EP3166771A1 - Mischelemente mit verbesserter dispergierwirkung - Google Patents
Mischelemente mit verbesserter dispergierwirkungInfo
- Publication number
- EP3166771A1 EP3166771A1 EP15736480.3A EP15736480A EP3166771A1 EP 3166771 A1 EP3166771 A1 EP 3166771A1 EP 15736480 A EP15736480 A EP 15736480A EP 3166771 A1 EP3166771 A1 EP 3166771A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- screw
- elements
- mixing elements
- outer diameter
- mixing
- 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- Withdrawn
Links
Classifications
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- 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
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
- B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
- B29B7/488—Parts, e.g. casings, sealings; Accessories, e.g. flow controlling or throttling devices
- B29B7/489—Screws
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
- B01F27/05—Stirrers
- B01F27/11—Stirrers characterised by the configuration of the stirrers
- B01F27/114—Helically shaped stirrers, i.e. stirrers comprising a helically shaped band or helically shaped band sections
- B01F27/1143—Helically shaped stirrers, i.e. stirrers comprising a helically shaped band or helically shaped band sections screw-shaped, e.g. worms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
- B01F27/40—Mixers with rotor-rotor system, e.g. with intermeshing teeth
- B01F27/42—Mixers with rotor-rotor system, e.g. with intermeshing teeth with rotating surfaces next to each other, i.e. on substantially parallel axes
- B01F27/421—Mixers with rotor-rotor system, e.g. with intermeshing teeth with rotating surfaces next to each other, i.e. on substantially parallel axes provided with intermeshing elements
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- 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
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
- B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
- B29B7/482—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws provided with screw parts in addition to other mixing parts, e.g. paddles, gears, discs
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- 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
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
- B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
- B29B7/486—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws with screws surrounded by a casing provided with grooves or cavities
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- 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
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
- B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
- B29B7/488—Parts, e.g. casings, sealings; Accessories, e.g. flow controlling or throttling devices
-
- 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
- B29B7/72—Measuring, controlling or regulating
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- 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
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- 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
- B29B7/86—Component parts, details or accessories; Auxiliary operations for working at sub- or superatmospheric pressure
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- 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
- B29B7/94—Liquid charges
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- 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
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- 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
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
- B29C48/405—Intermeshing co-rotating screws
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- 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
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/55—Screws having reverse-feeding elements
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- 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
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/56—Screws having grooves or cavities other than the thread or the channel
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- 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
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/585—Screws provided with gears interacting with the flow
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- 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
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/59—Screws characterised by details of the thread, i.e. the shape of a single thread of the material-feeding screw
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- 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
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/59—Screws characterised by details of the thread, i.e. the shape of a single thread of the material-feeding screw
- B29C48/60—Thread tops
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- 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
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/67—Screws having incorporated mixing devices not provided for in groups B29C48/52 - B29C48/66
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- 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
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/79—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling of preformed parts or layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F2101/00—Mixing characterised by the nature of the mixed materials or by the application field
- B01F2101/2805—Mixing plastics, polymer material ingredients, monomers or oligomers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F2215/00—Auxiliary or complementary information in relation with mixing
- B01F2215/04—Technical information in relation with mixing
- B01F2215/0413—Numerical information
- B01F2215/0418—Geometrical information
- B01F2215/0431—Numerical size values, e.g. diameter of a hole or conduit, area, volume, length, width, or ratios thereof
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92009—Measured parameter
- B29C2948/92085—Velocity
- B29C2948/92104—Flow or feed rate
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92009—Measured parameter
- B29C2948/92228—Content, e.g. percentage of humidity, volatiles, contaminants or degassing
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92323—Location or phase of measurement
- B29C2948/92447—Moulded article
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/926—Flow or feed rate
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92723—Content, e.g. percentage of humidity, volatiles, contaminants or degassing
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- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92933—Conveying, transporting or storage of articles
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- 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
- B29C48/251—Design of extruder parts, e.g. by modelling based on mathematical theories or experiments
- B29C48/2517—Design of extruder parts, e.g. by modelling based on mathematical theories or experiments of intermeshing screws
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- 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
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
- B29C48/402—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders the screws having intermeshing parts
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- 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
- B29C48/50—Details of extruders
- B29C48/76—Venting, drying means; Degassing means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
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- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working
Definitions
- the invention relates to mixing elements with an increased number of Basisgeometrieperioden per length and an improved dispersing effect for multi-shaft screw extruder with pairwise co-rotating screw shafts.
- the mixing elements have games which are designed according to the method of equidistant spacings or according to the method of longitudinal equidistants.
- the invention further relates to the use of the mixing elements in multi-screw extruders, a corresponding screw extruder containing the mixing elements and a method for the extrusion of plastic masses.
- DE 10 2007 055764 A1 discloses a screw for a twin-screw extruder having a screw main body formed by combining a plurality of segments with each other in the axial direction.
- the screw main body has a plurality of axial sections which perform various functions: a conveying section for conveying the kneading material, a kneading section for kneading the material to be kneaded, and an extruding section for pressurizing and extruding the material to be kneaded.
- One of the essential tasks performed on multi-screw extruders is to disperse liquid phases or liquid additives in polymer melts that are not homogeneously miscible or to disperse solids in polymer melts.
- Another essential task that is performed on multi-screw extruders is the dispersing of a gaseous phase in a polymer melt.
- a gaseous phase serves as entrainer in a degassing zone downstream of the dispersing zone.
- the entraining agent leads on the one hand to an (improved) foaming of the polymer melt with correspondingly larger free degassing surfaces and, on the other hand, to a partial pressure reduction of the volatiles to be degassed (monomers, oligomers,
- Solvent As entrainer, for example, water, carbon dioxide or nitrogen are known.
- the quality of the dispersion influences in many ways the operating behavior of a screw extruder.
- a poor dispersion of gaseous, liquid or solid additives reduces the product quality by inhomogeneities within the plastic masses.
- a poor dispersion of an entraining agent in the dispersing zone additionally leads to a reduction in the degassing capacity in a degassing zone downstream of the dispersing zone and, under certain circumstances, the required residual contents of monomers, oligomers and solvents in the plastic mass can no longer be achieved.
- Poor dispersion can be counteracted by increasing the speed or by reducing the throughput. Both measures have the disadvantage that this increases the temperature of the processed plastic material in the screw extruder and thus the product quality decreases due to an increased damage kinetics.
- mixing elements are known which are suitable for dispersing fillers and liquid additives in polymer melts. With regard to their geometry, these mixing elements are based on a recirculating, catchy conveying element with Erdmenger profile and have in their comb rows promoting grooves. Such mixing elements are known to those skilled in the art as tooth mixing elements (ZME).
- AI tooth mixer elements are disclosed in which the slope of the basic geometry is 0.2 to 0.35 times the outer diameter of the tooth mixing element, wherein the pitch is understood to mean the axial length for a complete rotation of the Screw profile is required.
- the pitch of the grooves is reported to be 2.5 to 6 times the outside diameter of the tooth mixing element.
- tooth mixing elements are known in which the slope of the Basisge- geometry is 0.1 to 0.5 times the outer diameter of the tooth mixing element.
- JP 2012 213996 A discloses tooth mixing elements in which the pitch of the base geometry is 0.1 to 0.3 times the outer diameter of the tooth mixing element.
- WO 2009/051279 AI discloses mixing elements in which the pitch of the base geometry is 0.50 to 1.50 times the outer diameter.
- the mixing elements have 10 to 30 grooves per base geometry period.
- mixing elements for multi-shaft screw extruders which allow the best possible dispersion, in particular gaseous additives, with the lowest possible energy input and the highest possible throughput.
- This object was achieved by providing the mixing elements according to the invention for multi-screw extruders with pairs of corotating screw shafts, wherein the mixing elements are characterized in that the mixing elements between pairs arranged mixing games in the range of 0.002 to 0.05, based on the Outer diameter of the mixing element, are present, the games are designed according to the method of the room equidistant or according to the method of longitudinal equidistants; and the number of basic geometry periods in a length corresponding to the length of the outer diameter of the mixing element is greater than or equal to 5.5 solved.
- An improved dispersion of gaseous, liquid or solid additives as well as of entrainers enables a better product quality of the plastic mass with regard to better homogeneity of the plastic mass and with regard to lower residual contents of monomers,
- the speed can be reduced until the previous product quality sets again, resulting in lower temperatures in the plastic mass and the specific energy consumption of the screw extruder decreases.
- the throughput can be increased until the previous product quality sets again, resulting in a lower temperatures in the plastic mass and the specific energy requirement of the screw extruder decreases and on the other hand reduce the fixed costs per produced product amount of plastic mass.
- the use of the mixing elements according to the invention thus makes it possible to reduce the specific energy input and thus to increase the quality of the product or the product throughput and still achieve a comparable with the prior art dispersion.
- screw extruder in the sense of the invention means a twin-screw extruder, multi-screw extruder or ring extruder.
- screw extruder is used as a generic term for these three types of screw extruders.
- a screw extruder comprises one or more housings having two or more substantially axially parallel and interpenetrating housing bores and two or more intermeshing screw shafts rotating in the same direction.
- the worm shafts may have any desired combination of conveying elements, kneading elements and / or mixing elements.
- a conveyor element is characterized by (see, for example, [1], pages 227-248) that the screw profile in the axial direction is continuously helically twisted and continued.
- the conveying element may be right-handed or left-handed and depending on the direction of rotation of the screw extruder be active in promoting or recirculating.
- the pitch T of the conveyor elements is preferably in the range of 0.1 to 10 times the outer diameter, the slope being understood to mean the axial length required for complete rotation of the screw profile.
- the axial length of a conveyor element is preferably made in integer multiples of T / Z for practical reasons, where Z is the number of flights.
- a kneading element is thereby characterized (see, for example, [1], pages 227-248) that the screw profile is continued in the axial direction in a batchwise manner in the form of kneading disks, which are each separated by a groove.
- the offset angle VW between the kneading disks is preferably in the range of 10 ° to 180 °.
- the arrangement of the kneading discs can be right or left handed.
- a kneading element can be actively conveying, promoting neutral or returning.
- the axial length of the kneading discs LK is preferably in the range of 0.02 times to 2 times the outer diameter.
- the axial length of the groove LN between two adjacent kneading disks is preferably in the range of 0.001 to 0.1 times the outer diameter.
- the pitch T of the kneading member is preferably in the range of 0.1 to 10 times the outer diameter.
- the axial length of a kneading element is preferably made in integer multiples of T / Z for practical reasons, where Z is the number of turns.
- mixing elements are formed thereby (see, for example, [1], pages 227-248) that conveying elements are implemented with openings in the screw combs.
- Such mixing elements can be right- or left-handed.
- the pitch T of such mixing elements is preferably in the range of 0.1 times to 10 times the outer diameter.
- the axial length of a mixing element is analogous to the conveying elements preferably in integer multiples executed by T / Z.
- the openings preferably have the shape of a u- or v-shaped groove.
- the grooves of a mixing element are preferably arranged parallel to the axis or counter-conveying to the gradient of the underlying conveying element.
- a mixing element can be active in promoting, promoting neutral or recirculating. Under the slope of the grooves becomes the axial
- Length is understood, which is required for a complete rotation of a groove about the longitudinal axis of the mixing element.
- Mixing elements are further formed by the fact that kneading elements are made with breakthroughs in the kneading disks.
- Such mixing elements can be right- or left-handed.
- the pitch T of such mixing elements is preferably in the range of 0.1 times to 10 times the outer diameter.
- the axial length of a mixing element is carried out analogously to the kneading elements, preferably in integer multiples of T / Z.
- the openings preferably have the shape of a u- or v-shaped groove.
- the grooves of a mixing element are preferably arranged axially parallel or counter-promoting to the pitch of the underlying kneading element. Depending on the slope of the underlying kneading element and depending on the number, size, shape and slope of the
- Grooves may be a mixing element promoting active, promoting neutral or recirculating.
- the pitch of the grooves is understood to mean the axial length required for complete rotation of a groove about the longitudinal axis of the mixing element.
- Mixing elements are further formed from an alternating sequence of pitchless rings in which apertures are present (see, for example, [1], pages 227-248).
- Alternating means that with a pair of shafts, the rings alternate on the shafts in the axial direction.
- the outer diameter of the rings is preferably in the range of 0.9 times to 0.998 times the inner diameter of the housing.
- the openings preferably have the shape of a u- or v-shaped groove.
- the grooves of a mixing element are preferably arranged axially parallel, conveying or counter-conveying.
- the pitch of the grooves is understood to mean the axial length required for complete rotation of a groove about the longitudinal axis of the mixing element.
- Such mixing elements are known to the person skilled in the art as tooth blocks (ZB) or as tooth mixing elements (TME).
- the geometry of the conveying element, kneading element or block of teeth on which a mixing element is based is referred to as the basic geometry of the mixing element or, in short, only as the basis geometry.
- a basic geometry period length tb is understood to be the axial length of the smallest, geometric repeat unit of the conveying element, kneading element or tooth block underlying a mixing element.
- the base geometry period length tb is understood to mean the length for an alternation of the rings on a pair of shafts.
- FIG. 1 shows a classical tooth mixing element (ZME) according to DE 41 34 026 A1, whose number of basic geometry periods is equal to 3.75 and whose groove pitch is 3.20 times the outside diameter of the mixing element.
- the left image shows the side view, the right image shows an isometric view.
- FIG. 2 shows a variant according to the invention of a tooth mixing element whose number of basic geometry periods is equal to 5.63 and whose groove pitch is 3.20 times the outer diameter of the mixing element.
- the left image shows the side view, the right image shows an isometric view.
- FIG. 3 shows a variant of a tooth mixing element according to the invention whose number of basic geometry periods is equal to 7.51 and whose groove pitch is 3.20 times the outer diameter of the mixing element.
- the left image shows the side view, the right image shows an isometric view.
- FIG. 4 shows a variant of a tooth mixing element according to the invention whose number of basic geometry periods is equal to 7.51 and whose groove pitch is 6.39 times the outer diameter of the mixing element.
- the left image shows the side view, the right image shows an isometric view.
- FIG. 5 shows a variant of a tooth mixing element according to the invention whose number of basic geometry periods is equal to 7.51 and whose groove pitch is 7.99 times the outer diameter of the mixing element.
- the left image shows the side view, the right image shows an isometric view.
- FIG. 6 shows a variant of a tooth mixing element according to the invention whose number of basic geometry periods is equal to 7.51 and whose groove pitch is 9.59 times the outer diameter of the mixing element.
- the left image shows the side view, the right image shows an isometric view.
- FIG. 7 shows a variant of a tooth mixing element according to the invention whose number of basic geometry periods is equal to 7.51 and whose groove pitch is 3.20 times the outer diameter of the mixing element, the grooves extending to the core diameter.
- the left image shows the side view, the right image shows an isometric view.
- FIG. 8 shows a variant of a tooth mixing element according to the invention whose number of basic geometry periods is equal to 7.51 and whose groove pitch is 3.20 times the outer diameter of the mixing element.
- the left image shows the side view, the right image shows an isometric view.
- Figure 9 shows a pair of tooth mixing elements whose number of base geometry periods is equal to 7.51 and whose groove pitch is 7.99 times the outer diameter of the mixing element.
- the upper picture shows the side view of the pair of tooth mixing elements, the lower one
- FIG. 10 shows a pair of tooth mixing elements according to the invention whose number of base geometry periods is equal to 7.51 and whose groove pitch is 7.99 times the outer diameter of the mixing element.
- the upper picture shows the side view of the pair of tooth mixing elements, the lower picture shows the detail A enlarged.
- the Jardinäquidistante is used, which leads to an equal radial play s_r and axial play s_a between the two mixing elements.
- the radial play s_r and the axial play is the
- Tooth thickness mechanically stable enough for use in production.
- FIG. 11 shows the basic structure of a dispersion zone of a degassing extruder according to the invention.
- FIG. 12 shows the experimental setup of a plexiglass extruder.
- Figure 13 shows a mixing element of the TME type.
- FIG. 14 shows a pair of tooth mixing elements according to the invention in a housing of a twin-screw extruder.
- the number of basic geometry periods nb in an axial length corresponding in length to the outside diameter of the mixing elements is greater than or equal to 5.5, preferably greater than or equal to 7, and less than or equal to 10. It has been established in that, for a value of more than 10, the strength of the screw combs or the kneading disks is no longer sufficiently guaranteed.
- the mixing elements according to the invention as the basic geometry to a recirculating conveyor element with a catchy screw profile after
- the pitch of the active conveying grooves of the tooth mixing elements according to the invention is at least 7 times the outer diameter of the mixing elements, more preferably at least 9 times the outer diameter of the mixing elements.
- the tooth mixing elements may have any number of grooves. Preferably, the number of grooves is in the range of 6 to 20, more preferably 8 to 16.
- the grooves may be u- or v-shaped.
- the mixing elements according to the invention have as base geometry an alternating sequence of pitch-free rings in which openings are present.
- These mixing elements are known to the person skilled in the art as tooth blocks (ZB) or TME.
- the tooth blocks can have any number of openings. Preferably, the number of openings in the range of 6 to 20, more preferably 8 to 16.
- the openings are preferably in the form of a u- or v-shaped groove.
- the present invention furthermore relates to the use of the mixing elements according to the invention in a multi-screw extruder.
- the mixing elements according to the invention are preferably used in twin-screw extruders.
- the mixing elements according to the invention can be combined with other screw elements, in particular with conveying elements, kneading elements and / or mixing elements.
- the present invention furthermore relates to a screw extruder comprising two or more screw shafts which have the following sequence of screw elements as dispersion zone:
- the screw shafts comprise the following sequence of screw elements as dispersing zone:
- At least one recirculating screw element preferably recirculating conveyor elements or recirculating kneading elements
- the screw extruder may contain a plurality of dispersion zones comprising the aforementioned sequences (i) to (v).
- the screw extruder contains 1 to 8, more preferably 1 to 6, most preferably 1 to 4 of the dispersion zones.
- the dispersing zones serve to disperse an additive, preferably entrainer, as finely as possible in a polymer melt.
- screw elements (i), (ii), (iv) and (v) conveying elements kneading elements and / or mixing elements can be used.
- conveying elements or kneading elements are used as screw elements (i) and (v).
- screw elements (ii) and (iv) conveying elements are preferably used
- incorporation of one or more recirculating, pressure-consuming screw elements (ii) can prevent a gaseous additive to be dispersed, which is preferably introduced downstream of (ii), from being able to escape upstream.
- Use of one or more pressure-consuming screw element (s) (iv) can be used to set the pressure level in the partial area of the dispersion zone comprising the mixing elements (iii) according to the invention.
- the mixing elements (iii) have a smaller outer diameter than at least one of the screw elements (i) and (ii) and at least one of the screw elements (iv) and (v).
- An important operating variable of a screw extruder is the volume flow V (unit [m 3 / s]).
- V unit [m 3 / s]
- the dimensionless volumetric flow Q is calculated from the volumetric flow V divided by the product of extruder speed n (unit [1 / s]) and the cube of the housing internal diameter Dg (unit [m 3 ]).
- the dimensionless internal flow rate AI is understood to mean that dimensionless throughput achieved by a screw element when the screw element is completely filled with a plastic mass and the pressure gradient along the screw element is equal to zero. Screw elements can, depending on the geometry of the screw element, have a positive AI
- AI 0 or have a negative AI.
- Promotionally active conveying and kneading elements have a positive AI.
- Returning conveying and kneading elements have a negative AI.
- the internal flow rate AI mixing elements according to the invention is at most 0.8 times, more preferably at most 0.6 times the dimensionless volume flow Q. This has the advantage that the mixing elements according to the invention are sufficiently filled even with small malfunctions or at lower system utilization.
- Another object of the present invention is a process for the extrusion of plastic masses in a screw extruder according to the invention.
- plastic mass By a plastic mass is meant a deformable mass.
- plastic compositions are polymer melts, especially of thermoplastics and elastomers, mixtures of polymer melts or dispersions of polymer melts with solids, liquids or
- the mixing elements (iii) are preferably used for dispersing gaseous, liquid or pulverulent additives, more preferably gaseous entrainers, in the plastic mass.
- a particularly preferred entraining agent is nitrogen.
- Plastic compositions which can be extruded according to the invention with high efficiency with simultaneous product protection are, for example, suspensions, pastes, glass, ceramic compositions, metals in the form of a melt, plastics, plastic melts, polymer solutions, elastomer and rubber compositions.
- thermoplastic polymer used is preferably at least one of the series polycarbonate, polyamide, polyester, in particular polybutylene terephthalate and polyethylene terephthalate, polyether, thermoplastic polyurethane, polyacetal, fluoropolymer, in particular polyvinylidene fluoride, polyether sulfone, polyolefin, in particular polyethylene and polypropylene, polyimide , Polyacrylate, in particular poly (methyl) methacrylate, polyphenylene oxide, polyphenylene sulfide, polyether ketone, polyaryletherketone, styrene polymers, in particular polystyrene, styrene copolymers, in particular styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene block copolymers and polyvinyl chloride.
- the process according to the invention is particularly preferably used in the production and compounding of polycarbonate. Here, it offers advantages especially in the color of the polycarbonate, in non-colored polycarbonate measured with the yellowness index (YI).
- YI yellowness index
- polycarbonates can be prepared by the interfacial process or melt transesterification process. In both production processes, polycarbonates are obtained which have residual contents of monomers, oligomers and / or solvents.
- the method according to the invention is suitable for at least partially removing these volatile constituents.
- solvents such as aromatic chlorohydrocarbons such as chlorobenzene and dichloromethane are used whose residual contents in the end product are undesirable since they interfere with the polycarbonate. Due to the increased dispersing effect of the mixing elements (iii) according to the invention, the residual contents can be further reduced or thermal damage and decomposition products can be avoided by reducing the rotational speed of the extruder compared with prior art processes.
- An efficient concentration of the polycarbonate solution and evaporation of the residual contents of solvent under Prevention of thermal damage is of paramount importance to obtain polycarbonates with good optical properties.
- the phosgenation of a disodium salt of a bisphenol (or a mixture of different bisphenols) in aqueous alkaline solution (or suspension) is carried out in the presence of an inert organic solvent or solvent mixture which forms a second phase.
- the resulting, mainly present in the organic phase oligocarbonates are condensed with the aid of suitable catalysts to high molecular weight, dissolved in the organic phase polycarbonates.
- the organic phase is finally separated and washed in a multi-step process to remove residuals of sodium and catalyst.
- the organic phase after the reaction contains 10-20 wt% polycarbonate.
- the polycarbonate must then be isolated from the organic phase.
- the conventional methods for concentrating the polycarbonate solution and for isolating the polycarbonate are described in the patent literature and in textbooks and are familiar to the person skilled in the art.
- the isolation of the polycarbonate from the solution is preferably carried out by evaporating the solvent by means of temperature or vacuum.
- a high-boiling (> 100 ° C.) solvent for example chlorobenzene.
- a mixture of one or more high-boiling solvents and the low-boiling dichloromethane is also used.
- the weight ratio of dichloromethane to the high boiling solvent is about 1: 1.
- Residual contents of diphenyl carbonate are, for example, in the range of 200 to 700 ppm. These substances also have a disturbing effect. During processing, such as injection molding and extrusion, they are partially released by the processor, where they lead to odor nuisance and environmental pollution. Furthermore, they can lead to deposits during injection molding and thus reduced service life. They can also pass from the polycarbonate into the food when it comes into contact with food, where it can lead to changes in the taste. Especially sensitive to changes in taste is water. Especially phenols tend to form halogenated phenols when polycarbonate food containers come into contact with chlorine-active agents or strong oxidizing agents in the presence of chlorine or bromine ions during cleaning and / or disinfection.
- polycarbonate Another possibility for producing polycarbonate consists in the phosgenation of bisphenols in the presence of pyridine or mixtures of pyridine and chlorobenzene, as described, for example, in US Pat. No. 3,114,432. Polycarbonates containing pyridine are completely unsuitable for food applications because of the intense unpleasant odor.
- Halogenated solvents show similarly low sensory thresholds as phenols and their halogenated derivatives. Although they have lower solubilities and migrate slower due to their lower diffusion constants, but depending on the conditions in water and thus cause changes in taste. In taste tests, subjects have already noticed taste changes at chlorobenzene levels in the water of 1 ppb. To safely exclude such a change in taste, a residual content of residual chlorobenzene in drinking water bottles made of polycarbonate of less than 10 ppm is required. Another possibility for the production of polycarbonate consists in the reaction in the phase interface with subsequent isolation of the polycarbonate from the organic solvent by injection of a heated gas, especially water vapor, to expel the volatile constituents.
- the polycarbonate solution is sprayed with the carrier gas, and polycarbonate precipitates as a solid, especially as a water-moist suspension.
- Other isolation methods are the crystallization and precipitation as well as the heating of the residues of the solvent in the solid Phase.
- the latter method requires the use of dichloromethane as a solvent.
- dichloromethane as a solvent.
- residual contents of dichloromethane interfere particularly in the polycarbonate, since dichloromethane, as is known, splits off hydrochloric acid together with residual moisture during the processing process and can thus lead to discoloration of the polycarbonate and corrosion of tools.
- dichloromethane can also lead to loss of quality, such as discoloration, during the work-up process
- Another method is the isolation of polycarbonate from solution by injecting vapors of aromatic, non-chlorinated aromatic compounds such as benzene, toluene, ethylbenzene or various xylenes in a polycarbonate solution in dichloromethane with subsequent solidification and drying, such as in DE 3 429 960 described. Residual contents of aromatic compounds can also have a taste-changing effect.
- a method for the safe removal of carbon tetrachloride and dichloromethane does not teach DE 3 429 960.
- a significant disadvantage of this method is evident in the industrial implementation. For reasons of economic efficiency and environmental protection, it is absolutely necessary to close the material cycle. Above all, the aromatics used must be returned to the process after removal from the polycarbonate.
- Low molecular weight constituents of the polycarbonate such as, for example, thermally unstable bisphenols
- bisphenols are converted to colored, especially yellow, compounds under temperature load. These colored compounds accumulate in the circulation, so that they lead to continuous deterioration of the colors of the produced polycarbonate in continuous operation.
- Residual contents of high-boiling solvents such as aromatic hydrocarbons and chlorinated hydrocarbons also have a disturbing effect.
- processing such as injection molding and extrusion, they are partially released from the processor and lead to odor nuisance and environmental pollution.
- polycarbonate solutions are repeatedly heated under slight overpressure to temperatures above the boiling point and then these superheated solutions are expanded into a container, wherein the container is at a lower pressure than the vapor pressure in the solution.
- the repetition of the process is generally favorable, since the concentration of polycarbonate in the solution after the reaction is relatively low and by repeating the process a strong overheating can be avoided.
- Common processes for the apparatus evaporation of polycarbonate solutions are familiar to the expert. For example, the superheated solution can be relaxed in a heated spiral tube, which opens into a separator.
- the screw extruder according to the invention can be used.
- an entrainer is preferably used to increase the degassing surface.
- an entrainment agent is used, according to the invention it is preferably supplied in the region of the mixing elements (iii) and dispersed by them in the polymer melt.
- entrainer nitrogen can preferably be used.
- the supplied entrainer volume flow should preferably be 0.05 mass to 0.3 mass.
- additives are premixed in a stream of polycarbonate, more preferably one
- Other preferred feedstocks are rubbers.
- the rubber at least one of styrene-butadiene rubber, natural rubber, butadiene rubber, isoprene rubber, ethylene-propylene-diene rubber, ethylene-propylene rubber, butadiene-acrylonitrile rubber, hydrogenated nitrile rubber, butyl rubber is preferably used.
- a combination of two or more of listed rubbers, or a combination of one or more rubber with one or more plastics is of course also possible.
- thermoplastics and elastomers can be used in pure form or as mixtures with fillers and reinforcing materials, in particular glass fibers, as mixtures with one another or with other polymers, or as mixtures with customary polymer additives
- additives are added to the plastic compositions, in particular the polymer melts and mixtures of polymer melts. These may be added to the extruder as solids, liquids or solutions together with the polymer, or at least some or all of the additives may be fed to the extruder via a side stream.
- Additives can impart a variety of properties to a polymer. These may include, for example, colorants, pigments, processing aids, fillers, antioxidants, reinforcing agents, UV absorbers and light stabilizers, metal deactivators, peroxide scavengers, basic stabilizers, nucleating agents, benzofurans and indolinones effective as stabilizers or antioxidants, mold release agents, flame retardant additives, antistatic agents, colorants and melt stabilizers , Exemplary of these are carbon black, glass fiber, clay, mica, graphite fiber, titanium dioxide, carbon fibers, carbon nanotubes, ionic liquids and natural fibers.
- the plastic materials supplied to the screw extruder contain monomers, oligomers and / or solvents which are at least partially removed by the process according to the invention.
- a gaseous entraining agent is dispersed in the plastic mass.
- the entrainer is removed in a later step by applying vacuum again.
- FIGS. 1 to 10 were generated by means of a computer program.
- dimensionless geometric sizes are formed for the outer diameter, core diameter, and screw clearance.
- the housing inner diameter Dg is used because this size is not changed on an extruder.
- the dimensionless quantities are specified to 3 decimal places, as well as the base geometry period length.
- the number of base geometry periods is specified to 2 decimal places.
- FIG. 1 describes a tooth mixing element according to the prior art with the teeth (1), the grooves (2), the helix thread (3), the internal toothing (4), the base geometry length tb and the outside diameter Da.
- the dimensionless outer diameter at the tips of the teeth (1) is 0.966.
- the dimensionless core diameter at the bottom of the flight (3) is 0.647.
- the dimensionless screw clearance is 0.017.
- the base geometry period length tb is 0.266 times the outer diameter of the tooth mixing element.
- the number of grooves (2) is 12 and the pitch of the grooves is 3.20 times the outer diameter of the tooth mixing element.
- Figure 2 describes a novel tooth mixing element with the teeth (1), the grooves (2), the
- the dimensionless outer diameter at the tips of the teeth (1) is 0.966.
- the dimensionless core diameter at the bottom of the flight (3) is 0.647.
- the dimensionless screw clearance is 0.017.
- the slope of the base geometry is 0.178 times the outer diameter of the tooth mixing element.
- the number of grooves (2) is 12 and the pitch of the grooves is 3.20 times the outer diameter of the tooth mixing element.
- FIG. 3 describes a novel tooth mixing element with the teeth (1), the grooves (2), the helix thread (3), the internal toothing (4), the base geometry length tb and the outside diameter Da.
- the dimensionless outer diameter at the tips of the teeth (1) is 0.966.
- the dimensionless core diameter at the bottom of the flight (3) is 0.664.
- the dimensionless screw clearance is 0.009.
- the slope of the base geometry is 0.133 times the outer diameter of the tooth mixing element.
- the number of grooves (2) is 12 and the pitch of the grooves is 3.20 times the outer diameter of the tooth mixing element.
- FIG. 4 describes a novel tooth mixing element with the teeth (1), the grooves (2), the helical thread (3), the internal toothing (4) and the base geometry length tb.
- the dimensionless outer diameter at the tips of the teeth (1) is 0.966.
- the dimensionless core diameter at the bottom of the flight (3) is 0.664.
- the dimensionless screw clearance is 0.009.
- the slope of the base geometry is 0.133 times the outside diameter of the tooth mixing element.
- the number of grooves (2) is 12 and the pitch of the grooves is 6.39 times the outer diameter of the tooth mixing element.
- FIG. 5 describes a novel tooth mixing element with the teeth (1), the grooves (2), the helical thread (3), the internal toothing (4) and the base geometry length tb.
- Outer diameter at the tips of the teeth (1) is 0.966.
- the dimensionless core diameter at the bottom of the flight (3) is 0.664.
- the dimensionless screw clearance is 0.009.
- the slope of the base geometry is 0.133 times the outside diameter of the tooth mixing element.
- the number of grooves (2) is 12 and the pitch of the grooves is 7.99 times the outer diameter of the tooth mixing element.
- FIG. 6 describes a novel dental teaching element with the teeth (1), the grooves (2), the helix thread (3), the internal toothing (4) and the base geometry length tb.
- the dimensionless outer diameter at the tips of the teeth (1) is 0.966.
- the dimensionless core diameter at the bottom of the flight (3) is 0.664.
- the dimensionless screw clearance is 0.009.
- the slope of the base geometry is 0.133 times the outside diameter of the tooth mixing element.
- the number of grooves (2) is 12
- FIG. 7 describes a novel dental kidney element with the teeth (1), the grooves (2), the helix thread (3), the internal toothing (4) and the base geometry length tb.
- Outer diameter at the tips of the teeth (1) is 0.966.
- the dimensionless core diameter at the bottom of the flight (3) is 0.664.
- the dimensionless screw clearance is 0.009.
- the slope of the base geometry is 0.133 times the outside diameter of the tooth mixing element.
- the number of grooves (2) is 12, the pitch of the grooves is 3.2 times the outer diameter of the tooth mixing element and the grooves extend down to the core diameter.
- FIG. 8 describes a novel dental teaching element with the teeth (1), the grooves (2), the helix thread (3), the internal toothing (4) and the base geometry length tb.
- the dimensionless outer diameter at the tips of the teeth (1) is 0.991.
- the dimensionless core diameter at the bottom of the flight (3) is 0.638.
- the dimensionless screw clearance is 0.009.
- the slope of the base geometry is 0.133 times the outside diameter of the tooth mixing element.
- the number of grooves (2) is 12 and the pitch of the grooves is 3.2 times the outer diameter of the tooth mixing element.
- the games can be different or equal in size between the worm and the housing and between the worm and the worm.
- the games can also be constant or, within the specified limits, variable. It is also possible to move a snail profile within the games. Possible
- Play strategies are the possibility of the axial distance magnification described in [1] on pages 28 ff, the longitudinal section equidistants and the space equidistants, all of which are known to the person skilled in the art.
- a smaller diameter screw profile is constructed and spaced apart by the amount of play between the screws.
- the longitudinal section profile curve (parallel to the axis) is shifted inwards by half the play of the worm screw.
- the Blending element in the direction perpendicular to the surfaces of the exact abschabenden profile to the game between worm and auger increases.
- the longitudinal section equidistant or the spatial equidistant particularly preferably the spatial equidistant, is used.
- FIG. 9 describes a pair of tooth mixing elements.
- the dimensionless outer diameter at the tips of the teeth (1) is 0.966.
- Worm gear (3) is 0.664.
- the dimensionless screw clearance is 0.009.
- the slope of the base geometry is 0.133 times the outside diameter of the tooth mixing element.
- the number of grooves (2) is 12 and the pitch of the grooves is 7.99 times the outside diameter of the tooth mixing element.
- the axial distance magnification is used.
- the radial clearance s_r is 0.009 times the outer diameter of the tooth mixing element. It can be seen that the radial clearance between the screws is much greater than the axial play.
- FIG. 10 describes a pair of tooth mixing elements according to the invention.
- the dimensionless outer diameter at the tips of the teeth (1) is 0.966.
- the dimensionless core diameter at the bottom of the flight (3) is 0.664.
- the dimensionless screw clearance is 0.009.
- the slope of the base geometry is 0.133 times the outside diameter of the tooth mixing element.
- the number of grooves (2) is 12 and the pitch of the grooves is 7.99 times the outer diameter of the tooth mixing element.
- the space equidistant is used.
- the radial clearance s_r and the axial play s_a is 0.009 times the outer diameter of the tooth mixing element. It can be seen that the radial play and the axial clearance between the screws is practically the same size.
- the longitudinal section equidistant particularly preferably the spatial equidistant, is preferably used for the tooth mixing elements according to the invention.
- FIG. 11 describes a typical dispersion zone of a degassing extruder.
- a dispersing zone consists essentially of 5 zones ZI to Z5.
- Zone ZI which consists of one or more conveying active conveying elements, is supplied with polymers, monomers and solvents.
- the task of the zone ZI is to build up the necessary pressure for driving over the zones Z2 to Z4.
- the zone Z2 consists of one or more pressure-consuming screw elements, preferably one or more neutral or back-conveying kneading elements, particularly preferably one or more return-conveying conveying elements.
- the pressure consumption in the zone Z2 prevents entraining agent, which is supplied in the zone Z3, from being able to escape upstream.
- Zone Z3 consists of one or more dispersing screw elements, preferably one or more kneading and mixing elements, and more preferably one or more tooth mixing elements.
- the task of the dispersing zone is to disperse the entrainers as finely as possible.
- Zone Z4 consists of one or more pressurized r screw element, preferably from one or more neutral or back-conveying kneading elements, particularly preferably from one or more recirculating conveying elements.
- Zone Z4 has the task of setting the pressure in dispersion zone Z3 to a desired pressure level.
- the last zone Z5 is a partially filled degassing zone in which the monomers and solvents, with the aid of the entraining agent, pass through a degassing dome
- Extruders are discharged while the polymer is transported downstream in the extruder.
- the zone Z5 consists of one or more actively conveying screw elements, preferably one or more conveying active conveying elements.
- the dispersion of gases is preferably carried out under high pressure, so that the entraining agent dissolves better in the polymer and thus in a subsequent degassing zone better foaming (larger surface area) is possible.
- FIG. 12 describes a plexiglass twin-screw extruder in which experiments can be carried out for visually assessing the gas-dispersing efficiency of various mixing elements.
- the housing inside diameter of the plexiglas extruder is 58.3 mm, the center distance between the two shafts is 48 mm.
- silicone oil is used in these experiments since silicone oil has a Newtonian flow behavior at room temperature, such as polycarbonate, at 300-350 ° C. From a template BAI silicone oil is pumped with a viscosity of 10 Pas at room temperature by means of a gear pump PAl into the extruder. At the beginning of the dispersing screw elements, nitrogen is metered into the extruder whose mass flow is measured via the measuring point F1.
- the pressure in the extruder can be adjusted. After the valve VI, the silicone oil is collected in a discharge barrel. The extruder is driven by the motor M and the extruder speed Sl is measured. Furthermore, the pressures PI and P2 at the inlet and the outlet and the temperatures Tl and T2 at the inlet and the outlet are measured. The mass flow F2 of silicone oil is detected by a balance.
- the Schneckenbesatz for the dispersing experiments consists in a first zone ZI from promoting active conveyor elements with a pitch of 60 mm, in a second zone Z2 of back-conveying conveyor elements with a pitch of 60 mm and a length of 30 mm, in a third Z3 from the dispersing screw elements and in a fourth zone Z4 of spacers.
- FIG. 13 shows a TME-type mixing element according to the prior art with the rings (5), the teeth (1), the grooves (2), the flight (3), the internal gear (4), the base geometry length tb and the Outer diameter Da.
- Figure 14 describes a pair of novel tooth mixing elements (6) having the outer diameter Da, the core diameter (7), the teeth (1), the grooves (2), the internal teeth (4) in a housing (8) of a twin-screw extruder with a housing inner diameter dg.
- the center distance between the two tooth mixing elements is equal to A.
- the number of grooves (2) is 12.
- Example 1 As dispersing screw elements, mixing elements with a double-flighted conveying-active conveying element were used as basic geometry and return-promoting grooves according to the prior art. These mixing elements are also known to the person skilled in the art as screw mixing elements (SME). The outside diameter at the tips of the teeth was 56.6 mm for one axial
- the basic geometry period length tb was 30 mm.
- the number of grooves was 8 and the pitch of the grooves was 120 mm corresponding to 2.12 times the outer diameter of the tooth mixing element.
- the center distance magnification was used.
- the pressure at the measuring point PI was 5.5 bar absolute.
- the speed of the extruder was 18 revolutions per minute.
- the mass flow of silicone oil was 22 kg / h. 10 NL / h (standard liters / h) of nitrogen were metered. The nitrogen was metered in via a metering point.
- the metered nitrogen was already distributed over the entire cross section at the metering point, since undesirably the nitrogen was partly conveyed backwards in accordance with the pressure gradient of a conveying-active screw mixing element. After an axial length of about 120 mm, elongated gas bubbles with a diameter of greater than 10 mm were frequently present.
- Example 2 Dental mixing elements according to the prior art were used as dispersing screw elements.
- the outer diameter at the tips of the teeth was 56.3 mm for an axial length of 150 mm.
- the base geometry period length tb was 15 mm.
- the number of grooves was 12 and the pitch of the grooves was 180 mm corresponding to 3.20 times the outer diameter of the tooth mixing element.
- the center distance magnification was used.
- the pressure at the measuring point PI was 5.5 bar absolute.
- the speed of the extruder was 18 revolutions per minute.
- the mass flow of silicone oil was 18 kg / h. 10 NL / h (standard liters / h) of nitrogen were metered.
- the nitrogen was metered in via two metering points, namely in the direction of rotation of the two shafts, each about 45 ° in front of the gusset.
- the metered nitrogen was predistributed in an axial length of about 60 mm. After an axial length of about 120 mm, elongated gas bubbles with a diameter of about 5 mm were frequently present.
- Example 3 Dental mixer elements according to the invention were used as dispersing screw elements.
- the outer diameter at the tips of the teeth was 57.8 mm for an axial length of 60 mm, then the outer diameter was 56.3 mm for an axial length of 90 mm.
- the basic geometry period length tb was 10 mm.
- the number of grooves was 12 and the pitch of the grooves was 180 mm corresponding to 3.11 times and 3.20 times the outer diameter of the tooth mixing element, respectively.
- the room equidistant was used as the game strategy.
- the pressure at the measuring point PI was 5.5 bar absolute.
- the speed of the extruder was 18 revolutions per minute.
- the mass flow of silicone oil was 18 kg / h. 10 NL / h (standard liters / h) of nitrogen were metered. The nitrogen was metered in via two metering points, namely in the direction of rotation of the two shafts, each about 45 ° in front of the gusset. The metered nitrogen was predistributed in an axial length of about 30 mm. After an axial length of about 120 mm, elongated gas bubbles with a diameter of about 3 mm were frequently present. EXAMPLE 4 Dental mixer elements according to the invention were used as dispersing screw elements.
- the outer diameter at the tips of the teeth was 57.8 mm for an axial length of 60 mm, then the outer diameter was 56.3 mm for an axial length of 90 mm.
- the base geometry period length tb was 7.5 mm.
- the number of grooves was 12 and the pitch of the grooves was 180 mm corresponding to 3.11 times and 3.20 times the outer diameter of the tooth mixing element, respectively.
- the room equidistant was used as the game strategy.
- the pressure at the measuring point PI was 5.5 bar absolute.
- the speed of the extruder was 18 revolutions per minute.
- the mass flow of silicone oil was 18 kg / h.
- Example 5 Dental mixing elements according to the invention were used as dispersing screw elements.
- the outer diameter at the tips of the teeth was 57.8 mm for an axial length of 60 mm, then the outer diameter was 56.3 mm for an axial length of 90 mm.
- the base geometry period length tb was 7.5 mm.
- the number of grooves was 12 and the pitch of the grooves was 450 mm, corresponding to 7.79 times and 7.99 times the outer diameter of the tooth mixing element, respectively.
- the room equidistant was used as the game strategy.
- the pressure at the measuring point PI was 5.5 bar absolute.
- the speed of the extruder was 18 revolutions per minute. Of the
- Mass flow of silicone oil was 18 kg / h. 10 NL / h (standard liters / h) of nitrogen were metered. The nitrogen was metered in via two metering points, namely in the direction of rotation of the two shafts, each about 45 ° in front of the gusset. The metered nitrogen was predistributed in an axial length of about 30 mm. After an axial length of about 120 mm, elongated gas bubbles with a diameter of about 2.5 mm were frequently present.
- the dimensionless natural flow rate AI of different tooth mixing elements was calculated by means of the flow simulation. It was the commercial software package Ansys Fluent version 13.0 used.
- the dimensionless outer diameter at the tips of the teeth was 0.983.
- the dimensionless core diameter at the bottom of the screw flight was 0.627.
- the dimensionless screw clearance was 0.011.
- the slope of the base geometry was 0.132 times the outer diameter of the tooth mixing element.
- the room equidistant was used as the game strategy.
- the number of grooves was 12.
- the pitch of the grooves was varied.
- the pitch of the grooves was 5.42 times the outer diameter of the tooth mixing element.
- the pitch of the grooves was 5.69 times the outer diameter of the tooth mixing element.
- the pitch of the grooves was 9.49 times the outside diameter of the tooth mixing element.
- the energy requirement when flowing through the various tooth mixing elements remains practically constant. It differs a maximum of 1%.
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Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP14176663.4A EP2965889A1 (de) | 2014-07-11 | 2014-07-11 | Mischelemente mit verbesserter Dispergierwirkung |
| PCT/EP2015/065706 WO2016005499A1 (de) | 2014-07-11 | 2015-07-09 | Mischelemente mit verbesserter dispergierwirkung |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP3166771A1 true EP3166771A1 (de) | 2017-05-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| EP14176663.4A Ceased EP2965889A1 (de) | 2014-07-11 | 2014-07-11 | Mischelemente mit verbesserter Dispergierwirkung |
| EP15736480.3A Withdrawn EP3166771A1 (de) | 2014-07-11 | 2015-07-09 | Mischelemente mit verbesserter dispergierwirkung |
| EP15736479.5A Active EP3166770B1 (de) | 2014-07-11 | 2015-07-09 | Mischelemente mit verbesserter dispergierwirkung |
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| Application Number | Title | Priority Date | Filing Date |
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| EP14176663.4A Ceased EP2965889A1 (de) | 2014-07-11 | 2014-07-11 | Mischelemente mit verbesserter Dispergierwirkung |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP15736479.5A Active EP3166770B1 (de) | 2014-07-11 | 2015-07-09 | Mischelemente mit verbesserter dispergierwirkung |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US10207424B2 (de) |
| EP (3) | EP2965889A1 (de) |
| JP (2) | JP6633048B2 (de) |
| CN (2) | CN106660251B (de) |
| WO (2) | WO2016005499A1 (de) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019121248A1 (de) | 2017-12-18 | 2019-06-27 | Covestro Deutschland Ag | Verfahren zur herstellung eines polycarbonats unter verwendung eines organischen lösungsmittels auf der grundlage von chlorkohlenwasserstoffen |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2965889A1 (de) * | 2014-07-11 | 2016-01-13 | Covestro Deutschland AG | Mischelemente mit verbesserter Dispergierwirkung |
| KR101993783B1 (ko) * | 2016-01-20 | 2019-06-28 | 주식회사 엘지화학 | 카본나노튜브 펠렛 제조장치 |
| WO2019070797A1 (en) * | 2017-10-05 | 2019-04-11 | Corning Incorporated | SCREW ELEMENTS FOR EXTRUSION APPARATUS AND METHODS OF MANUFACTURING HONEYCOMB BODY |
| CN109760333B (zh) * | 2017-11-09 | 2021-04-20 | 四川大学 | 挤出发泡装置用螺杆以及挤出发泡装置 |
| USD929799S1 (en) * | 2018-05-04 | 2021-09-07 | Buss Ag | Screw shaft element |
| USD961990S1 (en) * | 2018-05-04 | 2022-08-30 | Buss Ag | Screw shaft element |
| EP3659773B1 (de) * | 2018-11-30 | 2023-06-07 | Coperion GmbH | Verfahren und vorrichtung zur aufbereitung einer styrol-acrylnitril-schmelze |
| CN109693350B (zh) * | 2019-03-07 | 2021-10-08 | 广州一道注塑机械股份有限公司 | 用于金属粉末熔料注射的螺杆组件、料筒及注塑机 |
| JP2021041687A (ja) * | 2019-09-09 | 2021-03-18 | ダインス カンパニー リミテッドDAINS Co.,Ltd. | 遮蔽素材の製造装置 |
| CN111823523B (zh) * | 2020-07-13 | 2022-12-13 | 青岛科技大学 | 一种强化传热与混炼的竹节式返混螺杆 |
| US12514311B1 (en) | 2021-09-28 | 2026-01-06 | Austin Caldwell | Glove with deployable knife |
| DE102023203382A1 (de) * | 2023-04-13 | 2024-10-17 | Coperion Gmbh | Vorrichtung und Verfahren zur Herstellung einer Folie für elektrische Energiespeicher |
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- 2014-07-11 EP EP14176663.4A patent/EP2965889A1/de not_active Ceased
-
2015
- 2015-07-09 US US15/325,579 patent/US10207424B2/en active Active
- 2015-07-09 EP EP15736480.3A patent/EP3166771A1/de not_active Withdrawn
- 2015-07-09 WO PCT/EP2015/065706 patent/WO2016005499A1/de not_active Ceased
- 2015-07-09 US US15/329,430 patent/US20170210030A1/en not_active Abandoned
- 2015-07-09 JP JP2017501245A patent/JP6633048B2/ja not_active Expired - Fee Related
- 2015-07-09 JP JP2017501255A patent/JP6644761B2/ja active Active
- 2015-07-09 CN CN201580037703.4A patent/CN106660251B/zh not_active Expired - Fee Related
- 2015-07-09 EP EP15736479.5A patent/EP3166770B1/de active Active
- 2015-07-09 WO PCT/EP2015/065705 patent/WO2016005498A1/de not_active Ceased
- 2015-07-09 CN CN201580037729.9A patent/CN106470818B/zh active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2965889A1 (de) | 2016-01-13 |
| US20170136426A1 (en) | 2017-05-18 |
| CN106470818A (zh) | 2017-03-01 |
| JP6644761B2 (ja) | 2020-02-12 |
| JP2017524568A (ja) | 2017-08-31 |
| WO2016005499A1 (de) | 2016-01-14 |
| EP3166770A1 (de) | 2017-05-17 |
| JP2017519667A (ja) | 2017-07-20 |
| WO2016005498A1 (de) | 2016-01-14 |
| CN106470818B (zh) | 2020-01-07 |
| CN106660251B (zh) | 2020-01-17 |
| JP6633048B2 (ja) | 2020-01-22 |
| EP3166770B1 (de) | 2020-04-08 |
| US20170210030A1 (en) | 2017-07-27 |
| CN106660251A (zh) | 2017-05-10 |
| US10207424B2 (en) | 2019-02-19 |
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