outer surface and the surface of its pores, and loading the hydrophilized polymer substrate present in particles with the aqueous medium up to a loading of 10 to 95% by weight, based on the total weight of the loaded storage, by contacting the hydrophilized polymer substrate with the aque
  • a storage medium consisting of particles and loaded with an aqueous medium
  • a loading with the aqueous medium of 10 to 95% by weight, based on the Has total weight of the loaded storage, the particles being formed from a hydrophobic polymer substrate, having an average particle size between 50 and 5000 ⁇ m and having an at least partially open-pore structure and an average pore diameter between 1 ⁇ m and 200 ⁇ m.
  • the porous, particulate, hydrophobic polymer substrate used with an at least partially open-pored structure can have a sponge-like cellular structure or a network-like or coral-shaped microstructure.
  • the pore structure must be at least partially open-pore, ie the pores present in the polymer substrate must be in fluid communication with one another at least in partial areas of the substrate structure, and the particles of the polymer substrate must be open-pore at least in partial areas of their outer surface. This allows sufficient permeability speed for aqueous media and the loading capacity with aqueous media required according to the invention.
  • a particulate polymer substrate with an at least partially open-pore structure and an average pore size between 1 ⁇ m and 200 ⁇ m on the one hand enables water or aqueous media to be taken up, and on the other hand allows the water or the aqueous to be fixed Medium in the pore system of the carrier according to the invention, so that it can best be used as a storage matrix according to the invention for aqueous media.
  • the polymer substrate used according to the invention has an average pore diameter in the range between 5 and 100 ⁇ m. An average pore diameter in the range from 5 to 50 ⁇ m is particularly preferred.
  • Carriers according to the invention based on polymer substrates with such preferred pore diameters show good loading properties and an excellent ability to store aqueous media without the aqueous medium escaping from the carrier.
  • the porous supports according to the invention in the form of particles are distinguished by a good absorption capacity for aqueous media.
  • the absorption capacity for aqueous media is assessed on the basis of the water absorption capacity when the carrier according to the invention is brought into contact with water, on the one hand with regard to the loadability so-called in the context of the present invention, i.e. the amount of water that can be taken up by the particulate porous carrier according to the invention, and on the other hand based on the characteristic loading time, i.e. the time it takes to fill the pore volume with water.
  • the particulate carrier has a loadability with water of 10 to 95% by weight, based on the total weight of the loaded carrier.
  • the volume porosity of the polymer substrate used is expediently between 15 and 95% by volume.
  • the polymer substrate has a porosity in the range between 30 and 90% by volume.
  • Carriers according to the invention based on such polymer substrates preferably have a loadability with water of between 25 and 90% by weight.
  • a preferred memory based on such a polymer substrate has a loading in the range between 25 and 90% by weight.
  • Polymer substrates with a porosity between 50 and 85% by volume are particularly preferred.
  • Carriers according to the invention based on such particularly preferred polymer substrates preferably have a water loadability of between 45 and 85% by weight.
  • a high loading capacity with water and on the other hand a high mechanical stability is realized, which enables problem-free storage of carriers filled with aqueous media, for example in containers or sacks, without the aqueous medium coming from the Particles emerges.
  • a particularly preferred memory based on the particularly preferred polymer substrates mentioned has a loading with the aqueous medium in the range between 45 and 85% by weight.
  • the particulate porous supports according to the invention have a characteristic loading time of at most 120 min and particularly preferably of at most 90 min.
  • polymer substrates with a particle size between 50 and 5000 ⁇ m are preferred.
  • Polymer substrates with a particle size between 400 and 3000 ⁇ m are particularly preferred.
  • the particles of the polymer substrate and thus the particles of the carrier or memory according to the invention can have any shape exhibit.
  • the particles of the polymer substrate can be spherical, oval, cylindrical, or granular or have any other regular or irregular shape.
  • the polymer substrate can, for example, be impregnated with a solution of a hydrophilic polymer.
  • Suitable hydrophilic polymers are polymers such as, for example, polyethylene glycols, polyethylene oxides, polyacrylic amides, polyvinyl alcohols and the like. It is also possible to coat the surface of the polymer substrate with polymerizable hydrophilic monomers, a radical initiator and a crosslinking agent and to crosslink the monomer to form a hydrophilic layer on the surface.
  • surfactants are preferably used for the hydrophilization of the polymer substrate, i.e.
  • the porous polymer substrate is hydrophilized by being coated with a surfactant.
  • the hydrophilization in the processes according to the invention preferably takes place in that the polymer substrate with a solution of a surfactant in a volatile solvent which is essentially inert to the polymer substrate and the polymer substrate is essentially non-solvent, at least in part of its total, the outer surfaces and the surface of its surface comprising pores is impregnated.
  • surfactants are understood to mean substances whose molecules have at least one hydrophilic and one hydrophobic functional group, the hydrophilic and the hydrophobic parts of the molecules being in equilibrium with one another, as a result of which the molecules are able to separate from interfaces at aqueous surfaces Enrich phases. Furthermore, the surfactants have the ability to reduce the interfacial tension and to form so-called micelles.
  • the surfactants have a pronounced affinity for hydrophobic materials and so a good attachment of the surfactants to the surface of the porous hydrophobic polymer substrates used according to the invention and thus a good coating of the polymer substrates used according to the invention with the surfactants is possible.
  • the hydrophilic part of the surfactant molecules ensures the necessary pronounced affinity for aqueous media.
  • a volatile solvent or solvent mixture is understood to mean such a solvent or solvent mixture whose boiling point is below the boiling point or the decomposition temperature of the surfactant used.
  • the solvent or the solvent mixture preferably has a boiling point of at most 100 ° C.
  • the solvent or solvent mixture used to prepare the surfactant solution is one which is essentially inert to the polymer substrate, i.e. which does not substantially chemically react with the polymeric substrate and which does not substantially dissolve the polymeric substrate. In individual cases, however, a slight swelling of the polymer substrate under the influence of the solvent or the solvent mixture can be accepted.
  • the surfactants used are water-insoluble surfactants which are introduced into the polymer substrate by means of an organic solvent or solvent mixture.
  • water-soluble surfactants for hydrophilizing the polymer substrate.
  • the porous carrier is directly impregnated with an aqueous surfactant solution.
  • the aqueous medium containing the water-soluble surfactant is thus left in the polymer substrate and a complex drying step to be interposed is eliminated.
  • the loaded polymer substrate directly represents the memory according to the invention.
  • nonionic, anionic or cationic surfactants can be used for the hydrophilization.
  • non-ionic surfactants are used, preference is given to those which are selected from the group of fatty acid glycerides, such as, for example, monoglycerides or diglycerides, and polyglycol ether surfactants, such as, for example, fatty alcohol polyglycol ether, alkylphenol polyglycol ether, fatty acid polyglycol ether, fatty acid amide polyglycol ethers, the fatty acid glycol esters, such as fatty acid ethylene glycol esters or fatty acid diethylene glycol esters, the fatty acid mono-, fatty acid di- or fatty acid triesters of sorbitan or fatty acid amides, such as fatty acid monoethanolamide or fatty acid diethanolamide.
  • Fatty acid glycerides are particularly suitable, with particularly good results being achieved with glycerol monooleate or glycerol monostearate.
  • water-soluble non-ionic surfactants are used according to the invention, an assessment of the water solubility is possible on the basis of the HLB value.
  • the HLB value (Hydrophilic Lipophilic Balance) expresses the ratio of the strength of the hydrophilic portion to the strength of the hydrophobic portion in the molecule.
  • the HLB value is a measure of the water or oil solubility of predominantly nonionic surfactants and the stability of emulsions.
  • the HLB value of a surfactant can be calculated additively from all molecular parts of the amphiphile.
  • the type and number of the hydrophobic chain and the hydrophilic groups are involved.
  • the scale generally ranges from 1 to 20. HLB values ⁇ 7 characterize rather lipophilic molecules, which preferentially dissolve in the oil.
  • surfactants with HLB values of> 7 have sufficient solubility in water and can therefore be used as the water-soluble nonionic surfactants according to the invention.
  • water-soluble nonionic surfactants those with an HLB value between 10 and 15 are preferred.
  • the hydrophobic part of the surfactant molecule should be composed of a chain of 10 to 30 carbon atoms. In a preferred embodiment, the hydrophobic part of the surfactant molecule consists of a chain of 10 to 20 carbon atoms. The sales Use of surfactant molecules in which the hydrophobic part consists of a chain of 10 to 15 carbon atoms. In the event of the use of water-soluble non-ionic surfactants, the HLB value should then be 10 to 15.
  • water-soluble surfactants not only those from the group of non-ionic surfactants are to be used, but also ionic surfactants.
  • ionic surfactants both anionic and cationic, are predominantly water-soluble.
  • Anionic surfactants with one or more functional anion-active groups dissociate in aqueous solution to form anions, which are ultimately responsible for the surface-active properties.
  • Examples of typical anionic groups -COONa, -SO 3 Na, -OSO 3 Na.
  • Particularly suitable anionic surfactants are those selected from the group of soaps, alkyl sulfates, alkane sulfonates, alkyl arene sulfonates (eg dodecylbenzenesulfonate) or alkylbenzenesulfonates, ⁇ -olefin sulfonates, fatty alcohol sulfonates, fatty alcohol ether sulfonates or succinate sulfonates or dialkyl sulfates.
  • Cationic surfactants used with success are quaternary ammonium compounds of the general formula: (R 4 N + ) X " . These preferably include dimethyldisterylammonium chloride, trimethylpalmitylammonium chloride or dimethylcocbenbenzylammonium chloride.
  • the concentration of the surfactant in the particulate carrier according to the invention or in the storage matrix according to the invention is between 0.1 and 15% by weight and particularly preferably between 1 and 10% by weight. Very good results are achieved if the concentration between 3 and is 10% by weight.
  • the concentration is to be chosen as a function of the porosity of the porous polymer substrate used so that sufficient hydrophilization is achieved on the one hand and blocking, ie clogging of the pores by the coating with the surfactant, is avoided on the other hand.
  • the hydrophilized polymer substrate and thus the carrier according to the invention preferably have the same porous configuration as the uncoated polymer substrate.
  • the hydrophilization is therefore preferably carried out in such a way that the porous structure of the polymer substrate is essentially not changed by the hydrophilization, ie there is no clogging of the pores of the polymer substrate.
  • concentration of the surfactant in the solution is preferably 1 to 10% by weight in the methods according to the invention.
  • An organic solvent or solvent mixture is expediently used to wet the polymer substrate used with the surfactant solution, in particular if water-insoluble surfactants are used to prepare the surfactant solution. If water-soluble surfactants are used to prepare the surfactant solution, water is expediently used as the solvent.
  • organic solvent or solvent mixture is also to be understood as meaning one which contains portions of water, as long as the production of a homogeneous solution of the surfactants used is below the boiling point of the solvent or solvent mixture, preferably at temperatures in the range between 60 ° C. and 70 ° C. is possible and the polymer substrate is well wetted by the solution, so that the polymer substrate can be impregnated with the surfactant solution.
  • the organic solvent or solvent mixture is particularly preferably selected from the group of alcohols, ketones or esters or from mixtures of these substances. According to that Alcohol / water mixtures, for example, can also be used.
  • a preferred procedure consists in immersing the polymer substrate in the surfactant solution for a sufficiently long period of time in order to impregnate the entire surface that can be achieved.
  • An ultrasonic bath can also be used to support the impregnation process, or a vacuum can also be applied.
  • the polymer substrate is dried after impregnation with the surfactant solution. This can be done under elevated temperatures and / or under vacuum. The drying temperatures should be chosen so that the surfactant does not evaporate and does not decompose. Dielectric drying e.g. using microwaves is possible.
  • hydrophobic polymer substrates which are composed of polymers or mixtures of polymers from the group of the polyolefins, the fluoropolymers, the styrene polymers or a copolymer of these polymers.
  • Polyolefins which can be used particularly advantageously are polyethylene, ie HDPE, LDPE, LLDPE or UHMW-PE, polypropylene, poly (4-methyl-1-pentene), poly (l-butenes) or polyisobutene, and as copolymers ethylene-propylene copolymer or ethylene vinyl acetate copolymer.
  • fluoropolymers are polyvinylidene fluoride and polyvinyl fluoride and the copolymers poly (tetrafluoroethylene-co-hexafluoropropylene), poly (tetrafluoroethylene-co-perfluoroalkyl vinyl ether) and poly (ethylene-co-tetrafluoroethylene).
  • Particularly suitable as styrene polymers are polystyrene and Styrene-acrylonitrile copolymers, styrene-butadiene copolymers and acrylonitrile-butadiene-styrene copolymers.
  • Polymer substrates based on polyolefins and in particular based on polypropylene or polyethylene are particularly preferred.
  • the polymers or mixtures of polymers that make up the hydrophobic polymer substrates can contain additives such as e.g. Contain antioxidants, nucleating agents, fillers, UV absorbers and the like in order to modify the properties of the substrates in a targeted manner.
  • concentration of such additives is usually less than 10% by weight and preferably less than 2% by weight.
  • the particulate polymeric carriers for aqueous media according to the invention can best be used to produce polymer particles loaded with aqueous media, i.e. use for the production of a storage for aqueous media.
  • Polymer structures are produced that contain a high proportion of water and that are used for applications such as the foaming of thermoplastic polymers or as a substrate for air conditioning and / or moisture regulation of air can be used.
  • the production of masterbatches with additives, e.g. is initially available as a dispersion, is easily possible by means of the particulate polymeric carrier according to the invention by first filling a particulate polymeric carrier with a sufficient amount of the aqueous dispersion and then removing the water content by drying. As a result, the solids content remains in the pore structure.
  • the average particle size is determined microscopically on the basis of a representative sample quantity using a measuring eyepiece or using a suitable image evaluation method.
  • the average pore size is made using digitized SEM images of fracture images of the samples, which are evaluated using suitable image analysis software.
  • the pore diameter of approx. 50 to 100 pores in ⁇ m is measured from a SEM image.
  • the associated mean pore diameter is calculated from the individual values by averaging.
  • volume potential can be determined using methods known per se.
  • a pycnometric measurement method using water as the non-wetting liquid is suitable for determining the volume porosity of the hydrophobic polymer substrate.
  • the volume porosity can be carried out using suitable intrusion methods such as via mercury intrusion or intrusion of other suitable liquids.
  • Determining the loadability and the characteristic loading time The determination of the loadability and the characteristic loading time presupposes that the volume porosity of the material to be examined is known.
  • Approx. 10 to 30 g of the material to be examined are weighed into a 500 ml glass flask.
  • the amount of water added to the sample material is to be added ie the volume of water to be added, is determined by the porosity of the sample material or by the pore volume of the weighed sample material.
  • the pore volume of the sample material can be determined from the sample weight, the polymer density ppoiymer and the porosity ⁇ .
  • enough water is metered in that a complete absorption of the water by the sample material can be expected.
  • a water volume is added which corresponds to approx. 60% of the determined pore volume of the sample.
  • the glass flask is mixed with a suitable mixing device, e.g. connected to a rotary evaporator with a water bath heated to 25 ° C. Then mix until the sample material is dry on the outside and free-flowing. The loading time from the start of mixing to the complete absorption of the water is determined with a stopwatch.
  • a suitable mixing device e.g. connected to a rotary evaporator with a water bath heated to 25 ° C.
  • the glass bulb is then removed from the mixing device and a further amount of water is added, which corresponds to 5% of the pore volume.
  • the mixture is then mixed again and again the time is stopped until this amount of water has also been completely absorbed by the sample.
  • This process is repeated until the sample material is saturated with water, with an amount of water being added that corresponds to 5% of the pore volume.
  • the saturation is defined as the state in which water is still observed on the wall of the glass bulb and / or the particles of the sample material stick together even after a total loading time of 3 hours.
  • the characteristic loading time is the sum of the individual loading times determined by means of a stopwatch, for which a complete absorption of the amount of water from the sample took place.
  • the saturated sample material is then Weighed back and determined the total amount of water absorbed by the sample material from the difference with the weight.
  • the loadability of the carrier results from the ratio of the total amount of water taken up by the sample material and the weight of the saturated sample material in percent.
  • This polymer substrate was loaded with a 5% by weight solution of the nonionic surfactant Synperonic PE / L 121, a copolymer of a polyethylene glycol and a polypropylene glycol (Uniqema), in isopropanol.
  • the amount of surfactant solution and thus the amount of surfactant were measured so that after drying the treated polymer substrate a particulate carrier with a concentration of the surfactant of 5% by weight was obtained.
  • the hydrophilized polymer substrate had essentially the same porous configuration as the starting hydrophobic polymer substrate.
  • the particulate porous carrier coated with the surfactant showed a loadability with water of 50% by weight, based on the total weight of the loaded carrier, and a characteristic loading time of 90 min.
  • the carrier thus loaded simultaneously represents the store according to the invention with a loading of 50% by weight based on the total weight.
  • Example 2 The same porous polymer substrate as in Example 1 was used. 15 g of the polymer substrate were loaded with 45 g of a 5% by weight solution of the non-ionic surfactant Synperonic PE / L 121 in isopropanol for one hour. After drying by means of vacuum in a water bath heated to 70 ° C., a surfactant content of 13% by weight was obtained.
  • the dried, particulate porous carrier coated with the surfactant showed a loadability with water of 60% by weight, based on the total weight of the loaded carrier, and a characteristic loading time of 75 min.
  • the carrier thus loaded simultaneously represents the storage according to the invention with a loading of 60% by weight based on the total weight.
  • Example 2 The same porous polymer substrate as in Example 1 was used.
  • the polymer substrate was coated with the anionic surfactant AEROSOL ® MA; coated (Fa Cy ⁇ tec sodium di (1, 3-dimethylbutyl) sulfosuccinate.)) To give procedure as in Example 1.
  • Coated with the AEROSOL ® MA particulate porous carrier showed a loading capacity with water of 60 wt .-%, based on the total weight of loaded support, and min is a characteristic loading time of 5 avg.
  • the carrier thus loaded simultaneously represents the store according to the invention with a loading of 60% by weight, based on the total weight.
  • the HDPE polymer substrate was coated on its pore surface and on its outer surface according to the procedure outlined in Example 1 with 5% by weight glycerol monooleate.
  • the hydrophilized polymer substrate coated with glycerol monooleate also had essentially the same porous configuration as the starting hydrophobic polymer substrate.
  • the particulate porous carrier obtained had a water loadability of 60% by weight, based on the total weight of the loaded carrier, and a characteristic loading time of 100 minutes.
  • the carrier thus loaded simultaneously represents the store according to the invention with a loading of 60% by weight, based on the total weight.
  • Example 4 The same porous polymer substrate as in Example 4 was used. This polymer substrate was also loaded with a 5% by weight solution of glycerol monooleate in isopropanol. Here, 18 g of the polymer substrate were loaded with 42 g of the surfactant solution for one hour, so that after Drying by means of vacuum in a water bath heated to 70 ° C. a surfactant content of 10.4% by weight was obtained.
  • the particulate porous carrier coated with the surfactant showed a water loadability of 65% by weight, based on the total weight of the loaded carrier, and a characteristic loading time of 90 min.
  • the carrier thus loaded simultaneously represents the store according to the invention with a loading of 65% by weight based on the total weight.
  • Example 3 The same HDPE polymer substrate was used as in Example 3, which was coated on its pore surface and on its outer surface according to the procedure outlined in Example 1 with the non-ionic surfactant Span® 80 (sorbitan monooleate; Merck).
  • Span® 80 sorbitan monooleate
  • a porous support with a water loadability of 50% by weight, based on the total weight of the loaded support, and a characteristic loading time of 60 minutes was obtained.
  • the carrier thus loaded simultaneously represents the store according to the invention with a loading of 50% by weight based on the total weight.
  • the HDPE granulate also used in Example 4 was used as the particulate polymer substrate.
  • This polymer substrate was covered with a 5th Load the% by weight solution of the non-ionic surfactant Span ® 80 in isopropanol.
  • 18 g of the polymer substrate were loaded with 42 g of the surfactant solution for one hour. After drying by means of vacuum in a water bath heated to 70 ° C., a surfactant content of 10.4% by weight was obtained.
  • the dried, particulate porous carrier coated with the surfactant showed a loadability with water of 65% by weight, based on the total weight of the loaded carrier, and a characteristic loading time of 120 min.
  • the carrier thus loaded simultaneously represents the store according to the invention with a loading of 65% by weight based on the total weight.
  • the same porous particulate polymer substrate as used in Examples 4-7 was used.
  • This polymeric substrate was impregnated with the water-soluble anionic surfactant ARMA (sodium di (1,3-dimethylbutyl) sulphosuccinate, CYTEC Industries Inc., USA).
  • An aqueous surfactant solution with a surfactant content of 5% by weight was used.
  • 20 g of the polymer substrate were loaded with 30 g of the surfactant solution.
  • This product was a particulate memory loaded with 60% by weight (based on the total weight) of an aqueous medium.
  • the particulate polymer substrate loaded with the aqueous surfactant solution was then dried to examine water reloadability.
  • the dried, porous particulate carrier coated with the surfactant showed a loadability with water of 60% by weight, based on the total weight of the loaded carrier and a characteristic loading time of 35 minutes.
  • the loaded carrier in turn represents the storage according to the invention with a loading of 60% by weight based on the total weight.
  • Example 1 The polypropylene substrate used in Example 1 was examined for its loadability with water without further treatment. For this purpose, only a water volume was initially added which corresponded to approximately 10% of the determined pore volume of the sample. Even after 3 hours the sample material was still not dry on the outside, i.e. it did't taken up any water. The untreated polypropylene substrate showed no water loading.

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  • Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Biological Treatment Of Waste Water (AREA)
  • Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un support se présentant sous la forme de particules, ce support pouvant être chargé de milieux aqueux. Lesdites particules sont constituées d'un substrat polymère hydrophobe poreux, elles présentent une taille moyenne comprise entre 50 ñm et 5000 ñm et possèdent une structure au moins partiellement à pores ouverts, les pores présentant un diamètre moyen compris entre 1 ñm et 200 ñm. Ce support sous forme de particules peut être chargé d'eau dans une proportion comprise entre 10 % et 95 % en poids par rapport au poids total du support chargé, cette capacité de charge étant déterminée par mise en contact du support avec de l'eau. L'invention concerne également un dispositif de stockage à base de ce support, ce dispositif de stockage étant chargé d'un milieu aqueux. L'invention concerne en outre un procédé de production d'un tel support sous forme de particules à base d'un polymère hydrophobe, ledit support pouvant être chargé d'eau dans une proportion comprise entre 10 % et 95 % en poids. Selon ce procédé, le substrat polymère présent sous forme de particules est rendu hydrophile au niveau d'au moins une partie de sa surface totale, laquelle comprend la surface extérieure et la surface de ses pores.
EP04740186A 2003-07-03 2004-06-23 Support pour milieux aqueux Withdrawn EP1644432A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10330190 2003-07-03
PCT/EP2004/006761 WO2005003215A1 (fr) 2003-07-03 2004-06-23 Support pour milieux aqueux

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EP1644432A1 true EP1644432A1 (fr) 2006-04-12

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US (1) US20070042183A1 (fr)
EP (1) EP1644432A1 (fr)
JP (1) JP2007535581A (fr)
KR (1) KR20060121804A (fr)
CN (1) CN1816589A (fr)
BR (1) BRPI0412035A (fr)
CA (1) CA2531080A1 (fr)
MX (1) MXPA05014192A (fr)
WO (1) WO2005003215A1 (fr)

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DE10220038A1 (de) * 2002-05-04 2003-11-20 Membrana Gmbh Verfahren zur Herstellung geschäumter Polymerformkörper und geschäumter Polymerformkörper
DE102007050046A1 (de) 2007-10-17 2009-04-23 Byk-Chemie Gmbh Wasserspeicher
US8128872B2 (en) * 2008-07-30 2012-03-06 Temptime Corporation Freeze indicators, components therefor and preparative processes
TWI589632B (zh) * 2012-01-07 2017-07-01 克萊瑞特金融（Ｂｖｉ）有限公司 用於製造親水性聚苯乙烯物件之組成物
EP2662407A1 (fr) * 2012-05-09 2013-11-13 Clariant International Ltd. Composition de production de polystyrène hydrophile
EP2662408A1 (fr) * 2012-05-09 2013-11-13 Clariant International Ltd. Composition de production de matériau de polystyrène hydrophile
EP2928950B1 (fr) 2012-12-05 2018-10-17 Akzo Nobel Chemicals International B.V. Mélange maître comprenant un peroxyde de cétone cyclique
SG11201503897XA (en) 2012-12-05 2015-06-29 Akzo Nobel Chemicals Int Bv Peroxide masterbatch based on bioresin
EP2808371B1 (fr) 2013-05-28 2019-09-18 3M Innovative Properties Company Additif de dégazage pour adhésifs sensibles à la pression
IT201900022593A1 (it) * 2019-11-29 2021-05-29 Maflon S P A Granulo idrofilo, uso e preparazione
IT201900022596A1 (it) * 2019-11-29 2021-05-29 Maflon S P A Granulo idrofobico o oleofobico, uso e preparazione

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JPS63295652A (ja) * 1987-05-28 1988-12-02 Asahi Chem Ind Co Ltd 親水性多孔質体
JPS6465142A (en) * 1987-05-28 1989-03-10 Asahi Chemical Ind Polyolefin sinter and its production
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IT1243862B (it) * 1990-10-23 1994-06-28 Himont Inc Concentrati non estrusi di additivo antifiamma e processo per la loro preparazione.
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GB9606824D0 (en) * 1996-03-30 1996-06-05 Gore W L & Ass Uk Granular-type modified polytetrafluoroethlyene dispersions and fused articles prepared therefrom
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Also Published As

Publication number Publication date
US20070042183A1 (en) 2007-02-22
WO2005003215A1 (fr) 2005-01-13
CA2531080A1 (fr) 2005-01-13
MXPA05014192A (es) 2006-02-24
JP2007535581A (ja) 2007-12-06
CN1816589A (zh) 2006-08-09
KR20060121804A (ko) 2006-11-29
BRPI0412035A (pt) 2006-09-05

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