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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B7/00—Mixing; Kneading
  • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
  • B29B7/58—Component parts, details or accessories; Auxiliary operations
  • B29B7/60—Component parts, details or accessories; Auxiliary operations for feeding, e.g. end guides for the incoming material
  • B29B7/603—Component parts, details or accessories; Auxiliary operations for feeding, e.g. end guides for the incoming material in measured doses, e.g. proportioning of several materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B7/00—Mixing; Kneading
  • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
  • B29B7/7461—Combinations of dissimilar mixers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B7/00—Mixing; Kneading
  • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
  • B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
  • B29B7/748—Plants
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B7/00—Mixing; Kneading
  • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
  • B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
  • B29B7/7485—Systems, i.e. flow charts or diagrams; Plants with consecutive mixers, e.g. with premixing some of the components
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B7/00—Mixing; Kneading
  • B29B7/80—Component parts, details or accessories; Auxiliary operations
  • B29B7/82—Heating or cooling
  • B29B7/823—Temperature control
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B7/00—Mixing; Kneading
  • B29B7/80—Component parts, details or accessories; Auxiliary operations
  • B29B7/84—Venting or degassing ; Removing liquids, e.g. by evaporating components
  • B29B7/845—Venting, degassing or removing evaporated components in devices with rotary stirrers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
  • B29B7/00—Mixing; Kneading
  • B29B7/80—Component parts, details or accessories; Auxiliary operations
  • B29B7/88—Adding charges, i.e. additives
  • B29B7/885—Adding charges, i.e. additives with means for treating, e.g. milling, the charges
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
  • B29C48/375—Plasticisers, homogenisers or feeders comprising two or more stages
  • B29C48/385—Plasticisers, homogenisers or feeders comprising two or more stages using two or more serially arranged screws in separate barrels
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
  • B29C48/375—Plasticisers, homogenisers or feeders comprising two or more stages
  • B29C48/39—Plasticisers, homogenisers or feeders comprising two or more stages a first extruder feeding the melt into an intermediate location of a second extruder
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/92—Measuring, controlling or regulating
• • 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
  • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
  • C08J2383/04—Polysiloxanes

Definitions

• the invention relates to a process for the continuous production of hot vulcanizing silicone compositions based on diorgano (poly) siloxanes, which are referred to in the art as (High Te perature Vulcanizing) HTV silicone compositions.
• these HTV silicone compositions differ from the (Roo Temperature Vulcanizing) RTV silicone compositions. While the HTV silicone compositions only vulcanize at a temperature which is higher than room temperature via a radical reaction or addition reaction, vulcanization takes place with one-component RTV silicone compositions via a condensation reaction with atmospheric moisture, ie water, even at room temperature.
• One-component RTV silicone compositions have reinforcing fillers in amounts of at most 10% by weight.
• HTV silicone compositions are at least 20% by weight.
• RTV silicone compositions see also Winnacker, kuchler, Volume 6, Inorganic Technology II, 4th edition, 1982, Carl Hanser Verlag Kunststoff Vienna, pages 842 and 845, J. Bittera, rubber, rubber, plastics , 39th volume No. 1/86 or JC Weis in Progress of Rubber Technology, edited by SH Morell, Elsevier Applied Science Publishers, Ltd., England, 1984 pages 85-106.
• HTV silicone compositions differ from RTV silicone compositions in the following points in particular:
• HTV peroxides
• HTV siloxane diols
• RTV silicone oils
• HTV silicone masses are produced almost exclusively discontinuously in kneaders, internal mixers or mixing rolling mills by mixing the starting materials according to the current state of the art.
• EP-B-258159 a process for the continuous production of mother mixtures in the form of homogeneous and thick pastes is known, in order later to obtain hot-vulcanizable silicone elastomers, an endless double-screw kneader being fed with a polysiloxane-based polymer and a powdery batch becomes.
• the powdery batch is preferably silicon dioxide with a density above 0.1 kg / l.
• the object of the invention is to provide a process for the continuous production of HTV silicone compositions which avoids the disadvantages of the prior art.
• This object is achieved by a process for the continuous production of HTV silicone compositions, characterized in that 100 parts by weight of diorgano (poly) siloxane, the at 25 ° C has a viscosity of 50 to 100,000 Pas, mixed with at least 20 parts by weight of finely divided silicon dioxide, which has a tamped density above 0.01 kg / 1, and homogenized.
• HTV silicon compositions with positive product properties such as homogeneous and transparent appearance, good speck evaluation, constant Mooney viscosity and constant Shore hardness A.
• the HTV silicone compositions can contain further fillers, structure improvers, peroxides and, if appropriate, additives, such as, for example, hot air stabilizers, flame retardants and pigments.
• the uncrosslinked HTV silicone compositions obtained preferably have a Mooney viscosity (DIN 53523) of 15 to 130 Mooney units (final Mooney value, ML (1 + 4), 23 ° C.), which results after crosslinking with Peroxides and subsequent tempering elastomers with Shore hardness A (DIN 53505) of preferably 15 to 110, in particular 15 to 95, result.
• diorgano (poly) siloxanes with a viscosity at 25 ° C. of 50 to 100,000 Pas, preferably 500 to 50,000 Pas, are used.
• the organo residues in the diorgano (poly) siloxanes used according to the invention are preferably methyl, vinyl, phenyl and / or trifluoroalkyl residues.
• a preferred trifluoroalkyl radical is the 3,3,3 trifluoropropyl radical.
• vinyl and / or phenyl radicals are present in the chains of the diorgano (poly) siloxanes in addition to methyl and / or trifluoroalkyl radicals, a preferred quantitative range for these radicals is 0.001-30 mol%, in particular 0.001-25 mol%.
• Diorgano (poly) siloxanes which are terminated with trimethyl, dimethylvinyl, methyldivinyl and / or trivinylsiloxy groups are preferably used. For special applications, however, the use of diorgano (poly) siloxanes that are not or only partially stopped is necessary.
• Preferred diorgano (poly) siloxanes correspond to the general formulas
• R is methyl and / or vinyl and R 1 is methyl, vinyl and / or hydroxyl and n is within the limits from 500 to 10,000, preferably from 2,000 to 8,000, and n + m are within the limits of 500 to 10,000, preferably from 2,000 to 8,000, with the proviso that the quotient n / m is greater than or equal to 1, preferably within the limits of 3 to 10,000.
• the diorgano (poly) siloxanes in addition to units of the formula R 2 SiO, can counteract up to 0.05 mol%, preferably less than 0.02 mol%, of other, mostly more or less difficult to avoid, impurities 76rtige units of the formula Si0 4/2 and RSi0 3/2, where R is an organic radical, usually methyl, ethyl, vinyl, phenyl and / or trifluoroalkyl.
• Particulate silicon dioxide according to the invention has a tamped density (ISO 787/11) above 0.01 kg / 1, preferably in the range from 0.02 to 0.4 kg / 1.
• finely divided silicon dioxide are pyrogenic and / or precipitated silicon dioxide, which can be rendered hydrophobic by treatment with, for example, organosilanes, -silazanes or -siloxanes or by etherification of hydroxyl groups to give alkoxy groups.
• Equally advantageous is wetting and densification of finely divided, hydrophilic silicon dioxide, the tamped density of which is less than 0.1 kg / l, with diorgano (poly) siloxane and / or low-viscosity polymethylsiloxane diol, as hereinafter referred to as diorgano (poly) siloxane and / or structure improver described, on tamped densities of preferably 0.03-0.5 kg / 1.
• the wetting and resulting increase in the tamped density of finely divided silicon dioxide is carried out with preferably 30 to 100%, in particular 50 to 100%, of the parts by weight, structural improvers present in the composition of the HTV silicone compositions prepared according to the invention.
• the temperature here is preferably less than 180 ° C., in particular 10 to 120 ° C. If the formulation requires the use of hydrophobic silicon dioxide, preferably hydrophobic silicon dioxide with a carbon content of more than 1% by weight, based on the total weight of hydrophobic silicon dioxide, in particular from 2 to 8% by weight, and tamped densities of greater than 0.05 kg / 1, in particular 0.2 to 0.4 kg / 1, used.
• hydrophobic silicon dioxide preferably hydrophobic silicon dioxide with a carbon content of more than 1% by weight, based on the total weight of hydrophobic silicon dioxide, in particular from 2 to 8% by weight, and tamped densities of greater than 0.05 kg / 1, in particular 0.2 to 0.4 kg / 1, used.
• reinforcing fillers to be used with a BET surface area (DIN 66131) of preferably more than 50 m 2 / g are finely divided hydrophilic or hydrophobic silicon dioxide with a tamped density less than 0.1 kg / 1, preferably 0.01-0 , 09 kg / 1, furnace black and acetylene black. Preferred amounts of these substances are 0 to 60 parts by weight.
• Non-reinforcing fillers such as quartz, diatomaceous earth, calcium silicate, zirconium silicate, zeolites, metal oxide powders such as aluminum, titanium, iron or zinc oxide, barium silicate, barium sulfate, calcium carbonate, gypsum, and plastic powders such as polyacrylonitrile powder can also be used become.
• Other fillers are fibrous components such as glass fibers and plastic fibers. The BET surface area of these fillers is generally less than 50 m 2 / g.
• these are preferably polydimethylsiloxane diols with a viscosity at 25 ° C. of preferably 10 to 200 Pas, in particular 20 to 150 mPas. They can contain phenyl groups and, in particular, to influence the hardness of the vulcanizate, vinyl groups can also be present in the chain of these polydimethylsiloxane diols, the vinyl group density being recorded via the iodine number (DIN 53241).
• the iodine number is preferably 1 to 75 g iodine per 100 g siloxane diol, in particular 7 to 70 g per 100 g.
• the preparation of these polydimethylsiloxane diols is generally known and is described, for example, on pages 20 to 22 in A. Tomanek, Silicone undtechnik, Hanser Verlag.
• pigments and crosslinkers from the group of alkyl or aroyl peroxides are also preferably incorporated.
• alkyl peroxides are dicumyl peroxide, di-tert-butyl peroxide and 2,5-di-tert-butyl peroxy-2,5-dimethylhexane.
• aroyl peroxides are benzoyl peroxide, bis (2,4-dichlorobenzoyl) peroxide and bis (4-methylbenzoy1) peroxide.
• compositions of the HTV silicone compositions prepared according to the invention are as follows:
• R is methyl and R 1 are vinyl radicals
• n + m are within the limits of 2000 to 8000 and n / m are within the limits of 200 to 8000
• R and R 1 are methyl radicals and n + m are within the limits of 500 to 8000 and n / m are within the limits of 3 to 50, with the proviso that the sum of the amounts used is 100 parts by weight.
• the total length can be used here as a mixing zone, but is preferably divided into a mixing and a degassing zone, the mixing and degassing zone being separated, for example, by a baffle plate.
• the separation of the two zones is, however, also by two successive kneaders connected in series possible, the mixing process taking place in the first kneader and the degassing process taking place in the second kneader.
• Such vocational step kneaders are also known in the art as kneading kneaders (Ulimann's Encyclopedia of Industrial Chemistry, 4th edition, volume 2, page 296, Verlag Chemie, Weinheim / Berg ⁇ strasse BR Germany) or as Buss kneaders (Buss kneader) .
• the mix can be kept at a predetermined temperature level during the entire mixing process by heating or cooling.
• the diorgano (poly) siloxanes used according to the invention are either taken from an upstream, continuous polymer reactor (2), preferably also from a vocational step kneader, and fed to the mixing zone of the single-shaft vocational step kneader without further intermediate storage, the material flow based on the metered amounts of Reaction components in the polymer reactor are known and freely adjustable, or from storage containers, such as intermediate tanks, and suitable metering devices, such as liquid differential metering scales, into the mixing zone, preferably in the range of 0-4D, in particular 0-2D, of the single-shaft ⁇ vocational step kneader pumped.
• the diorgano- (poly) siloxanes are preferably fed from the polymer reactor using a conveyor element such as, for example, a discharge screw and / or a gear pump (3), the diorgano (poly) siloxane preferably entering the single-shaft pilger kneader over a polymer cooler (4), such as a plate cooler.
• a conveyor element such as, for example, a discharge screw and / or a gear pump (3)
• the diorgano (poly) siloxane preferably entering the single-shaft pilger kneader over a polymer cooler (4), such as a plate cooler.
• the distance from the conveyor element should be as small as possible and preferably not exceed 10 m.
• one or more diorgano (poly) siloxanes from continuous polymer reactors and / or storage containers, as described above can be fed to the mixing zone of the single-shaft pilger step kneader in a controlled, time-constant mass flow.
• the silicon dioxide used according to the invention and, if appropriate, further reinforcing or non-reinforcing fillers are preferably introduced into the mixing zone of the single-shaft vocational kneader, preferably in the range from 0.5 to 10D, in particular 2-8D, using differential metering scales (5) and / or running-in aids. In particularly preferred embodiments, this takes place via at least two metering points distributed over this area. Cylindrical or conical vessels with built-in rotating helixes or screws can be used as entry aids, or alternatively single or multiple-shaft entry screws rotating in the same or opposite directions.
• silicon dioxide which results from the wetting of finely divided, hydrophilic silicon dioxide with structural improvers, this wetting takes place in continuous or discontinuous high-speed mixers (6).
• metering pumps (7) such as piston pumps, diaphragm pumps or gear pumps, with a flow meter and control circuit.
• the structure improver metering should preferably take place in the area of the polymer metering point, preferably in the range 0-4D, in particular before metering in the silicon dioxide used according to the invention and, if appropriate, further fillers used.
• Another variant which may be used is the feeding of the structural improver in whole or in part into the mixing zone or into the degassing zone shortly before the discharge element, preferably in the range from 5 to 1D before the discharge element, of the single-shaft vocational kneader.
• additives can be added.
• the place of addition and the quantity are not critical, they are based on the requirements of the recipe.
• the formulation-specific dosed components are mixed, homogenized and degassed in the mixing and degassing zone.
• the temperature control depends on the respective recipe. It is advantageous if the mixing and degassing zones are equipped with separate temperature control circuits.
• the temperature within the single-shaft pilger kneader is preferably 20 to 280 ° C, in particular 80 to 220 ° C.
• the degassing is preferably carried out in a vacuum.
• the evacuation is preferably carried out with the aid of vacuum pumps (8) such as water ring pumps, optionally combined with rotary piston pumps or jet pumps. Working with a slight inert gas drag stream in the mixing and / or degassing zone is also possible. Nitrogen is then preferably used as the inert gas.
• a discharge screw or a discharge pump is preferably used as the discharge element.
• the mass is then preferably fed to a screening device, for example a screening head (9) with an automatic changing device.
• a screening device for example a screening head (9) with an automatic changing device.
• the pressure build-up required for this is preferably carried out using extruders (10) or gear pumps.
• the resulting mass is preferably fed to a continuous rolling system (11), such as a shear roller extruder, for cooling to temperatures of preferably less than or equal to 100 ° C., in particular 40 to 100 ° C.
• crosslinking agents and / or pigments and / or other additives are incorporated into these rolling mills after cooling. These substances are preferably metered via differential metering scales.
• the masses which are preferably cooled to 20 to 90 ° C., can finally be converted into ready-to-sell goods preferably via pressure build-up machines, such as a single-shaft extruder, with subsequent shaping (12).
• the systems used in the process according to the invention may contain further components known per se, such as metering and other conveying devices, measuring and control devices, for example for pressure, temperature and volume flows, valves Parts required for degassing and cooling, conveying and packaging devices, devices for charging the goods with inert gas, and devices for drying such gases.
• metering and other conveying devices such as metering and other conveying devices, measuring and control devices, for example for pressure, temperature and volume flows, valves Parts required for degassing and cooling, conveying and packaging devices, devices for charging the goods with inert gas, and devices for drying such gases.
• the kneader was heated to 150 ° C. and the speed of the screw was set to 100 rpm. After a premixing section for the polymer of approximately 2 D, finely divided hydrophobic silica was metered in over a process length of a further 2 D using a powder differential metering scale. Total dosage: 30 kg / h. The stamp density of the silica is 0.30 kg / 1. The metered silica was homogenized with the polymer via 11 D and then discharged via a gear pump. The melt temperature (Pilger step kneader outlet) was 185 ° C during the test (duration: 3 h) and was only subject to slight fluctuations in the range of 183-187 ° C. The product could be characterized by the following properties.
• Screw diameter 80 mm, process length: 20 D, temperature control of housing and screw: 150 ° C speed: 40 rpm
• the melt temperature during the test (duration: 3 h) was 182-194 ° C with peaks up to 210 ° C.
• the product can be characterized by the following properties.

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• Mechanical Engineering (AREA)
• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Polymers & Plastics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
• Silicon Polymers (AREA)
• Silicon Compounds (AREA)

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• 1991
  • 1991-02-07 DE DE4103602A patent/DE4103602A1/de not_active Withdrawn
  • 1991-12-28 TW TW080110220A patent/TW229221B/zh not_active IP Right Cessation
• 1992
  • 1992-01-07 CZ CS9234A patent/CZ280578B6/cs not_active IP Right Cessation
  • 1992-01-16 RU RU9293054013A patent/RU2091222C1/ru active
  • 1992-01-16 DE DE59201026T patent/DE59201026D1/de not_active Expired - Lifetime
  • 1992-01-16 WO PCT/EP1992/000080 patent/WO1992013694A1/de active IP Right Grant
  • 1992-01-16 US US08/074,819 patent/US6124392A/en not_active Expired - Lifetime
  • 1992-01-16 EP EP92902131A patent/EP0570387B1/de not_active Expired - Lifetime
  • 1992-01-16 KR KR1019930702264A patent/KR970000921B1/ko not_active Expired - Lifetime
  • 1992-01-16 JP JP4502487A patent/JP2531912B2/ja not_active Expired - Lifetime
  • 1992-01-16 AT AT92902131T patent/ATE115903T1/de not_active IP Right Cessation
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