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
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01C—PLANTING; SOWING; FERTILISING
  • A01C1/00—Apparatus, or methods of use thereof, for testing or treating seed, roots, or the like, prior to sowing or planting
  • A01C1/06—Coating or dressing seed
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23K—FODDER
  • A23K40/00—Shaping or working-up of animal feeding-stuffs
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
  • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
  • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
  • A23L5/30—Physical treatment, e.g. electrical or magnetic means, wave energy or irradiation
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
  • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
• • 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
  • C08J2201/00—Foams characterised by the foaming process
  • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
  • C08J2201/032—Impregnation of a formed object with a gas
• • 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
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/06—CO2, N2 or noble gases
• • 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
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/08—Supercritical fluid
• • 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

• the present invention relates to a method of impregnating a carrier matrix with solid and/or liquid compounds using compressed gases or gas mixtures, and materials impregnated in this manner.
• gases in the compressed state can be used not only for selective extraction of substances, that is to say for separations, but also for impregnation, that is to say depositing what are termed “impregnation materials” onto a carrier matrix.
• impregnation materials that is to say depositing what are termed “impregnation materials” onto a carrier matrix.
• An impregnation material can be deposited in a targeted manner in the carrier matrix via targeted control of the solution properties.
• aroma substances are first extracted from tea and collected, the caffeine is thereupon removed from the tea and then the aroma substances are restored to the decaffeinated tea (“restoration by impregnation”).
• the aroma substances are extracted here using dry carbon dioxide, while the caffeine is extracted using water as entrainer.
• Low solubility is taken to mean, in particular, if 30 to 100 parts (sparingly soluble), 100-1000 parts (slightly soluble) or 1000 or more parts, in particular up to 10,000 parts (very slightly soluble) of the solvent are required to dissolve 1 part of impregnation material.
• An object of the present invention was thus to develop a method for impregnating a carrier matrix with solid and/or liquid compounds using compressed gases, in which the impregnation materials can be transported efficiently from the surface into the interior of the respective carrier matrix, in which case an application spectrum as broad as possible is to be covered.
• This object was achieved according to the invention by the means that the solid and/or liquid compound(s) (impregnation material) and the insoluble carrier matrix are brought into contact with a compressed gas (mixture) at gas densities of at least 0.15 to 1.3 kg/l under at least 2, preferably at least 3, more preferably at least 5, and particularly preferably at least 10, unsymmetrical pressure change cycles (pulsations) in such a manner that, per individual pulsation of a period of at least 5 s to 60 min, preferably from at least 50 s to 20 min, particularly preferably of at least 100 s to 10 min, the respective time period to achieve the pressure maximum is greater than the time period of the pressure reduction to the minimum.
• a compressed gas mixture
• gas densities of at least 0.15 to 1.3 kg/l under at least 2, preferably at least 3, more preferably at least 5, and particularly preferably at least 10, unsymmetrical pressure change cycles (pulsations) in such a manner that, per individual pulsation of a period of at least 5 s to
• This method thus exploits the differing solubility of the impregnation materials at different densities of the compressed gases in the near-critical region, in order to transport the impregnation material actively from the exterior into the interior of the carrier matrix.
• the near-critical region is generally defined by a reduced temperature of a compressed gas in the range from 0.9 to 1.5 and a reduced pressure in the range from 0.8 to 5, these said differential quantities each being the ratios of the working temperature and the working pressure to the critical temperature and the critical pressure, respectively.
• the number of pressure pulsations, the time of the pulsation cycles and the pressure and density differences, respectively, generally depend on the impregnation material, the carrier matrix which is to be impregnated, the plant-specific preconditions, and the targeted extent to which the desired impregnation materials are to be distributed into/in the matrix.
• the time period to achieve the respective peak maximum (t to max ) per pulsation is greater than the time period for the pressure reduction to the peak minimum (t to min ): t to max >t to min .
• the duration of an individual pulsation is at least 5 s to 60 min, preferably at least 50 s to 20 min, particularly preferably at least 100 s to 10 min.
• t to max >>t to min , where t to max is in particular 5 to 30 times, preferably 9 to 25 times, greater than t to min since then back-transport of the impregnation materials from the carrier matrix can be most effectively suppressed.
• the minimum time period for pressure and density reduction, respectively can also be limited by the fact that the carrier matrix becomes “unstable”, that is to say is damaged, by the rapid density change, and, in particular, formally “collapses”.
• the course of the process can be set empirically in such a manner that this damage to the matrix can be excluded.
• the present method can be used for producing a multiplicity of products and intermediates in which impregnation materials are introduced into a carrier matrix.
• Suitable representatives of impregnation materials have proved to be all biologically active compounds, such as pharmaceutical, agrochemical and cosmetic active compounds, technical substances, for example surface-active or surface-modifying compositions (hydrophobization or hydrophilization) or organometallic compounds.
• Compounds which are used in this context are, in particular, vitamins, nutraceuticals, plant-treatment compositions, insecticides, fungicides, herbicides (that is to say biocides in general), phytohormones, for example cytokinins, but also aroma substances, pigments and other impregnation materials which have another functionality, such as dispersants, emulsifiers or chemically reactive compounds, for example surface-reactive compounds. It is thus also possible in the context of the present invention that, after introducing the impregnation materials into the carrier matrix, a chemical reaction is induced in-situ in the process, for example by a temperature increase or feeding in reaction initiators, in order to achieve chemical bonding of the impregnation material on the carrier matrix.
• the sole precondition for suitability as an impregnation material is its ability to dissolve in the compressed gas(mixture).
• carrier matrices are all materials of biological origin, for example foods, feeds, seed material, and other organic and inorganic carrier matrices which preferably have large and/or poorly accessible internal surface areas. This also includes carrier matrices which increase their volume under the process conditions, which is generally achieved by swelling, and as a result of which the external surface areas and also their internal surface areas increase.
• compounds which are suitable are according to the invention synthetic, semi-synthetic and natural organic polymers, for example polyethylenes (PE), polypropylenes (PP) or polyglycolic acids (for example polylactic-glycolic acid, PLGA) or carbohydrates, for example starches and cyclodextrins, in addition inorganic carrier materials, in particular those having large internal surface areas, for example silicon dioxides, such as precipitated or pyrogenic silicic acids or silica gels, alumosilicates or other catalyst base materials, for example zeolites, and aluminium oxides, activated carbons, titanium dioxides, bentonites, which can all be used in chemically or physically modified form.
• the carrier matrices having an open or closed pore internal structure can be (pre)swollen, or can be extruded or foamed matrices.
• a very large density range of the compressed, that is to say near-critical or supercritical, gases or gas mixtures can be utilised; it is in the limits essential to the invention of at least 0.15 to 1.3 kg/l, preferably from at least 0.4 to 1.0 kg/l, and particularly preferably from at least 0.5 to 0.9 kg/l.
• the process pressures according to the invention vary from at least 5 to 800 bar, with pressure ranges from at least 30, in particular at least 50 to 500 bar, being preferred.
• the process temperature should preferably be above the critical temperature of the gas or gas mixture used, in particular at least 31° C. to 200° C., preferably at least 40° C. to 150° C., particularly preferably at least 50° C. to 100° C.
• gases/gas mixtures also depends essentially on the impregnation material or the mixture of different impregnation materials which are being introduced into the carrier matrix. Fundamentally, therefore, gases/gas mixtures come into consideration whose critical state parameters are within industrially practicable limits. Inter alia the critical temperature of the gas system is particularly important, which, at excessive values, may cause thermal damage to both the impregnation materials and also the carrier matrix.
• Suitable gases for the present method have thus proved to be carbon dioxide, propane, butane, ethane, ethylene, dimethyl ether, ammonia, halogenated hydrocarbons, comprising fluorinated, chlorinated, brominated and iodated branched or unbranched hydrocarbons from C 1 to C 4 , in particular partially or completely fluorinated hydrocarbons, or their mixtures.
• a precondition for being able to carry out the method of the invention is that the impregnation materials, in the pressure peak maximum, have partly a substantially higher solubility in the gas(mixture) than in the pressure trough minimum.
• the impregnation matrix that is to say the carrier matrix, under the given processing conditions, must be insoluble both in the near-critical and also in the supercritical state of the gas(mixture).
• the absolute pressure minimum is set in this case by the minimum dissolving power of the gas(mixture) for the impregnation material and the absolute pressure maximum is set by the maximum solubility of the impregnation materials in the compressed gas(mixture).
• the pressure range from the absolute pressure minimum to the absolute pressure maximum is the range in which operations can take place in principle, but which need not be exploited completely.
• the pressure in the pressure maximum of a pulse is 1.1 times, more preferably 1.3 times, still more preferably 1.5 times, still more preferably twice, most preferably 5 times, the pressure at the pressure minimum.
• the dissolving power of the gas(mixture) in the pressure maximum is preferably at least twice, preferably at least 10 times, better than the dissolving power of the gas(mixture) in the pressure minimum.
• the density difference during the individual pulsation should be as large as possible.
• the most expedient practical lower limit of the density minimum then occurs when the gases or the gas mixtures no longer have any dissolving power for the impregnation materials.
• density there is, for the method, in principle, no upper limit in the peak maximum.
• the method is based on the principle of transport of the gas influx or gas efflux in the carrier matrix at different densities, it is in practice no longer expedient, and also generally uneconomic, to use more than 10 times the supercritical pressure of the corresponding gas or gas mixture, since the density then experiences markedly lower changes than in the near-critical state range of the gas system.
• the invention envisages that their periods can differ from one another. That is to say the period of an individual pulsation can be shorter or also longer than the preceding and/or subsequent pulsation, an individual pulsation lasting from at least 5 s to 60 min, preferably from at least 50 s to 20 min, particularly preferably from at least 100 s to 10 min.
• the respective time periods within different individual pulsation periods differ from one another, which means nothing other than that the time periods for the pressure increase and/or the time periods for the pressure reduction differ from one another from individual pulsation to individual pulsation.
• the time period for the pressure increase is always greater than the time period for the pressure reduction. It is also possible to choose the pressure minima and/or pressure maxima differently in the individual pulses.
• liquid aids that improve in particular the solubility of the impregnation materials, can also be added to the near-critical gas or to the gas mixtures, particularly preferably at atmospheric pressure.
• suitable aids are, for example, water or organic solvents selected from the group consisting of short-chain alcohols, ketones and esters, branched or unbranched, having chain lengths from C 1 to C 10 , preferably C 1 to C 8 , particularly preferably from C 2 to C 3 , and/or having surface activity, which can be used, typically, in concentrations up to 20% by weight, preferably from 1% by weight to 10% by weight, particularly preferably from 2% by weight to 5% by weight.
• entrainers can also be used, which, for example, set a suitable pH environment in the process gas.
• Those which are suitable, in particular, for this are organic amines, for example triethylamine or ammonia, which can additionally improve the solubility of the impregnation materials.
• aids and/or entrainers which are mentioned as preferred, but also all other suitable aids and/or entrainers, can also be added to the impregnation material, which again should preferably be performed at atmospheric pressure.
• Other substances which can be used not only as actual impregnation materials, but also as aids, are surface-active substances, since they themselves have good solubility in the supercritical gas(mixture) (what are termed “gasophilic surfactants”).
• the surfactants not only improves the solubility of certain impregnation materials in the gas(mixture), the surfactants acting in this case as aid, they also facilitate the penetration of the impregnation materials into the carrier matrix, since the diffusivity of the mass system impregnation materials/gas(mixture) is increased by a further reduction in surface tension.
• the “gasophilic surfactants” are used as actual impregnation materials, the purpose of the impregnation process can be modification of the surface properties of the carrier matrix, for example the improvement or reduction of their water-wettability and the associated properties.
• the method is carried out in an autoclave, and preferably in a discontinous batch process.
• a preliminary stage is provided for the inventive method, in which preliminary stage, after the autoclave is filled with the carrier matrix and the impregnation materials, the plant system is brought, by the suitable gas(mixture), to the corresponding pressure at which the impregnation materials exhibit the abovedescribed solubility behaviour.
• the gas or the gas mixture is then, in the supercritical state, circulated in such a manner that the impregnation materials are distributed on the carrier matrix and the concentration gradient of the active compounds in the bed of the carrier matrix achieves an acceptable minimum value.
• the process pressure, and thus the density of the gas system is then reduced in such a manner that the impregnation materials settle (precipitate; are deposited) on the surfaces of the carrier matrix.
• an alternative procedure can also be suitable, especially if the solubility of the impregnation materials, even in the supercritical state of the gas(mixture), is only low, and a long process time is required for recirculating the gas or the gas mixture in the autoclave, to achieve the desired distribution in the carrier matrix packed bed, that is to say to minimise its concentration gradient in the packed bed.
• the invention provides precoating the carrier matrix with the impregnating materials by means of conventional technology, such as, in particular, the known methods for spray coating, in particular in the fluidized bed, or else melt coating.
• the impregnating materials are applied to the wall of the carrier matrix particles, without the impregnating materials being able to penetrate, at any rate essentially, into the internal region of the matrix particles.
• the material thus prepared is then also subjected to the pulsation process essential to the invention for impregnation, as a result of which the impregnation materials are only then transported into the interior of the carrier matrix.
• This procedure can have enormous economic advantages, since the actual transport path which must be overcome by the impregnating material that is dissolved in the gas(mixture) is very short, that is to say only from the surface of the matrix particles into their interior.
• the individual loading of the matrix particles with impregnating material can be controlled and ensured markedly better.
• the present method thus has great potential, especially, for introducing pharmaceutical active compounds into a suitable carrier matrix having a large internal surface area, as required in the production of preparations having delayed release of active compound.
• a further application example is impregnating or disinfecting seed material, the critical advantage of the inventive process being that the plant treatment composition does not, as hitherto in the prior art, remain solely in the outer regions of the seed grain, but can be introduced into the internal region of the seed body. For certain applications, this can lead to an improved effect with simultaneously lower dosages.
• the impregnating materials used can also be organometallic substances which are to be introduced into a matrix, as is customary in particular in the production of supported catalysts.
• the present invention also relates to all impregnated substances produced using this method.
• the insert vessel which was completely filled with rice grains was inserted into the pressure autoclave of a high-pressure extraction system.
• the autoclave was first brought at 50° C. (set by means of jacket heating) to a pressure of 150 bar (pressure minimum) with carbon dioxide.
• the pressure was then slowly increased to 500 bar over a period of 5 min, using a high-pressure pump (pressure maximum) and then rapidly reduced back to 100 bar in the course of 15 s via a pressure control valve.
• This pulsation operation was repeated in the same manner 20 times.
• the rice grains were taken out and the result of impregnation was compared with the starting material.
• the red-stained pigment zone had disappeared from the edge regions and in the light microscope, an even staining of the starch body over the entire cross section of the rice grain with ⁇ -carotene was observed.
• ketoprofen 5 g were dissolved in 150 ml of methanol and the solution, together with 15 g of Endobon® (Merck; porous hydroxyapatite granules; 2.8 to 5.6 mm), was transferred to a round-bottomed flask. The solvent was removed under reduced pressure on a rotary evaporator with agitation.
• the starting material thus pretreated was introduced into an insert vessel (volume 0.5 l) which was sealed at the top and bottom with metal sinter plates.
• the insert vessel was inserted into the pressure autoclave of a high-pressure extraction system.
• the autoclave was first, at 50° C. (set using jacket heating), brought to a pressure of 100 bar (pressure minimum) with carbon dioxide which contained 1% by weight of methanol as entrainer.
• the pressure was then slowly increased to 250 bar (pressure maximum) over a period of 3 min, using a high-pressure pump, and then rapidly reduced to 100 bar via a pressure control valve in the course of 20 s. This pulsation operation was repeated 10 times in the same manner.
• the impregnated carrier matrix was removed.
• the release rate of ketoprofen on the carrier matrix was determined in a dissolution test and compared with a starting material that had not been subjected to the pulsation impregnation, and with a sample which had been treated with symmetrical pulsation cycles (1.5 min in each case for pressure rise and decrease).
• the sample from Example 2 (invention) showed the longest release curve, followed by the symmetrically treated pulsation material (comparison); the shortest release curve was shown by the precoated starting material that had not been subjected to a pressure treatment.
• Accurel® granules (Akzo; high-porosity polypropylene) were introduced into an insert vessel (volume 0.5 l) which was closed at the top and bottom with metal sinter plates.
• the insert vessel was inserted into the pressure autoclave of the high-pressure extraction system.
• the autoclave was first, at 96° C. (set by means of jacket heating), brought to a pressure of 100 bar with propane.
• silicone oil dimethylpolysiloxane having a viscosity of 10,000 mpas
• propane isothermically and isobarically, in order to achieve uniform distribution of the silicone oil in the packed bed of the Accurel carrier matrix.
• the pressure was then reduced to 43 bar, which decreased the solubility of the silicone oil in the propane.
• the invention thus relates in particular to a method of impregnating a carrier matrix with solid and/or liquid compounds using compressed gases which is essentially characterized in that the solid and/or liquid compound(s) (impregnating material) and the insoluble carrier matrix are brought into contact with a compressed gas(mixture) at gas densities between 0.15 and 1.3 kg/l under at least two unsymmetrically preceding pressure-change cycles (pulsations) in such a manner that, per individual pulsation of a duration between 5 s and 60 min, the respective time period to achieve the pressure maximum is greater than the time period for pressure reduction to the minimum, the absolute pressure minimum being established by the minimum dissolving power of the gas(mixture) for the impregnating material and the absolute pressure maximum being established by the maximum solubility of the impregnating materials in the compressed gas(mixture).
• the method is distinguished in that not only a multiplicity of impregnation materials, for example biologically active compounds, industrial substances or organometallic compounds, can be used but also carrier matrices of biological origin and organic or inorganic substances, which all have large and/or poorly accessible internal surface areas.
• this method which is preferably carried out using compressed carbon dioxide, propane, butane, ethane or ammonia, not only can untreated carrier material be handled but also already precoated material.
• impregnated materials are obtained whose internal surfaces are substantially homogeneously coated with the impregnation materials and which can be used, especially, in the pharmaceutical, agrochemical, cosmetic and technical sectors.

Landscapes

• Life Sciences & Earth Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Polymers & Plastics (AREA)
• Food Science & Technology (AREA)
• Environmental Sciences (AREA)
• Nutrition Science (AREA)
• Zoology (AREA)
• General Health & Medical Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Pest Control & Pesticides (AREA)
• Agronomy & Crop Science (AREA)
• Medicinal Chemistry (AREA)
• Materials Engineering (AREA)
• Plant Pathology (AREA)
• Toxicology (AREA)
• Dentistry (AREA)
• Wood Science & Technology (AREA)
• Soil Sciences (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Catalysts (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Paper (AREA)
• Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
• Inert Electrodes (AREA)
• Manufacture Of Alloys Or Alloy Compounds (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)
• Materials For Medical Uses (AREA)
• Medicinal Preparation (AREA)
• Filling Or Discharging Of Gas Storage Vessels (AREA)

Priority Applications (1)

Applications Claiming Priority (3)

Related Child Applications (1)

Publications (1)

Family

ID=7653262

Family Applications (2)

Family Applications After (1)

Country Status (17)

Cited By (3)

Families Citing this family (12)

Citations (5)

Family Cites Families (13)

• 2000
  • 2000-08-22 DE DE10041003A patent/DE10041003A1/de not_active Withdrawn
• 2001
  • 2001-08-20 TW TW090120425A patent/TWI302114B/zh not_active IP Right Cessation
  • 2001-08-21 DE DE50114570T patent/DE50114570D1/de not_active Expired - Lifetime
  • 2001-08-21 AU AU2001291786A patent/AU2001291786A1/en not_active Abandoned
  • 2001-08-21 JP JP2002524644A patent/JP5015405B2/ja not_active Expired - Fee Related
  • 2001-08-21 EP EP01971946A patent/EP1313569B1/de not_active Expired - Lifetime
  • 2001-08-21 RU RU2003107840/12A patent/RU2257961C2/ru not_active IP Right Cessation
  • 2001-08-21 MX MXPA03001554A patent/MXPA03001554A/es not_active Application Discontinuation
  • 2001-08-21 KR KR20037002512A patent/KR20030065467A/ko not_active Application Discontinuation
  • 2001-08-21 DK DK01971946T patent/DK1313569T3/da active
  • 2001-08-21 PT PT01971946T patent/PT1313569E/pt unknown
  • 2001-08-21 BR BR0113361-6A patent/BR0113361A/pt not_active IP Right Cessation
  • 2001-08-21 WO PCT/EP2001/009669 patent/WO2002020177A1/de active Application Filing
  • 2001-08-21 ES ES01971946T patent/ES2317934T3/es not_active Expired - Lifetime
  • 2001-08-21 CN CNB018143547A patent/CN100421821C/zh not_active Expired - Fee Related
  • 2001-08-21 US US10/362,136 patent/US20040101623A1/en not_active Abandoned
  • 2001-08-21 AT AT01971946T patent/ATE416852T1/de active
• 2003
  • 2003-01-21 IN IN75KO2003 patent/IN2003KO00075A/en unknown
• 2006
  • 2006-11-09 US US11/598,484 patent/US7713581B2/en not_active Expired - Fee Related

Patent Citations (5)

Also Published As

Similar Documents

Legal Events