WO2020120119A1 - Procédé de préparation d'une matière à mouler dotée de propriétés ameliorées - Google Patents

Procédé de préparation d'une matière à mouler dotée de propriétés ameliorées Download PDF

Info

Publication number
WO2020120119A1
WO2020120119A1 PCT/EP2019/082498 EP2019082498W WO2020120119A1 WO 2020120119 A1 WO2020120119 A1 WO 2020120119A1 EP 2019082498 W EP2019082498 W EP 2019082498W WO 2020120119 A1 WO2020120119 A1 WO 2020120119A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
polycarbonate
molding composition
continuous single
reinforcing filler
Prior art date
Application number
PCT/EP2019/082498
Other languages
German (de)
English (en)
Inventor
Michael Erkelenz
Reiner Rudolf
Hans-Jürgen THIEM
Original Assignee
Covestro Intellectual Property Gmbh & Co. Kg
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro Intellectual Property Gmbh & Co. Kg filed Critical Covestro Intellectual Property Gmbh & Co. Kg
Publication of WO2020120119A1 publication Critical patent/WO2020120119A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • B29B7/002—Methods
    • B29B7/007—Methods for continuous mixing
    • 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
    • B29B7/40—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft
    • B29B7/42—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft with screw or helix
    • 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
    • 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
    • B29B7/726—Measuring properties of mixture, e.g. temperature or density
    • 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
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • 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
    • 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
    • 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
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • 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
    • B29C48/285—Feeding the extrusion material to the extruder
    • B29C48/297—Feeding the extrusion material to the extruder at several locations, e.g. using several hoppers or using a separate additive feeding
    • 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
    • B29C48/397—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 a single screw
    • 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
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
    • 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
    • B29C48/765—Venting, drying means; Degassing means in the extruder apparatus
    • B29C48/766—Venting, drying means; Degassing means in the extruder apparatus in screw extruders
    • B29C48/767—Venting, drying means; Degassing means in the extruder apparatus in screw extruders through a degassing opening of a barrel
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/267—Magnesium carbonate

Definitions

  • the present invention relates to a method for producing a molding composition with improved properties.
  • the present invention relates to the production of a molding composition containing a polycarbonate and a reinforcing filler, preferably selected from one or more members of the group comprising the members titanium dioxide (T1O2), talc (MgsSfiOioCOHJ), dolomite CaMg [C03] 2, kaolinite ALtKOH ⁇ ISfiOio ] and wollastonite CasfS OJ, preferably selected from one or more members of the group comprising the members titanium dioxide (T1O2) and talc (MgsSfiOioCOHJ).
  • the content of reinforcing filler is 3 to 40% by weight, preferably 10 to 35% by weight, particularly preferably 12 to 32% by weight, very particularly preferably 15 to 30% by weight, in each case based on the total mass of Molding compound.
  • this molding composition is obtainable by compounding a polycarbonate and the reinforcing filler by means of a continuous single-shaft kneader.
  • the method according to the invention has the following steps:
  • polycarbonate, reinforcing filler and, if appropriate, other constituents can be added to the continuous single-shaft kneader simultaneously or in succession.
  • the reinforcing filler can be added either before the polycarbonate has melted or after the polycarbonate has melted, or both before and after the polycarbonate has melted.
  • the content of polycarbonate in the molding composition according to the invention is 97 to 60% by weight, preferably 90 to 65% by weight, particularly preferably 88 to 68% by weight, very particularly preferably 85 to 70% by weight. %, each based on the total mass of the molding compound.
  • the molding composition may also contain other ingredients.
  • the content of the other ingredients in the molding composition containing a polycarbonate and a reinforcing filler is from 0 to 37% by weight, preferably from 0 to 20% by weight, particularly preferably 0 to 10% by weight, in each case based on the total mass of the molding composition .
  • the sum of all components of the molding composition is 100% by weight.
  • a molding composition containing a polycarbonate is also called a polycarbonate molding composition below.
  • [1] Klemens Kohlgrüber: The co-rotating twin-screw extruder, 2nd, revised and expanded edition, Hanser Verlag Kunststoff 2016, p. 47 ff)
  • polymer molding compounds such as A molding composition containing a polycarbonate is also one of these polymer molding compositions, by admixing additives, for example fillers, in such a way that these polymer molding compositions achieve a desired profile of properties.
  • This preparation also called compounding, is usually carried out in a twin-screw extruder.
  • Improved dispersion of fillers in a polymer molding composition also has the effect, inter alia, that the molding composition has improved properties, in particular improved surface properties and improved mechanical properties such as e.g. has a higher toughness, a higher force absorption and greater elongation during the puncture test.
  • Length of the twin-screw extruder increases, which corresponds to four times the outer diameter of a screw element that cleans the inner wall of the twin-screw extruder.
  • the object of the present invention is therefore to provide a method for producing an improved polycarbonate molding composition containing a reinforcing filler.
  • polycarbonate molding composition according to the invention should improve the following
  • a process for producing a molding composition comprising a polycarbonate and a reinforcing filler, preferably selected from one or more members of the group comprising the members titanium dioxide (T1O2) talc (Mg3SiiOio (OH) 2), dolomite CaMg [C03] 2, kaolinite AL [(OH) g
  • the content of reinforcing filler is 3 to 40% by weight, preferably 10 to 35% by weight, particularly preferably 12 to 32% by weight, particularly preferably 15 to 30% by weight, in each case based on the total mass of the polycarbonate molding composition.
  • Improved polycarbonate molding compositions are obtained with the process according to the invention. This solution of the task is particularly surprising because continuous single-screw kneaders have so far not been used for a particular dispersive mixer Mixing effect were known, that is, when using a significantly improved dispersion and the resulting improvements were not expected.
  • a reinforcing filler is understood to be a mineral filler which is suitable for increasing the rigidity of the polycarbonate molding composition produced according to the invention.
  • the process according to the invention gives polycarbonate molding compositions which have the following improved properties:
  • improved surface properties in particular fewer impurities, in particular fewer impurities in the form of elevations or depressions in the surface, caused by incompletely dispersed reinforcing filler particles.
  • Incompletely dispersed reinforcing filler particles can be determined, for example, by visual analysis of images of molded articles produced from the molding composition according to the invention; the particle size distribution of the incompletely dispersed reinforcing filler particles can be assessed using a classification;
  • Such a polycarbonate molding composition produced in accordance with the invention has better, that is to say improved, properties than polycarbonate molding compositions which have been produced by processes according to the prior art, the polycarbonate molding compositions which have been produced according to the prior art having the same constituents in the same proportions as the polycarbonate molding composition produced according to the invention.
  • the term “molded body” is understood to mean an object which is the result of further processing of the molding composition.
  • both an object obtainable from the molding compound by injection molding and a film or plate obtainable by extrusion of the molding compound are to be regarded as molded articles.
  • the modification rutile with a grain size dso of 0.1 mhi to 5 pm, preferably 0.3 to 3 pm, is preferably used as titanium dioxide (T1O2).
  • titanium dioxide which can be used according to the invention are selected from the products titanium dioxide Kronos 2230 and titanium dioxide Kronos 2233; Kronos Titan GmbH Leverkusen is the manufacturer of both products.
  • Talc (Mg3SiiOio (OH) 2) is preferably used with a grain size dso of 0.1 mhi to 10 pm, preferably 0.3 to 3 mhi.
  • talc the commercially available products Jetfine 3CA from Imerys Tale (Luzenac Europe SAS) or talc HTP Ultra 5C from IMI Fabi S.p.A. be used.
  • the grain size dso is mass-related in each case and was determined in accordance with ISO 1333 17-3 with a Sedigraph 5100 from Micrometrics, Germany.
  • Mixtures of titanium dioxide and talc can be used in any mixing ratio.
  • the mixing ratio of titanium dioxide to talc is preferably 1:60 to 1: 1, preferably 1:30 to 1: 5, in each case based on the mass.
  • the particles of the respective mineral from which the reinforcing filler is made preferably have an aspect ratio of 1: 1 to 1: 7.
  • polycarbonate means both homopolycarbonates and copolycarbonates.
  • the polycarbonates can be linear or branched in a known manner. Mixtures of polycarbonates can also be used according to the invention.
  • Some, up to 80 mol%, preferably from 20 mol% to 50 mol%, of the carbonate groups in the polycarbonates used according to the invention can be replaced by preferably aromatic dicarboxylic acid ester groups.
  • Such polycarbonates which contain both acid residues of carbonic acid and acid residues of, preferably aromatic, dicarboxylic acids incorporated into the molecular chain, are referred to as aromatic polyester carbonates.
  • the carbonate groups are replaced by the aromatic dicarboxylic acid ester groups essentially stoichiometrically and also quantitatively, so that the molar ratio of the reactants is also found in the finished polyester carbonate.
  • the aromatic dicarboxylic acid ester groups can be incorporated either statistically or in blocks.
  • thermoplastic polycarbonates including the thermoplastic polyester carbonates, have average molecular weights Mw determined by GPC (gel permeation chromatography in Methylene chloride with polycarbonate as standard) from 15 kg / mol to 50 kg / mol, preferably from 20 kg / mol to 35 kg / mol, particularly preferably from 23 kg / mol to 33 kg / mol.
  • GPC gel permeation chromatography in Methylene chloride with polycarbonate as standard
  • the preferred aromatic polycarbonates and aromatic polyester carbonates are prepared in a known manner from diphenols, carbonic acid or carbonic acid derivatives and, in the case of the polyester carbonates, preferably aromatic dicarboxylic acids or dicarboxylic acid derivatives, optionally ketene terminators and branching agents.
  • aromatic polycarbonates and polyester carbonates takes place e.g. by reacting diphenols with carbonic acid halides, preferably phosgene, and / or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, according to the phase interface method, optionally using chain terminators and optionally using trifunctional or more than trifunctional branching agents, part of the carbonic acid derivatives being used to prepare the polyester carbonates is replaced by aromatic dicarboxylic acids or derivatives of dicarboxylic acids, depending on the requirement of the carbonate structural units to be replaced in the aromatic polycarbonates, by aromatic dicarboxylic acid ester structural units. It is also possible to use a melt polymerization process by reacting diphenols with, for example, diphenyl carbonate.
  • Dihydroxyaryl compounds suitable for the preparation of polycarbonates are those of the formula (1)
  • Z is an aromatic radical having 6 to 30 carbon atoms, which may contain one or more aromatic nuclei, may be substituted and may contain aliphatic or cycloaliphatic radicals or alkylaryls or heteroatoms as bridging elements.
  • Z in formula (1) preferably represents a radical of formula (2)
  • R6 and R7 independently of one another for H, CI - to C18-alkyl, CI - to C18-alkoxy, halogen such as CI or Br or for optionally substituted aryl or aralkyl, preferably for H or CI to C12 alkyl, particularly preferably for H or CI to C8 alkyl and very particularly preferably H or methyl, and
  • X is preferably a single bond, CI to C5 alkylene, C2 to C5 alkylidene, C5 to C6 cycloalkylidene, -O-, -SO-, -CO-, -S-, -S02- or one Rest of formula (2a)
  • Diphenols suitable for the preparation of the polycarbonates are, for example, hydroquinone, resorcinol, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ethers, bis ( hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, a-a'-bis (hydroxyphenyl) diisopropylbenzenes, phthalimidines derived from isatin or phenolphthalein derivatives and their nuclear alkylated, kemarylated and kemhalogenated compounds.
  • Preferred bisphenols are 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) -1-phenylpropane, 1,1-bis (4-hydroxyphenyl) phenylethane, 2,2-bis (4-hydroxyphenyl) ) propane (bisphenol A (BPA)), 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene
  • R ' is in each case Ci-C i-alkyl, aralkyl or aryl, preferably methyl or phenyl.
  • bisphenols are 4,4'-dihydroxydiphenyl, l, l-bis (4-hydroxyphenyl) phenylethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A (BPA)), 2,2- Bis (3,5-dimethyl-4-hydroxyphenyl) propane, l, l-bis (4-hydroxyphenyl) cyclohexane and l, l-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC (BPTMC)) and the dihydroxy compounds of the formulas (IV), (V) and (VI), in which R 'is in each case Ci-C i-alkyl, aralkyl or aryl, preferably methyl or phenyl.
  • BPA bisphenol A
  • BPTMC bisphenol TMC
  • diphenols are e.g. in US-A 3 028 635, US-A 2 999 825, US-A 3 148 172, US-A 2 991 273, US-A 3 271 367, US-A 4 982 014 and US-A 2 999 846, in DE-A 1 570 703, DE-A 2063 050, DE-A 2 036 052, DE-A 2 211 956 and DE-A 3 832 396, in FR-A 1 561 518, in the monograph "H. Schnell , Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964 "and in JP-A 62039/1986, JP-A 62040/1986 and JP A 105550/1986.
  • polycarbonates according to the invention are composed only of atoms selected from one or more of the elements carbon (C), hydrogen (H), oxygen (O), nitrogen (N), sulfur (S) and chlorine (CI).
  • Polycarbonate-polyorganosiloxane copolymers are preferably excluded as copolycarbonates.
  • Suitable carbonic acid derivatives are, for example, phosgene or diphenyl carbonate.
  • Suitable chain terminators which can be used in the production of the polycarbonates are monophenols.
  • Suitable monophenols are, for example, phenol itself, alkylphenols such as cresols, p-tert-butylphenol, cumylphenol and mixtures thereof.
  • Preferred chain terminators are the phenols which are mono- or polysubstituted by C 1 to C 30 alkyl, linear or branched, preferably unsubstituted, or substituted by tert-butyl. Particularly preferred chain terminators are phenol, cumylphenol and / or p-tert-butylphenol.
  • the amount of chain terminator to be used is preferably 0.1 to 5 mol%, based on moles of diphenols used in each case.
  • the chain terminators can be added before, during or after the reaction with a carbonic acid derivative.
  • Suitable branching agents are the tri- or more than trifunctional compounds known in polycarbonate chemistry, in particular those with three or more than three phenolic OH groups.
  • Suitable branching agents are, for example, 1,3,5-tri- (4-hydroxyphenyl) benzene, 1,1,5-tri- (4-hydroxyphenyl) ethane, tri- (4-hydroxyphenyl) phenylmethane, 2,4- Bis- (4-hydroxyphenylisopropyl) phenol, 2,6-bis (2-hydroxy-5'-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenylj- propane, tetra- (4-hydroxyphenyl) methane, tetra- (4- (4-hydroxyphenylisopropyl) phenoxyj-methane and 1,4-bis - ((4 ', 4 "-dihydroxytriphenyl) methyl) benzene and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.
  • the amount of the branching agents to be used is preferably 0.05 mol% to 2.00 mol%, based on moles of diphenols used in each case.
  • the branching agents can either be introduced with the diphenols and the chain terminators in the aqueous alkaline phase or added in solution in an organic solvent before the phosgenation. In the case of the transesterification process, the branching agents are used together with the diphenols.
  • Particularly preferred polycarbonates are the homopolycarbonate based on bisphenol A, the homopolycarbonate based on 1,3-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and the copolycarbonates based on the monomer bisphenol A on the one hand and a monomer from one of the group comprising l, l-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and the bisphenols of the formulas (IV) to (VI) in which R 'is in each case Ci-C i-alkyl, aralkyl or aryl, preferably methyl or phenyl, on the other hand.
  • Preferred methods of producing the polycarbonates to be used according to the invention, including the polyester carbonates, are the known interfacial process and the known melt transesterification process (cf., for example, WO 2004/063249 A1, WO 2001/05866 A1, WO 2000/105867, US 5,340,905 A, US 5,097,002 A, US-A 5,717,057 A).
  • polycarbonate is aromatic polycarbonate based on bisphenol A.
  • the polycarbonate molding composition according to the invention can also be used for other purposes Components are added.
  • the content of the other ingredients in the polycarbonate molding composition produced according to the invention is from 0 to 37% by weight, preferably from 0 to 20% by weight, particularly preferably 0 to 10% by weight.
  • these other ingredients are, for example, other fillers customary for polycarbonate molding compositions, other thermoplastics, for example acrylonitrile-butadiene-styrene copolymers or polyester, or other additives such as UV stabilizers, IR stabilizers, thermal stabilizers, antistatic agents, dyes and pigments in the usual amounts become; if necessary, the demolding behavior, the flow behavior, and / or the flame resistance can be improved by adding external mold release agents, flow agents, and / or flame retardants (e.g.
  • alkyl and aryl phosphites alkyl and aryl phosphites, phosphates, phosphines, low molecular weight carboxylic acid esters, halogen compounds, salts) , Chalk, quartz powder, glass and carbon fibers, pigments and their combinations, such compounds are described, for example, in WO 99/55772, pp. 15-25, and in "Plastics Additives", R. Gumbleter and H.
  • a carboxylic anhydride-modified alpha-olefin polymer in particular a maleic anhydride-modified alpha-olefin polymer is preferred as the stabilizer, such carboxylic anhydride-modified alpha-olefin polymers being known, for example, from WO2018037037A1.
  • the aforementioned polyesters are to be distinguished from the polyester carbonates described above.
  • the polyesters in the sense of the present invention are in particular those described in the sections [0131] to [0138] of US 2014/357769 A1.
  • the proportion of polyester in the molding composition is at most 0.9% by weight, preferably at most 0.5% by weight, particularly preferably at most 0.2% by weight, particularly preferably at most 0.1% by weight, entirely particularly preferably from 0 to 0.1% by weight.
  • the proportion of polyester in the molding composition is very particularly preferably 0% by weight.
  • Suitable additives are described, for example, in “Additives for Plastics Handbook, John Murphy, Elsevier, Oxford 1999", in “Plastics Additives Handbook, Hans Doubt, Hanser, Kunststoff 2001”.
  • Suitable antioxidants or thermal stabilizers are, for example:
  • Organic phosphites, phosphonates and phosphanes are preferred, mostly those in which the organic radicals consist wholly or partly of optionally substituted aromatic radicals.
  • Suitable complexing agents for heavy metals and for neutralizing traces of alkali are o / m phosphoric acids, fully or partially esterified phosphates or phosphites.
  • Suitable light stabilizers are 2- (2'-hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, esters of substituted and unsubstituted benzoic acids, acrylates, sterically hindered amines, oxamides and 2- (hydroxyphenyl) -l, 3,5- triazines or substituted hydroxyalkoxyphenyl, 1,3,5-triazoles, substituted benzotriazoles such as, for. B.
  • Polypropylene glycols alone or in combination with e.g. B. sulfones or sulfonamides as stabilizers can be used against damage by gamma rays.
  • Processing aids such as mold release agents, usually derivatives of long-chain fatty acids, can also be added.
  • Z are preferred.
  • Suitable flame retardant additives are phosphate esters, i.e. H. Triphenyl phosphate, resorcinol diphosphoric esters, bromine-containing compounds such as brominated phosphoric esters, brominated oligocarbonates and polycarbonates, and preferably salts of fluorinated organic sulfonic acids.
  • Suitable impact modifiers are butadiene rubber with grafted-on styrene-acrylonitrile or methyl methacrylate, ethylene-propylene rubbers with grafted-on maleic anhydride, ethyl- and butyl-acrylate rubbers with grafted-on methyl methacrylate or styrene-acrylonitrile, interpenetrating siloxane-acrylate-acrylate-acrylate-acrylate-acrylate-acrylate-acrylate-or acrylate-nitrate networks.
  • colorants such as organic dyes or pigments or inorganic pigments, IR absorbers, individually, in a mixture or in combination with stabilizers, glass fibers, glass (hollow) spheres, inorganic, in particular mineral, fillers can be added, of which mineral Fillers also include the reinforcing fillers, in particular titanium dioxide (T1O2), talc (Mg3Si40io (OH) 2), dolomite CaMg [C03] 2, kaolinite ALi [(OF [) 8
  • mineral Fillers also include the reinforcing fillers, in particular titanium dioxide (T1O2), talc (Mg3Si40io (OH) 2), dolomite CaMg [C03] 2, kaolinite ALi [(OF [) 8
  • polycarbonate molding composition according to the invention optionally in a mixture with other thermoplastics and / or customary additives, can be used wherever known polycarbonate molding compositions are used.
  • a continuous single-shaft kneader has a single rotating worm shaft which performs an axial back-and-forth movement in synchronism with the rotation, so that an oscillating movement, in particular a sinusoidal oscillating back-and-forth movement, results.
  • the maximum length of the distance in the axial direction that the worm shaft moves during the outward movement or also travels the movement, is also called stroke, the length of the distance covered by the worm shaft during the forward movement being equal to the length of the distance covered by the worm shaft during the moving movement.
  • the screw set of a continuous single-shaft kneader consists of screw elements that can be arranged modularly on the screw shaft.
  • the screw elements can have different lengths and have kneading flight profiles with different geometries and pitches. Both 3- and 4-wing screw elements can be used.
  • Kneading bolts are located in the housing surrounding the worm shaft and are mounted in a fixed position. Usually there are 3 rows (3-wing) or 4 rows (4-wing) of kneading pins along the housing of the continuous single-shaft kneader.
  • the kneading pins can have, for example, a round or a diamond-shaped cross section and different lengths and cross-sectional areas.
  • the housing and the screw shaft of the continuous single-shaft kneader can be designed to be both heatable and coolable.
  • the outside diameter of a screw element is also referred to as a DA.
  • the core radius of a screw element is called DI.
  • the L / D ratio is the quotient of the length of the section of the screw shaft which is occupied by screw elements and the outer diameter of a screw element.
  • a separate discharge device is usually used to discharge the melt from the continuous single-shaft kneader, for example via a nozzle plate, since the continuous single-shaft kneader itself cannot generate enough pressure to overcome the nozzle plate.
  • the discharge device can be, for example, a single-screw extruder, a twin-screw extruder or a melt pump.
  • These discharge elements are located behind the continuous single-shaft kneader, preferably directly behind the continuous single-shaft kneader, but possibly also at a distance from it by a chute or a flange.
  • Continuous single-shaft kneaders in and of themselves are known, for example, from: DE1908414A1, DD71190A, as well as from the book “Introduction to plastics processing”, Carl Hanser Verlag, Kunststoff, 8th edition, 2017, pages 104-105, the publication “Der Ko-Kneter in the plastics industry ”in the magazine Schweizer Maschinenrat, 1960, pages 54-61 and the book“ Mixing in polymer processing ”, Marcel Dekker Inc., 1991, pages 200-219.
  • a method for producing a polycarbonate molding composition containing a reinforcing filler preferably selected from one or more members of the group comprising the members titanium dioxide (TiCE), talc (Mg3SiiOio (OH) 2), dolomite CaMg [C03] 2 , Kaolinite ALt [(OH) g
  • a reinforcing filler preferably selected from one or more
  • Such a polycarbonate molding composition produced in accordance with the invention has better properties than polycarbonate molding compositions which are compared to polycarbonate molding compositions which have been produced by processes according to the prior art, the polycarbonate molding compositions which have been produced according to the prior art having the same constituents in the same proportions as that Polycarbonate molding composition produced according to the invention.
  • a continuous single-shaft kneader with a DA / stroke ratio of 4 to 7, particularly preferably 5.5 to 6.7.
  • the continuous single-shaft kneader has an L / D ratio of 9 to 27, particularly preferably 15 to 21. Further preferably according to the invention, the continuous single-shaft kneader has a DA / DI ratio of 1.5 to 1.8, particularly preferably 1.55 to 1.71.
  • the screw elements of the continuous single-shaft kneader preferably have an outer diameter DA of 30 to 200 mm. Further preferably according to the invention, the continuous single-shaft kneader has a flight depth, defined as (DA-DI) / 2, of 5 to 92 mm.
  • the continuous single-shaft kneader used according to the invention can be, for example, a Buss co-kneader with the designations Mx or MKS or MDK from Buss AG (Switzerland) as well as single-shaft kneaders with the designation SJW from Xinda (China) and single-shaft kneaders with the Trade name CK from X-Compound (Switzerland).
  • the present invention also relates to a molding composition which is produced by the process according to the invention.
  • the molding compound After cooling to ambient temperature, the molding compound can be used for direct injection molding without further processing.
  • the invention furthermore relates to the use of the molding composition according to the invention for the production of a molding, in particular an object obtainable by injection molding or a film or plate obtainable by extrusion of the molding composition, or a reflector for a lamp or a structural component, for example for automobile construction.
  • the tests described in comparative examples 1.1, 1.2, 3.1, 3.2, 5.1 and 5.2 were carried out using a ZE60A UTXi twin-screw extruder from KraussMaffei Berstorff GmbH.
  • the twin-screw extruder used has an inside diameter of 65 mm and an L / D ratio of 43.
  • the basic structure of the extruder used is shown in FIG. 1.
  • the twin-screw extruder has a housing consisting of 11 parts, in which 2 co-rotating shafts meshing with each other (not shown) are arranged.
  • a conveying zone for a polycarbonate granulate, a titanium dioxide powder and the other molding compound components In the area of the housings 2 to 7 there is a conveying zone for a polycarbonate granulate, a titanium dioxide powder and the other molding compound components.
  • plasticizing zone which consists of different two- and three-course kneading blocks of different widths as well as tooth blocks.
  • a mixing zone which consists of kneading elements, tooth blocks and conveying elements.
  • the degassing opening 13 is located in the housing part 11 and is connected to a suction device (not shown).
  • the pressure build-up zone is located in housing 12, followed by a nozzle plate with 29 holes.
  • the measurement of the melt temperature was carried out in Examples 1.1, 1.2, 3.1, 3.2, 5.1 and 5.2 by inserting a thermocouple into the emerging melt of the middle melt strand directly in front of the nozzle.
  • the experiments described in Examples 2.1, 2.2, 4, 6 and 7 according to the invention were carried out with a continuous single-shaft kneader of the type Ko-Kneader Mx 58 from Buss AG.
  • the co-kneader used has an inside diameter of 58.4 mm, an outside screw element diameter DA of 57.7 mm in the area of the bearing points, an outside screw element diameter DA of 56.3 mm in the area outside the bearing points, an L / D Ratio of 15, a DA / DI ratio of 1.55 from the start of the kneader shaft to the accumulation ring at the end of the melting zone, a DA / DI ratio of 1.71 after the accumulation ring to the end of the kneader shaft and a DA / stroke ratio of 5.5.
  • the total length of the areas of the bearing points is approximately 15% of the total length of the screw shaft of the continuous single-shaft kneader.
  • the basic structure of the continuous single-shaft kneader used is shown in FIG. 2.
  • the continuous single-shaft kneader has a housing consisting of 3 parts, in which a rotating screw shaft (not shown) which simultaneously executes an axial back and forth movement is arranged.
  • the molding compound components can be fed to the continuous single-shaft kneader via the feed funnels 14 and 15.
  • a single-screw extruder (not shown in FIG. 2) with an inner housing diameter of 110 mm and an L / D ratio of 6 is used to discharge the melt from the continuous single-shaft kneader.
  • the single-screw extruder is flanged directly to the continuous single-shaft kneader and is only used to build up pressure to granulate the polycarbonate molding compound.
  • the melt strands emerging from the nozzle plate were granulated by means of hot-cut granulation.
  • a conveying zone for a polycarbonate granulate, a titanium dioxide powder and the other molding compound components.
  • a plasticizing zone consisting of various mixing and kneading elements.
  • a retaining ring with an inside diameter of 43 mm.
  • the housing 18 In the area of the housing 18 there is a conveying zone consisting of conveying elements and two mixing zones consisting of different mixing and kneading elements; one at the beginning and one at the end of the case. Furthermore, there is a degassing zone in the housing 18 between the mixing zones, which zone consists of conveying elements. In the housing part 18 there is the degassing opening 20, which is connected to a suction device (not shown).
  • Example 4 all of the constituents of the polycarbonate molding composition were metered in via the main intake in housing 16 via the intake funnel 14 shown.
  • a conveying zone for a polycarbonate granulate, a titanium dioxide powder and the other molding compound components.
  • a plasticizing zone consisting of various mixing and kneading elements.
  • a retaining ring with an inside diameter of 43 mm.
  • the housing 18 In the area of the housing 18 there is a conveyor zone consisting of conveyor elements and two mixing zones consisting of different mixing and kneading elements; one at the beginning and one at the end of the case. Furthermore, there is a degassing zone in the housing 18 between the mixing zones, which zone consists of conveying elements.
  • the degassing opening 20 which is connected to a suction device (not shown).
  • Example 6 all of the constituents of the polycarbonate molding composition were metered in via the main intake in housing 16 via the intake funnel 14 shown.
  • a conveying zone for a polycarbonate granulate, a titanium dioxide powder and the other molding compound components.
  • a plasticizing zone consisting of various mixing and kneading elements.
  • a retaining ring with an inside diameter of 43 mm.
  • the housing 18 In the area of the housing 18 there is a conveyor zone consisting of conveyor elements and two mixing zones consisting of different mixing and kneading elements; one at the beginning and one at the end of the case. Furthermore, there is a degassing zone in the housing 18 between the mixing zones, which zone consists of conveying elements.
  • the degassing opening 20 which is connected to a suction device (not shown).
  • Example 7 all of the constituents of the polycarbonate molding composition were metered in via the main intake in housing 16 via the intake funnel 14 shown. In the area of the housing 16 there is a conveying zone for a polycarbonate granulate and the titanium dioxide powder.
  • a plasticizing zone consisting of various mixing and kneading elements.
  • a retaining ring with an inside diameter of 43 mm.
  • the housing 18 In the area of the housing 18 there is a conveyor zone consisting of conveyor elements and two mixing zones consisting of different mixing and kneading elements; one at the beginning and one at the end of the case. Furthermore, there is a degassing zone in the housing 18 between the mixing zones, which zone consists of conveying elements.
  • the degassing opening 20 which is connected to a suction device (not shown).
  • the polycarbonate molding compound produced in Examples 1.1, 1.2, 2.1 and 2.2 was then processed into sheets with a glossy surface using an injection molding process.
  • the moldings were produced by injection molding on an FM160 injection molding machine from Klöckner. This injection molding machine has a cylinder diameter of 45 mm. For this purpose, the polymer mixtures were pre-dried at 110 ° C. within 4 hours. Injection molding was carried out under the conditions characteristic of polycarbonates. In the production of plates with a size of 150 mm x 105 mm x 3.2 mm, the melt or melt temperatures were 260 ° C, the mold temperature 80 ° C, the cycle time 43 seconds, the injection speed 40 mm / sec and the dynamic pressure at 150 bar. An injection mold with glossy polish (ISO NI) was used to manufacture the panels.
  • ISO NI injection mold with glossy polish
  • a suitable measuring method for the quantitative detection of surface defects is the observation of the molded part surfaces in a reflected light microscope - e.g. Zeiss Axioplan 2 motorized - through a lens with 2.5x magnification in the bright field, when illuminated with a halogen 100 light source.
  • a surface area of 4 cm x 4 cm was viewed by meandering scanning and photos of this surface were taken with a CCD camera - eg Axiocam HRC.
  • an image analysis software - eg KS 300 Zeiss - the photos were taken Number and size of the surface defects determined.
  • optically determined surface defects on molded parts made of polymer mixtures with the above-mentioned compositions are caused in particular by agglomerates or aggregates of titanium dioxide particles which are insufficiently broken up when the components are compounded in the extruder.
  • the polycarbonate molding composition produced in Examples 3.1, 3.2 and 4 was subsequently converted into flat bars with a length of 80 mm, a width of 10 mm and a thickness of 3 mm and into step plates with a length of 75 mm, a width of 50 mm and Injection molded to a thickness of 2mm in the flat half and 3mm in the thicker half.
  • the impact strength of the polycarbonate molding composition was then determined on the flat bars in an impact test according to DIN EN ISO 179 / leU at 23 ° C. and at -30 ° C. In each case 10 test specimens were tested and the arithmetic mean was determined from these results.
  • the step plates were then photographed with a camera. The photos produced (see FIGS.
  • the photos were taken with a Canon EOS 80D digital SLR camera 22 with an attached Canon EF Macro 50mm F2.5 lens and an f / 5.6 aperture, an exposure time of 1/250 seconds and an ISO film speed of 100 added.
  • the camera was aligned axially to the light source, inclined at an angle of 30 ° to the step plate surface and focused on the area of the step plate that directly connected to the area of the step plate that was illuminated by the light source.
  • the dispersion quality of the titanium dioxide powder was determined by means of visual evaluation of extruded foils.
  • 150 ⁇ m thick films were produced from the polycarbonate molding compound produced by means of a film extrusion system, consisting essentially of a single-screw extruder with a subsequent rolling mill.
  • These foils were then placed on a commercial light table in transmitted light with an applied scale using a Canon EOS 80D camera with a Canon EF Macro 50mm F2.5 lens and an f / 5.6 aperture, an exposure time of 1/200 seconds and an ISO film speed of 100 photographed.
  • the camera was aligned at a 90 ° angle to the film surface and it was focused on the film surface.
  • Viscosity h Gb i 1.31 (measured in CH2CI2 as solvent at 25 ° C and at a
  • Example 7 the mixture components that are fed into the extruder consist of:
  • Comparative examples 1.1 and 1.2 differ with regard to the speed of the extruder.
  • the extruder speed is 600 1 / min, in example 1.2 250 1 / min with the same throughput of 720 kg / h each.
  • This speed / throughput range covers a range, customary for the twin-screw extruder used, between low and high energy input for the compounded molding compound.
  • the increase in the speed of rotation does not lead to an improved dispersion, as can be seen from the higher number of defects on the surface of the injection mold plates from Example 1.1 compared to the plates from Example 1.2 (see Table 1), but to around 43 ° C. higher melt temperature, which promotes polymer degradation in a manner known to those skilled in the art.
  • Examples 2.1 and 2.2 according to the invention was to achieve an at least comparable surface quality as in Comparative Examples 1.1 and 1.2, but with a significantly lower melt temperature.
  • speeds and throughputs of the method according to the invention were selected which cover the range between low and high energy input which is customary for the continuous single-shaft kneader used.
  • Table 1 the number of surface defects could be significantly reduced with the process according to the invention with a significantly lower melt temperature.
  • Comparative examples 3.1 and 3.2 differ with regard to the speed of the extruder.
  • the extruder speed is 200 1 / min, in example 1.2 300 1 / min with the same throughput of 450 kg / h each.
  • This speed / throughput range covers one for the one used Twin screw extruder usual range between low and high energy input for the compounded molding compound.
  • Example 4 was to achieve a higher impact strength of the flat bars and a better surface quality of the injection-molded step plates than in Comparative Examples 3.1 and 3.2 at a comparable or lower melt temperature.
  • higher impact strength and better surface quality with the same molding composition are achieved by better dispersion of the titanium dioxide particles contained in the molding composition.
  • a high speed of 600 1 / min and a throughput of 150 kg / h of the method according to the invention were selected.
  • the impact strength could be increased significantly with the process according to the invention with a simultaneously lower melt temperature (Example 4 compared to Example 3.2) or with a slightly higher melt temperature, the impact strength could be increased by at least 60% (non-broken flat bars have one Impact strength of at least 250 kJ / m 2 ).
  • the surface quality of the step plates could be significantly improved despite the lower or slightly higher melt temperature, ie lower or slightly higher energy input.
  • Comparative examples 5.1 and 5.2 differ with regard to the speed of the extruder.
  • the extruder speed is 600 1 / min, in example 5.2 225 1 / min with the same throughput of 690 kg / h each.
  • This speed 1 - / D u rc h s atz- B c r c ic h covers a range between low and high energy input for the compounded molding compound that is customary for the twin-screw extruder used.
  • the increase in speed leads to improved dispersion, however, as can be seen from the lower number of defects on the surface of the injection molding plates of Example 5.1 compared to the plates of Example 5.2 (see Table 1 and also FIGS. 6 and 7) a melt temperature which is 58 ° C. higher, which promotes polymer degradation in a manner known to those skilled in the art.
  • Example 6 was to achieve a better surface quality of the films than in Comparative Examples 5.1 and 5.2 at a comparable or lower melt temperature.
  • better surface quality with the same molding composition is achieved by better dispersion of the titanium dioxide particles contained in the molding composition.
  • a high speed of 650 1 / min and a throughput of 160 kg / h of the method according to the invention were selected.
  • Table 1 and Figure 8 it can be seen that the surface quality of the film could be decisively improved with the process according to the invention with a melt temperature which was at the same time lower by 70 ° C., ie substantially less energy input.
  • Example 7 (according to the invention) The aim of Example 6 according to the invention was to obtain a comparable one with a titanium dioxide content which was doubled compared to Example 6 according to the invention

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un procédé de préparation d'une matière à mouler dotée de propriétés améliorées. L'invention concerne notamment la préparation d'une matière à mouler contenant un polycarbonate et une charge de renfort choisie de préférence parmi un ou plusieurs éléments du groupe constitué des éléments suivants : dioxyde de titane (TiO2), talc (Mg3Si4O10(OH)2), dolomite (CaMg[CO3]2), kaolinite (Al4[(OH)8|Si4O10]) et wollastonite (Ca3[Si3O9]), de préférence choisie parmi un ou plusieurs éléments du groupe constitué des éléments suivants : dioxyde de titane (TiO2) et talc (Mg3Si4O10(OH)2). La teneur en charge de renfort est de 3 à 40 % en poids, de préférence de 10 à 35 % en poids, de façon plus préférée de 12 à 32 % en poids et de façon encore plus préférée de 15 à 30 % en poids, respectivement par rapport à la masse totale de la matière à mouler.
PCT/EP2019/082498 2018-12-12 2019-11-26 Procédé de préparation d'une matière à mouler dotée de propriétés ameliorées WO2020120119A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP18211945.3 2018-12-12
EP18211945 2018-12-12

Publications (1)

Publication Number Publication Date
WO2020120119A1 true WO2020120119A1 (fr) 2020-06-18

Family

ID=64901837

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2019/082498 WO2020120119A1 (fr) 2018-12-12 2019-11-26 Procédé de préparation d'une matière à mouler dotée de propriétés ameliorées

Country Status (1)

Country Link
WO (1) WO2020120119A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022199879A1 (fr) 2021-03-26 2022-09-29 Blach Verwaltungs Gmbh & Co Kg Dispositif et procédé d'acheminement et d'augmentation de la prévention du dérapage et/ou du glissement d'un matériau contenant des produits en vrac
WO2022199878A1 (fr) 2021-03-26 2022-09-29 Blach Verwaltungs Gmbh & Co Kg Appareil d'alimentation en matériau comprenant une matière en vrac et dispositif de dosage et procédé de production d'un composé de moulage aux propriétés améliorées

Citations (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2991273A (en) 1956-07-07 1961-07-04 Bayer Ag Process for manufacture of vacuum moulded parts of high molecular weight thermoplastic polycarbonates
US2999825A (en) 1958-12-12 1961-09-12 Gen Mills Inc Epoxy-polyamide-ester resin reaction product
US2999846A (en) 1956-11-30 1961-09-12 Schnell Hermann High molecular weight thermoplastic aromatic sulfoxy polycarbonates
US3028635A (en) 1959-04-17 1962-04-10 Schlumberger Cie N Advancing screw for gill box
US3148172A (en) 1956-07-19 1964-09-08 Gen Electric Polycarbonates of dihydroxyaryl ethers
US3271367A (en) 1955-03-26 1966-09-06 Bayer Ag Thermoplastic polycarbonates of dihydroxydiarylene sulfones and their preparation
FR1561518A (fr) 1967-03-10 1969-03-28
DE1908414A1 (de) 1968-03-08 1969-11-06 Buss Ag Verfahren zum Behandeln von staub- und pulverfoermigen Materialien und Einrichtung zur Ausuebung des Verfahrens
DE1570703A1 (de) 1964-10-07 1970-02-12 Gen Electric Hydrolytisch stabile Polycarbonate sowie Verfahren zu deren Herstellung
DE2036052A1 (en) 1970-07-21 1972-01-27 Milchwirtschafthche Forschungs und Untersuchungs Gesellschaft mbH, 2100 Hamburg Working up of additives in fat and protein - contng foodstuffs
DE2063050A1 (de) 1970-12-22 1972-07-13 Bayer Verseifungsbeständige Polycarbonate
DE2211956A1 (de) 1972-03-11 1973-10-25 Bayer Ag Verfahren zur herstellung verseifungsstabiler blockcopolycarbonate
JPS6162039A (ja) 1984-09-04 1986-03-29 Fuji Xerox Co Ltd 電子写真用感光体
JPS6162040A (ja) 1984-09-04 1986-03-29 Fuji Xerox Co Ltd 電子写真用感光体
JPS61105550A (ja) 1984-10-29 1986-05-23 Fuji Xerox Co Ltd 電子写真用感光体
DE3832396A1 (de) 1988-08-12 1990-02-15 Bayer Ag Dihydroxydiphenylcycloalkane, ihre herstellung und ihre verwendung zur herstellung von hochmolekularen polycarbonaten
US4982014A (en) 1988-08-12 1991-01-01 Bayer Aktiengesellschaft Dihydroxydiphenyl cycloalkanes, their production and their use for the production of high molecular weight polycarbonates
US5097002A (en) 1988-07-11 1992-03-17 Ge Plastics Japan Ltd. Melt, catalytic process for preparing polycarbonates from carbonic acid diester
US5340905A (en) 1992-11-12 1994-08-23 Bayer Aktiengesellschaft Process for the preparation of thermoplastic polycarbonates
US5717057A (en) 1994-12-28 1998-02-10 General Electric Company Method of manufacturing polycarbonate
WO1999055772A1 (fr) 1998-04-24 1999-11-04 Ciba Specialty Chemicals Holding Inc. Augmentation de la masse moleculaire de polyesters
WO2001005866A1 (fr) 1999-07-19 2001-01-25 Bayer Aktiengesellschaft Procede de production de polycarbonates modifies
WO2001005867A1 (fr) 1999-07-19 2001-01-25 Bayer Aktiengesellschaft Polycarbonate et articles moules en polycarbonate
WO2004063249A1 (fr) 2003-01-10 2004-07-29 Bayer Materialscience Ag Procede de preparation de polycarbonates
US20110260116A1 (en) * 2010-04-22 2011-10-27 Arkema France Thermoplastic and/or elastomeric composite based on carbon nanotubes and graphenes
EP2639271A1 (fr) * 2010-11-08 2013-09-18 Idemitsu Kosan Co., Ltd. Composition de résine polycarbonate, article moulé et élément de structure pour la production d'énergie solaire photovoltaïque
US20140357769A1 (en) 2013-06-04 2014-12-04 Sabic Global Technologies B.V. Thermal plastic blends with improved impact strength and flow
WO2018037037A1 (fr) 2016-08-24 2018-03-01 Covestro Deutschland Ag Composition de polycarbonate comprenant du talc

Patent Citations (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3271367A (en) 1955-03-26 1966-09-06 Bayer Ag Thermoplastic polycarbonates of dihydroxydiarylene sulfones and their preparation
US2991273A (en) 1956-07-07 1961-07-04 Bayer Ag Process for manufacture of vacuum moulded parts of high molecular weight thermoplastic polycarbonates
US3148172A (en) 1956-07-19 1964-09-08 Gen Electric Polycarbonates of dihydroxyaryl ethers
US2999846A (en) 1956-11-30 1961-09-12 Schnell Hermann High molecular weight thermoplastic aromatic sulfoxy polycarbonates
US2999825A (en) 1958-12-12 1961-09-12 Gen Mills Inc Epoxy-polyamide-ester resin reaction product
US3028635A (en) 1959-04-17 1962-04-10 Schlumberger Cie N Advancing screw for gill box
DE1570703A1 (de) 1964-10-07 1970-02-12 Gen Electric Hydrolytisch stabile Polycarbonate sowie Verfahren zu deren Herstellung
FR1561518A (fr) 1967-03-10 1969-03-28
DE1908414A1 (de) 1968-03-08 1969-11-06 Buss Ag Verfahren zum Behandeln von staub- und pulverfoermigen Materialien und Einrichtung zur Ausuebung des Verfahrens
DE2036052A1 (en) 1970-07-21 1972-01-27 Milchwirtschafthche Forschungs und Untersuchungs Gesellschaft mbH, 2100 Hamburg Working up of additives in fat and protein - contng foodstuffs
DE2063050A1 (de) 1970-12-22 1972-07-13 Bayer Verseifungsbeständige Polycarbonate
DE2211956A1 (de) 1972-03-11 1973-10-25 Bayer Ag Verfahren zur herstellung verseifungsstabiler blockcopolycarbonate
JPS6162039A (ja) 1984-09-04 1986-03-29 Fuji Xerox Co Ltd 電子写真用感光体
JPS6162040A (ja) 1984-09-04 1986-03-29 Fuji Xerox Co Ltd 電子写真用感光体
JPS61105550A (ja) 1984-10-29 1986-05-23 Fuji Xerox Co Ltd 電子写真用感光体
US5097002A (en) 1988-07-11 1992-03-17 Ge Plastics Japan Ltd. Melt, catalytic process for preparing polycarbonates from carbonic acid diester
DE3832396A1 (de) 1988-08-12 1990-02-15 Bayer Ag Dihydroxydiphenylcycloalkane, ihre herstellung und ihre verwendung zur herstellung von hochmolekularen polycarbonaten
US4982014A (en) 1988-08-12 1991-01-01 Bayer Aktiengesellschaft Dihydroxydiphenyl cycloalkanes, their production and their use for the production of high molecular weight polycarbonates
US5340905A (en) 1992-11-12 1994-08-23 Bayer Aktiengesellschaft Process for the preparation of thermoplastic polycarbonates
US5717057A (en) 1994-12-28 1998-02-10 General Electric Company Method of manufacturing polycarbonate
WO1999055772A1 (fr) 1998-04-24 1999-11-04 Ciba Specialty Chemicals Holding Inc. Augmentation de la masse moleculaire de polyesters
WO2001005866A1 (fr) 1999-07-19 2001-01-25 Bayer Aktiengesellschaft Procede de production de polycarbonates modifies
WO2001005867A1 (fr) 1999-07-19 2001-01-25 Bayer Aktiengesellschaft Polycarbonate et articles moules en polycarbonate
WO2004063249A1 (fr) 2003-01-10 2004-07-29 Bayer Materialscience Ag Procede de preparation de polycarbonates
US20110260116A1 (en) * 2010-04-22 2011-10-27 Arkema France Thermoplastic and/or elastomeric composite based on carbon nanotubes and graphenes
EP2639271A1 (fr) * 2010-11-08 2013-09-18 Idemitsu Kosan Co., Ltd. Composition de résine polycarbonate, article moulé et élément de structure pour la production d'énergie solaire photovoltaïque
US20140357769A1 (en) 2013-06-04 2014-12-04 Sabic Global Technologies B.V. Thermal plastic blends with improved impact strength and flow
WO2018037037A1 (fr) 2016-08-24 2018-03-01 Covestro Deutschland Ag Composition de polycarbonate comprenant du talc

Non-Patent Citations (11)

* Cited by examiner, † Cited by third party
Title
"Mixing in polymer processing", 1991, MARCEL DEKKER INC., pages: 200 - 219
"neu bearbeitete und erweiterte Auflage", 2016, HANSER VERLAG, article "Klemens Kohlgrüber: Der gleichläufige Doppelschneckenextruder", pages: 47
"Zeitschrift Schweizer Maschinenmarkt", 1960, pages: 54 - 61
BUCH: "Einführung in die Kunststoffverarbeitung", vol. 8, 2017, CARL HANSER VERLAG, pages: 104 - 105
D. FREITAGU. GRIGOP.R. MÜLLERH. NOUVERTNE: "Encyclopedia of Polymer Science and Engineering", vol. 11, 1988, article "Polycarbonates", pages: 648 - 718
H. SCHNELL: "Chemistry and Physics of Polycarbonates", 1964, INTERSCIENCE PUBLISHERS
HANS ZWEIFEL: "Plastics Additives Handbook", 2001, HANSER
JOHN MURPHY: "Additives for Plastics Handbook", 1999, ELSEVIER
R. GÄCHTERH. MÜLLER: "Plastics Additives", 1983, HANSER PUBLISHERS
SCHNELL: "Chemistry and Physics of Polycarbonates", POLYMER REVIEWS, vol. 9, 1964
U. GRIGOK. KIRCHNERP.R. MÜLLER: "Polycarbonate, Polyacetale, Polyester, Celluloseester", vol. 3/1, 1992, CARL HANSER VERLAG, article "Polycarbonate'' in Becker/Braun, Kunststoff-Handbuch", pages: 117 - 299

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022199879A1 (fr) 2021-03-26 2022-09-29 Blach Verwaltungs Gmbh & Co Kg Dispositif et procédé d'acheminement et d'augmentation de la prévention du dérapage et/ou du glissement d'un matériau contenant des produits en vrac
WO2022199878A1 (fr) 2021-03-26 2022-09-29 Blach Verwaltungs Gmbh & Co Kg Appareil d'alimentation en matériau comprenant une matière en vrac et dispositif de dosage et procédé de production d'un composé de moulage aux propriétés améliorées
DE102021001601A1 (de) 2021-03-26 2022-09-29 Blach Verwaltungs GmbH + Co. KG Vorrichtung zum Einzug eines Schüttgut aufweisenden Materials dessen Gleit- und/oder Rutschhemmung erhöht wird sowie Verfahren zur Erhöhung der Gleit- und/oder Rutschhemmung
DE102021001602A1 (de) 2021-03-26 2022-09-29 Blach Verwaltungs GmbH + Co. KG Vorrichtung zum Einzug eines Schüttgut aufweisenden Materials und Dosiergerät sowie Verfahren zur Herstellung einer Formmasse mit verbesserten Eigenschaften

Similar Documents

Publication Publication Date Title
EP2354182B1 (fr) Produits dotés d'une résistance aux flammes améliorée
EP2593288B1 (fr) Dispositif et procédé de fabrication de produits à partir de mélanges polymères contenant des pigments
WO2020048750A1 (fr) Procédé de préparation d'une matière à mouler dotée de propriétés ameliorées
EP2558515A1 (fr) Compositions de polycarbonates à propriétés optiques et thermiques améliorées
EP3575362A1 (fr) Recouvrements pour sources lumineuses à led
WO2020120119A1 (fr) Procédé de préparation d'une matière à mouler dotée de propriétés ameliorées
WO2016087295A1 (fr) Amélioration de l'écoulabilité des compositions de polycarbonate
DE102006051306A1 (de) Substratmaterialien für Extrusionsfolien mit geringen Oberflächenstörungen
EP2333014B1 (fr) Film obtenu à partir d'une composition de polycarbonate
EP3502182B1 (fr) Compositions de polycarbonate chargées et stabilisées
EP4077515B1 (fr) Procédé de fabrication d'un lot maître et d'une matière de moulage aux propriétés améliorées
EP3458510B2 (fr) Compositions a base de polycarbonate contenant de l'acide carboxylique et leurs esters de glycerol ou diglycerol
EP4077514A1 (fr) Procédé de production d'un composé de moulage présentant des propriétés de surface améliorées
EP3502183B1 (fr) Compositions de polycarbonate chargées de talc
EP2955201A1 (fr) Compositions à base de polycarbonate renforcées en fibres de verre
DE202017007301U1 (de) Transparente Formteile mit geringer Dicke
WO2023202910A1 (fr) Méthode de production d'un composé plastique ayant des propriétés ameliorées
WO2023280608A1 (fr) Composition et procédé de production d'un composé de moulage de polycarbonate/polyméthacrylate de méthyle thermoplastique transparent
WO2022112406A1 (fr) Compositions de polycarbonate contenant du dioxyde de titane et des flocons de verre comprenant un revêtement de dioxyde de titane
EP4092070A1 (fr) Réduction de la teneur en sel spécial d'acide sulfonique, de sulfonamide ou de dérivés de sulfonimide dans les eaux usées
EP4378492A1 (fr) Dispositif médical doté d'une résistance élevée aux lipides intra-lipides à partir d'un matériau polycarbonate

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19808809

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19808809

Country of ref document: EP

Kind code of ref document: A1