EP1490421A1 - Polycarbonate a viscosite a l'expansion elevee - Google Patents

Polycarbonate a viscosite a l'expansion elevee

Info

Publication number
EP1490421A1
EP1490421A1 EP03709802A EP03709802A EP1490421A1 EP 1490421 A1 EP1490421 A1 EP 1490421A1 EP 03709802 A EP03709802 A EP 03709802A EP 03709802 A EP03709802 A EP 03709802A EP 1490421 A1 EP1490421 A1 EP 1490421A1
Authority
EP
European Patent Office
Prior art keywords
polycarbonate
containers
polycarbonates
bis
hydroxyphenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03709802A
Other languages
German (de)
English (en)
Inventor
Klaus Horn
Ralf Hufen
Markus Krieter
Dirk-Jacques Dijkstra
Jens Hepperle
Helmut MÜNSTEDT
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Bayer MaterialScience AG
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
Priority claimed from DE10213230A external-priority patent/DE10213230A1/de
Priority claimed from DE2002129594 external-priority patent/DE10229594A1/de
Application filed by Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Publication of EP1490421A1 publication Critical patent/EP1490421A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
    • B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
    • 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
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • 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
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C2049/023—Combined blow-moulding and manufacture of the preform or the parison using inherent heat of the preform, i.e. 1 step blow moulding
    • 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
    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/07—Preforms or parisons characterised by their configuration
    • B29C2949/0715—Preforms or parisons characterised by their configuration the preform having one end closed
    • 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
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/04—Extrusion blow-moulding
    • 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
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/06—Injection blow-moulding
    • 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
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/20—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor of articles having inserts or reinforcements ; Handling of inserts or reinforcements
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages
    • B29L2031/7126—Containers; Packaging elements or accessories, Packages large, e.g. for bulk storage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages
    • B29L2031/7158—Bottles

Definitions

  • the present invention relates to polycarbonate with high expansion viscosity and containers containing this polycarbonate.
  • the present invention further relates to the manufacture and use of these containers.
  • containers containing polycarbonate are known. These containers are made, for example, from compositions (also called compounds) that contain polycarbonate and conventional additives. These compositions of the polymer (polycarbonate) and the additives are also referred to as plastic.
  • the additives, which are also called additives, are, for example, stabilizers, processing aids and others.
  • the container containing polycarbonate can also include other components, such as seals made of rubber or handles made of metal or others
  • Containers containing polycarbonate have numerous advantageous properties such as high transparency, good mechanical properties, high resistance to environmental influences and long life, as well as low weight and easy, inexpensive to manufacture.
  • the containers containing polycarbonate can be produced, for example, by the extrusion blow molding process or by the injection blow molding process.
  • the polycarbonate is usually melted with a single-shaft extruder and shaped into a free-standing tube through a nozzle.
  • the hose usually hangs down from the nozzle.
  • the hose is then enclosed in a blow mold that squeezes the hose together at the lower end.
  • the tube is then inflated within the mold so that the hose is given the desired shape. After a cooling period, the mold is opened and the container (hollow body) can be removed.
  • the injection blow molding process is a combination of injection molding and blow molding.
  • the injection blow molding process takes place in three stages:
  • the injection blow molding process is disclosed, for example, in Anders, S., Kaminski, A., Kappenstein, R., "Polycarbonate” in Becker, / Braun, Kunststoff-Handbuch, Volume 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag Kunststoff, Vienna 1992, pages 223 to 225.
  • the cause of this mechanical failure is often an uneven wall thickness of the container.
  • the non-uniform wall thickness of the containers which are known from the prior art, results from their manufacture, since the polycarbonate melt gives uneven wall thicknesses during processing by the extrusion blow molding process or by the injection blow molding process.
  • the present invention is therefore based on the object of providing a polycarbonate which enables the production of containers with the most homogeneous possible
  • This polycarbonate is the subject of the present invention.
  • the determination of the shear viscosity as a function of time is preferably carried out in a rotary rheometer at low shear rates.
  • the shear viscosity can also be determined in a rotary rheometer with oscillating deformation and converted to a time-dependent viscosity using common methods.
  • the structure and use of rotational rheometers are described in common textbooks. For example, in M. Pahl, W. Gleissle, H.-M. Laun: Practical Rheology of Plastics and Elastomers, VDI Verlag, 1995.
  • the expansion viscosity as a function of time is preferably determined using a Münstedt expansion rheometer.
  • the uniaxial stretching test can also be carried out with a number of other rheometers, for example with the commercially available stretching rheometer from Meissner. This is described in J. Meissner, Rheologica Acta 8, Volume 78 (1969) and in J.S. Schulze et al., Rheol. Acta, Volume 40 (2001) pages 457-466.
  • the Hencky strain ⁇ is a dimensionless quantity.
  • the expansion viscosity ⁇ E has the unit Pascal multiplied by seconds.
  • the shear viscosity ⁇ also has the unit Pascal multiplied by seconds.
  • the quotient S serves as a measure of the relative increase in the expansion viscosity ⁇ .
  • the quotient S is dimensionless.
  • S is the quotient of the expansion viscosity T
  • the total strain ⁇ (unit: dimensionless) is linked to the sample length L o (unit: meter) and the current sample length L (unit: meter) as well as the strain rate ⁇ and time t (unit: second) via:
  • a polycarbonate is particularly preferred in which the ratio S at a temperature of 200 ° C. is greater than 1.3 with a Hencky strain ⁇ of 2.0 and a strain rate range ⁇ between 0.1 and 0.01, and that it is with a
  • Hencky strain ⁇ of 2.5 and a strain rate range ⁇ between 0.1 and 0.01 is greater than 1.5.
  • the present invention furthermore relates to a container containing the polycarbonate according to the invention.
  • a container the polycarbonate for example as wall material.
  • a container made of completely different materials that only contains the polycarbonate as a filling.
  • the present invention furthermore relates to a method for producing this container by extrusion blow molding or by injection blow molding.
  • the person skilled in the art can set various parameters of the polycarbonates in a targeted manner. For example, it can influence the molar mass and the degree of branching.
  • the choice of monomers and comonomers in the case of copolycarboants or of the end groups also has an influence on the stretching rheological properties of the polycarbonates.
  • the person skilled in the art can also use suitable additives in order to obtain the desired rheological properties according to the invention.
  • the present invention is therefore based on the fact that the person skilled in the art combines the polycarbonates according to the invention with the expansion rheological ones according to the invention
  • Another object of the present invention is the production of the container according to the invention.
  • Another object of the present invention is the use of the container according to the invention.
  • the advantage of the polycarbonate according to the invention is that it allows the containers according to the invention to be produced with their advantageous properties.
  • the containers according to the invention have the advantage that they have high mechanical strength for a given amount of polycarbonate per container. They also have the advantage that they can be manufactured with a homogeneous wall thickness distribution.
  • the containers according to the invention have numerous other advantages. They are resistant to mechanical loads, i. H. unbreakable and also have an advantageous range of other mechanical properties. They have good optical properties, in particular they have high transparency. They have a high heat resistance. Because of the high thermal stability, the containers according to the invention can be cleaned with hot water or sterilized with superheated steam. They have a high resistance to the usual cleaning agents that are used, for example, for cleaning water bottles for reusable use, an area of application for the containers according to the invention. They can be produced easily and inexpensively by known methods. The good processing properties of the polycarbonate are advantageously expressed here. They show a low aging of the material in use and therefore a long service life. For a reusable use that may occur, this means many usage cycles.
  • Containers in the sense of the present invention can be used for packaging, storage or transport of liquids, solids or gases.
  • Containers for packaging, storing or transporting liquids are preferred, containers for packaging, storing or transporting water (water bottles) are particularly preferred.
  • Containers within the meaning of the invention are preferably hollow bodies with a volume of 0.1 1 to 50 1, preferably 0.5 1 to 50 1, very particularly preferably volumes of 1 1, 51, 121 and 20 1.
  • the containers preferably have an empty weight of preferably 0.1 g to 3000 g, preferably 50 g to 2000 g and particularly preferably 650 g to 900 g.
  • the wall thicknesses of the containers are preferably 0.5 mm to 5 mm, preferably 5 0.8 mm to 4 mm.
  • Containers in the sense of the present invention preferably have a length of preferably 5 mm to 2000 mm, particularly preferably 100 mm to 1000 mm.
  • the containers preferably have a maximum circumference of preferably 10 mm to 250 mm, preferably 50 mm to 150 mm and very particularly preferably 70 to 90 mm.
  • Containers in the sense of the invention preferably have a bottle neck with a length 15 of preferably 1 mm to 500 mm, preferably from 10 mm to 250 mm, particularly preferably from 50 mm to 100 mm and very particularly preferably from 70 to 80 mm.
  • the wall thickness of the bottle neck of the containers preferably varies between 0.5 mm and 10 mm, particularly preferably from 1 mm to 10 mm and very particularly preferably from 5 mm to 7 mm.
  • the diameter of the bottle neck preferably varies between 5 mm and 200 mm. 10 mm to 100 mm are particularly preferred and 45 mm to 75 mm are very particularly preferred. 5
  • the bottle bottom of the containers according to the invention has a diameter of preferably 10 mm to 250 mm, preferably 50 mm to 150 mm, and very particularly preferably 70 to 90 mm.
  • Containers in the sense of the present invention can have any geometric shape, for example they can be round, oval or polygonal or angular with for example 3 to 12 sides. Round, oval and hexagonal shapes are preferred.
  • the design of the containers can be based on any surface structure.
  • Surface structures are preferably smooth or ribbed.
  • the containers according to the invention can also have several different surface structures. Ribs or beads can run around the circumference of the container. You can have any distance or several different distances.
  • the surface structures of the containers according to the invention can have roughened or integrated structures, symbols, ornaments, coats of arms, company logos, trademarks, names, manufacturer information, material identification and or volume information.
  • the containers according to the invention can have any number of handles, which can be located on the side, above or below.
  • the handles can be on the outside and integrated in the container contour.
  • the handles can be foldable or fixed.
  • the handles can have any contour, t z. B. oval, round or polygonal.
  • the handles preferably have a length of 0.1 mm to 180 mm, preferably of 20 mm to 120 mm.
  • the containers according to the invention may contain other substances to a lesser extent, e.g. B. rubber seals or handles made of other materials.
  • the containers according to the invention are preferably produced by the extrusion blow molding process or by the injection stretch blow molding process.
  • the polycarbonates according to the invention are processed on extruders with a smooth or grooved, preferably a smooth, feed zone.
  • the drive power of the extruder is selected according to the screw diameter. An example is that with a screw diameter of 60 mm the drive power of the extruder is approx. 30 to 40 kW, with a screw diameter of 90 mm approx. 60 to 70 kW.
  • a screw diameter of 50 to 60 mm is preferred for the production of containers of volume 1 1.
  • a screw diameter of 70 to 100 mm is preferred for the production of containers of volume 20 1.
  • the length of the screws is preferably 20 to 25 times the diameter of the screw.
  • the blow molding tool is preferably set to 50 to
  • the bottom area and the jacket area can be temperature controlled separately from one another.
  • the blow molding tool is preferably closed with a pinch force of 1000 to 1500 N per cm of pinch seam length.
  • the polycarbonate according to the invention is preferably dried so that the optical quality of the containers is not impaired by streaks or bubbles and the polycarbonate is not hydrolytically degraded during processing.
  • the residual moisture content after drying is preferably less than 0.01% by weight.
  • a drying temperature of 120 ° C. is preferred. lower
  • Polycarbonates is 230 ° to 300 ° C.
  • the containers according to the invention can be used for packaging, storage or transport of liquids, solids or gases.
  • the preferred embodiment is as a container, which is used, for example, for packaging, storage or transport of liquids.
  • the embodiment as a water bottle is particularly preferred and can be used, for example, for packaging, storage or transport of water.
  • polycarbonates are preferably thermoplastically processable aromatic polycarbonates. Both homopolycarbonates and copolycarbonates can be used.
  • Particularly preferred polycarbonates are the homopolycarbonate based on bisphenol A, the homopolycarbonate based on l, l-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and the copolycarbonates based on the two monomers bisphenol A and l, l bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.
  • Polycarbonates in which up to 80 mol%, in particular from 20 mol% to 50 mol%, of the carbonate groups have been replaced by aromatic dicarboxylic acid ester groups also belong to the polycarbonates according to the invention.
  • Such polycarbonates which contain both acid residues of carbonic acid and acid residues of aromatic dicarboxylic acids built into the molecular chain, are also referred to as aromatic polyester carbonates.
  • the polycarbonates according to the invention can be prepared in a known manner from diphenols, carbonic acid derivatives, optionally chain terminators and optionally ner branches. To produce the polyester carbonates, some of the carbonic acid derivatives are replaced by aromatic dicarboxylic acids or derivatives of dicarboxylic acids. This is done in accordance with the ones to be replaced in the aromatic polycarbonates thanks to aromatic dicarboxylic acid ester structural units.
  • the polycarbonates including the polyester carbonates, preferably have average molecular weights Mw of 12,000 to 120,000 g / mol (determined by measuring the relative viscosity at 25 ° C. in methylene chloride at a concentration of 0.5 g polycarbonate per 100 ml methylene chloride). 15,000 to 80,000 g / mol are preferred, and 15,000 to 60,000 g / mol are particularly preferred.
  • Diphenols suitable for the preparation of the polycarbonates according to the invention are, for example, hydroquinone, resprcin, dihydroxydiphenyl, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxy ⁇ henyl) ethers, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides , ( ⁇ , ⁇ '-bis (hydroxyphenyl) -diisopropylbenzenes, as well as their nuclear alkylated and nuclear halogenated compounds.
  • Preferred diphenols are 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) -l-phenyl-propane, 1,1-bis (4-hydroxyphenyl) -phenyl-ethane, 2,2-bis- (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) -m / p diisopropylbenzene, 2,2-bis- (3-methyl-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis- (3,5-dimethyl-4-hydroxy ⁇ henyl) sulfone, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (3,5-dimethyl -4-hydroxyphenyl) -m / p-di
  • Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, l, l-bis (4-hydroxyphenyl) phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3rd , 5-dimethyl-4-hydroxyphenyl) -prop - n, 1, 1-bis (4-hydroxyphenyl) -cyclohexane, 1, 1-bis (4-hydroxy-phenyl) -m / p diisopropylbenzene and l, l-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.
  • Copolycarbonates are used several diphenols, of course the diphenols used (also called bisphenols), as well as all the other diphenols used (also called bisphenols), as well as all the other diphenols used (also called bisphenols), as well as all the other diphenols used (also called bisphenols), as well as all the other diphenols used (also called bisphenols), as well as all the other
  • Synthesis added chemicals and auxiliaries with those from their own Synthetic impurities may be contaminated, although it is desirable to work with raw materials that are as clean as possible.
  • Suitable chain terminators which can be used in the production of the polycarbonates are both monophenols and monocarboxylic acids.
  • Suitable monophenols are, for example, phenol, alkylphenols such as cresols, p-tert-butylphenol, pn-octylphenol, p-iso-octylphenol, pn-nonylphenol and p-iso-nonylphenol, halophenols such as p-chlorophenol, 2,4-dichlorophenol, p- Bromophenol and 2,4,6-tribromophenol, or their mixtures.
  • alkylphenols such as cresols, p-tert-butylphenol, pn-octylphenol, p-iso-octylphenol, pn-nonylphenol and p-iso-nonylphenol
  • halophenols such as p-chlorophenol, 2,4-dichlorophenol, p- Bromophenol and 2,4,6-tribromophenol, or their mixtures.
  • Suitable monocarboxylic acids are, for example, benzoic acid, alkylbenzoic acids and halobenzoic acids.
  • Preferred chain terminators are the phenols of the formula (I)
  • R 6 is H or a branched or unbranched Ci -C 8 alkyl radical.
  • the amount of chain terminator to be used is preferably 0.5 mol% to 10 mol%, based on moles of diphenols used in each case.
  • the additions of the chain terminators can be made before, during or after. the phosgenation.
  • the polycarbonates can be branched.
  • Suitable branching agents which can be used to branch the polycarbonates are the tri- or more than xifunctional compounds known in polycarbonate chemistry, in particular those with three or more than three phenolic OH groups.
  • Suitable branching agents are, for example, phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2,4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) - heptane, 1,3,5- Tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxy- ⁇ henyl) -phenylmethane, 2,2-bis- [4,4-bis - (4-hydroxyoxyphenyl) cyclohexyl] propane, 2,4-bis (4-hydroxyphenyl-isopropyl) phenol, 2,6-bis (2-hydroxy-5'-methyl-benzyl) -4-methylphenol , 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, hexa- (4- (4-hydroxyphenyl-isopropyl) phenyl) ortho
  • the amount of branching agents which may be used is preferably 0.05 mol% to 2.5 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 dissolved in an organic solvent before the phosgenation.
  • Aromatic dicarboxylic acids suitable for the production of the polyester carbonates are, for example, phthalic acid, terephthalic acid, isophthalic acid, tert-butylisophthalic acid,, 3,3'-diphenyldicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4-benzophenone dicarboxylic acid, 3,4 ' -Benzophenone dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4 , -diphenyl sulfone dicarboxylic acid, 2,2-bis (4-carboxyphenyl) propane, trimethyl-3-phenylindm-4,5'-dicarboxylic acid.
  • terephthalic acid and / or isophthalic acid are particularly preferably used.
  • Derivatives of the dicarboxylic acids are, for example, the dicarboxylic acid dihalides and the dicarboxylic acid dialkyl esters, in particular the dicarboxylic acid dichlorides and the dicarboxylic acid dimethyl esters.
  • 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.
  • the polycarbonates to be used according to the invention are preferably produced by the phase boundary process or the known melt reorganization process.
  • phosgene is preferably used as the carbonic acid derivative, in the latter case preferably diphenyl carbonate.
  • phosgene is preferably used as the carbonic acid derivative, in the latter case preferably diphenyl carbonate.
  • melt transesterification process is described in particular in H. Schnell, "Chemistry and Physis of Polycarbonates", Polymer Reviews, Volume 9, pp. 44 to 51, Interscience Publishers, New York, London, Sidney, 1964 and in DE-A 1 031 512, in US-A 3,022,272, in US-A 5,340,905 and in US-A 5,399,659.
  • the polycarbonates according to the invention can also contain the usual additives, for example pigments, UV stabilizers, thermal stabilizers, antioxidants and mold release agents, in the amounts customary for polycarbonates.
  • additives for example pigments, UV stabilizers, thermal stabilizers, antioxidants and mold release agents, in the amounts customary for polycarbonates.
  • the compositions of polycarbonate and additives or additives are also called polycarbonate molding compositions.
  • the polycarbonate molding compositions according to the invention can be processed to moldings on the customary processing machines by known methods under the processing parameters customary for polycarbonate.
  • raw materials and auxiliary materials with a low level of impurities are preferred.
  • the bisphenols and carbonic acid derivatives used should be as free as possible from alkali ions and alkaline earth ions.
  • Such pure raw materials can be obtained, for example, by recrystallizing, washing or distilling the carbonic acid derivatives, for example carbonic acid esters, and the bisphenols.
  • the reaction of the bisphenol and the carbonic acid diester can be carried out continuously or batchwise, for example in stirred tanks, thin-film evaporators, falling film evaporators, stirred tank cascades, extruders, kneaders, simple disk reactors and high-viscosity disk reactors.
  • Carbonic acid diesters that can be used to produce polycarbonates are, for example, diaryl esters of carbonic acid, the two aryl radicals preferably each having 6 to 14 carbon atoms.
  • the diesters of carbonic acid based on phenol or alkyl-substituted phenols, for example diphenyl carbonate or dicresyl carbonate, are preferably used.
  • the carbonic diesters are preferably used in an amount of 1.01 to 1.30 mol, particularly preferably in an amount of 1.02 to 1.15 mol.
  • Chain terminators This means that they limit the maximum achievable average molar mass. They can either be added together with the monomers required for the production of the polycarbonate or in a later phase of the polycarbonate synthesis. They act as monofunctional compounds in the sense of polycarbonate synthesis and therefore act as chain terminators.
  • the phenol, alkylphenols and / or arylphenols optionally used in the production of the polycarbonate are preferably used in an amount of 0.25 to 10 mol%, based on the sum of the bisphenols used in each case.
  • alkylphenols and / or arylphenols optionally used in the production of the polycarbonate lead to alkylphenyl end groups or to arylphenyl end groups.
  • other end groups can occur in the resulting polycarbonate, such as. B. phenolic OH end groups or chlorocarbonic acid end groups,
  • Arylphenols are used without the addition of other substances that can act as chain terminators.
  • Suitable other substances which can act as chain terminators are both monophenols and monocarboxylic acids.
  • Suitable monophenols are, for example Phenol, p-chlorophenol or 2,4,6-tribromophenol.
  • Suitable monocarboxylic acids are benzoic acid, alkylbenzoic acids and halobenzoic acids.
  • the preferred further substances which can act as chain terminators are phenol, p-tert. Butylphenol, cumylphenol and isooctylphenol.
  • the amount of other substances which can act as chain terminators is preferably between 0.25 and 10 mol%, based on the sum of the bisphenols used in each case.
  • a cylindrical polycarbonate sample (dimensions: diameter approximately between 4 and 5 mm, length approximately between 20 and 25 mm) is fixed at the ends using clamping jaws and clamped in an expansion rheometer.
  • the sample is then tempered by means of an oil bath, which has approximately the same density as the polycarbonate at the measuring temperature of 200 ° C.
  • the deformation is specified via the trigger rod, which is connected to the clamping jaws at one end of the sample.
  • a constant Hencky strain rate ⁇ is specified. This means that the withdrawal speed u increases exponentially with time.
  • the tensile force is measured as a function of time or total elongation.
  • the uniaxial expansion viscosity can be determined by referring the determined tensile stress to the time-dependent cross-sectional area.
  • the total elongation was not always achieved in the polycarbonates examined, since the samples can tear off or fail beforehand.
  • the uniaxial stretching test is evaluated as follows. The logarithm of the single elongation viscosity value and the triple shear viscosity value are shown together in a diagram as a function of time. It was surprisingly found that the polycarbonates in particular are suitable for the production of containers in which the expansion viscosities increase significantly compared to three times the shear viscosity (see FIG. 1). The polycarbonates in which the elongation viscosities do not increase significantly compared to three times the shear viscosity (see FIG. 2) are less or not suitable for the production of water bottles.
  • 3 ⁇ (t) for a polycarbonate which is suitable for the production of water bottles (produced according to the example according to the invention).
  • the triple shear viscosity 3 ⁇ (t) is shown as a solid line.
  • the uniaxial expansion viscosities ⁇ (t, ⁇ ) for three different expansion rates ⁇ of 0.3, 0.1 and 0.01 (unit: 1 divided by second) are shown as lines with symbols. It can be seen that for all strain rates, the strain viscosities increase sharply with time and come to be above three times the shear viscosity.
  • the triple shear viscos act 3 ⁇ (t) is shown as a solid line.
  • the uniaxial expansion viscosities ⁇ (t, ⁇ ) for three different expansion rates ⁇ of 0.2, 0.1 and 0.05 (unit: 1 divided by second) are shown as lines with symbols. It can be seen that for all strain rates the strain viscosities do not increase very sharply with time and come to be in the triple shear viscosity range.
  • the time axis t for a curve with a certain Hencky strain rate ⁇ can be converted into the Hencky strain ⁇ , since the following applies:
  • Hencky strain ⁇ Hencky strain rate ⁇ multiplied by time t
  • Fig. 4 shows the location of the measuring points on the bottles, where in the examples
  • FIG. 5 shows the course of the wall thickness shown in Table 2 in graphic form.
  • the wall thickness in mm is plotted over the measuring points 1 to 46.
  • the bottle made of the polycarbonate according to the invention shows a regular course
  • the bottle made of the polycarbonate according to the comparative example shows an irregular course (triangular symbols).
  • a polycarbonate was produced with the rheological properties according to the invention (according to the example). Water bottles with a volume of 5 gallons were then made from the plastic granulate and the
  • the alkaline phase was separated from the organic phase.
  • the organic phase was adjusted to pH 1 with dilute phosphoric acid or hydrochloric acid. It was then washed with deionized water until it was free of electrolytes.
  • the polycarbonate was isolated in a known manner using an evaporation extruder.
  • the polycarbonate thus obtained had a relative solution viscosity, measured at a concentration of 0.5 g polycarbonate in 100 ml methylene chloride at 25 ° C. of 1.325.
  • isatin biscresol As in the example above, 6.91 g of isatin biscresol and 78.4 g of phenol were used. A polycarbonate with a relative solution viscosity of 1.305 was obtained. Isatin biscresol is commercially available and has the correct name 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.
  • the bottles were produced with an extrusion blow molding machine KBS 2-20 from SIG Blowtec with the following masc equipment.
  • An extruder with a screw of 100 mm in diameter and a length of 25 D was used, which introduced little frictional heat into the material at relatively low screw speeds.
  • the plasticizing capacity was between approx. 145 to 190 kg / h with a bottle weight of approx. 750 g net and a quantity of 130 to 144 bottles / hour.
  • the plasticizing cylinder was equipped with controlled heating zones and blowers, which guarantee exact and constant temperature control.
  • the drive was carried out via a thyristor-controlled direct current unit, which ensured an even material feed and a constant torque.
  • the double heart curves offset by 180 ° create an inner and outer tube and convey the melt flow into the storage space.
  • the mandrel and nozzle in the head tool were conical.
  • the mandrel was axially displaced with respect to the conical nozzle via a thickness control program.
  • a weight-optimized Mation of the bottle and adjustment of the wall thicknesses in the corresponding bottle areas such as. B. in the floor area.
  • the extruder temperatures were 110 ° C in the feed area and between 245 ° C and 265 ° C in the individual heating zones.
  • the head temperatures ranged from 245 ° C to
  • the determined ' melt temperature was 267 ° C.
  • the average cycle time was 25.8 s +0.2 s, with a tube ejection time of 5.3 s, which corresponds to a quantity of 138 to 140 bottles per hour.
  • a conventional vertical wall thickness profile for 5-gallon polycarbonate bottles was used to control the wall thickness. The produced
  • Bottles had a net weight of 750 g to 850 g and were annealed directly afterwards using infrared radiation.
  • the tempering served for the rapid relaxation of the material and the associated process-related internal tension relief.
  • An infrared radiation oven from Process Dynamics Inc., USA with the model name Protherm 850-3, serial number: KRK was used
  • the set temperatures of the existing seven heating zones were chosen so that a surface temperature of the bottles of 130 ° C + 2 ° C was guaranteed.
  • the wall thicknesses were measured with an ultrasonic warth thickness meter from the company
  • ALPHA DFR-P a nominal frequency of 22 MHz and a coupling area of 6.4 mm are used.
  • the wall thickness measurements were carried out at 46 measuring points (see FIG. 4) directly on the bottle using an ultrasound coupling agent. Table 2
  • melts of the polycarbonates which are unsuitable for the production of water bottles, can sometimes not be deformed to high total strains ( ⁇ > 2.5) because the samples constrict and / or fail.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un récipient contenant du polycarboante qui a des propriétés rhéologiques d'expansion déterminées. L'invention a également pour objet la réalisation et l'utilisation de ce récipient.
EP03709802A 2002-03-25 2003-03-20 Polycarbonate a viscosite a l'expansion elevee Withdrawn EP1490421A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10213230A DE10213230A1 (de) 2002-03-25 2002-03-25 Polycarbonat mit hoher Dehnviskosität
DE10213230 2002-03-25
DE10229594 2002-07-02
DE2002129594 DE10229594A1 (de) 2002-07-02 2002-07-02 Behälter aus Kunststoff mit homogener Wanddicke
PCT/EP2003/002901 WO2003080706A1 (fr) 2002-03-25 2003-03-20 Polycarbonate a viscosite a l'expansion elevee

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EP1490421A1 true EP1490421A1 (fr) 2004-12-29

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EP03709802A Withdrawn EP1490421A1 (fr) 2002-03-25 2003-03-20 Polycarbonate a viscosite a l'expansion elevee

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JP2010247510A (ja) * 2009-03-24 2010-11-04 Tohcello Co Ltd 透明耐熱ポリ乳酸系成形体の成形方法
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BR112013020026B1 (pt) 2011-02-07 2021-03-02 Swimc Llc artigo, composição de revestimento, e, método
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US10316211B2 (en) 2012-08-09 2019-06-11 Swimc Llc Stabilizer and coating compositions thereof
ES2849526T3 (es) 2012-08-09 2021-08-19 Swimc Llc Composiciones para contenedores y otros artículos y métodos de utilización de los mismos
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MXPA04009267A (es) 2005-01-25
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AU2003214142A1 (en) 2003-10-08
WO2003080317A1 (fr) 2003-10-02
RU2004131569A (ru) 2005-06-27
RU2004131566A (ru) 2005-06-27
US20030181628A1 (en) 2003-09-25
EP1490206A1 (fr) 2004-12-29
PL372483A1 (en) 2005-07-25
CN1655919A (zh) 2005-08-17
CN1656143A (zh) 2005-08-17
KR20040105812A (ko) 2004-12-16
US20030209553A1 (en) 2003-11-13
CA2480097A1 (fr) 2003-10-02
JP2005520898A (ja) 2005-07-14
BR0303578A (pt) 2005-02-01
AU2003214142B2 (en) 2008-12-18
AU2003214141A1 (en) 2003-10-08
WO2003080706A1 (fr) 2003-10-02
US6713594B2 (en) 2004-03-30
TW200400981A (en) 2004-01-16
CA2480274A1 (fr) 2003-10-02
MXPA04009198A (es) 2004-11-26
PL372350A1 (en) 2005-07-11
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KR20040091777A (ko) 2004-10-28

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