EP1660425A1 - Polycarbonates et copolycarbonates ayant une absorption d'eau reduite et une aptitude a l'ecoulement amelioree, leur production et leur utilisation - Google Patents

Polycarbonates et copolycarbonates ayant une absorption d'eau reduite et une aptitude a l'ecoulement amelioree, leur production et leur utilisation

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Publication number
EP1660425A1
EP1660425A1 EP04764166A EP04764166A EP1660425A1 EP 1660425 A1 EP1660425 A1 EP 1660425A1 EP 04764166 A EP04764166 A EP 04764166A EP 04764166 A EP04764166 A EP 04764166A EP 1660425 A1 EP1660425 A1 EP 1660425A1
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Prior art keywords
mol
polycarbonates
hydroxyphenyl
bisphenol
copolycarbonates
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German (de)
English (en)
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Helmut-Werner Heuer
Rolf Wehrmann
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Covestro Deutschland AG
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Bayer MaterialScience AG
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Publication of EP1660425A1 publication Critical patent/EP1660425A1/fr
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    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/252—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers
    • G11B7/253—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates
    • G11B7/2533—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins
    • G11B7/2534—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of layers other than recording layers of substrates comprising resins polycarbonates [PC]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
    • C07C39/17—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings containing other rings in addition to the six-membered aromatic rings, e.g. cyclohexylphenol
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to polycarbonates and copolycarbonates with reduced water absorption and improved flowability, processes for their production and their use in the production of certain products, and the products obtainable therefrom.
  • the invention further relates to new bisphenols and processes for their preparation and their use.
  • Aromatic polycarbonates belong to the group of engineering thermoplastics. They are characterized by the combination of the technologically important properties of transparency, heat resistance and toughness.
  • the alkali salts of bisphenols are reacted with phosgene in a two-phase mixture.
  • the molecular weight can be determined by the amount of monophenols such as e.g. Phenol or tert-butylphenol can be controlled. These reactions almost exclusively produce linear polymers. This can be demonstrated by end group analysis.
  • branching agents as a rule multiply hydroxylated compounds, branched polycarbonates are also obtained.
  • the bisphenols are reacted with diaryl carbonates, usually diphenyl carbonate, in the presence of catalysts such as alkali salts, ammonium or phosphonium compounds.
  • melt transesterification process is described, for example, in Encyclopedia of Polymer Science, Vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, Vol. 9, John Wiley and Sons, Inc. (1964) and DE-C 1031 512.
  • the polycarbonates or copolycarbonates described in the prior art are unsatisfactory due to their water absorption and the resulting limited dimensional stability, or they have the disadvantage that when used as data carrier materials they reading wavelengths in the blue or blue-green range are limited or may not be optimal.
  • the object was therefore to make available polycarbonates or copolycarbonates and processes for their preparation which avoid these disadvantages.
  • This task is surprisingly achieved by using the bisphenol of the general formulas (1) according to the invention.
  • R * and R ⁇ for hydrogen or linear or branched C 1 -C alkyl preferably for hydrogen or linear or branched CC 6 alkyl, particularly preferably for hydrogen or linear or branched C 1 -C 4 alkyl, very particularly preferably for hydrogen and C alkyl stand,
  • R4 to Rl2 are hydrogen or linear or branched -Cjo alkyl, preferably hydrogen or linear or branched CC 6 alkyl, particularly preferably hydrogen or linear or branched Cj-C alkyl, very particularly preferably hydrogen and C alkyl and
  • n and m independently of one another represent an integer from 0 to 10, preferably from 1 to 8, particularly preferably from 1 to 6, very particularly preferably from 2 to 4.
  • n stands for an integer from 1 to 6.
  • melt viscosity of the polycarbonates obtained had lower values than the prior art, both at low and at higher shear rates (with an otherwise comparable molecular weight). This is especially for the production of larger injection molded parts, such as Car windows, of importance. This makes it easier to fill the molds with common injection molding machines.
  • bisphenols according to the invention can be prepared from phenol derivatives and ketones in an acid-catalyzed reaction.
  • the synthesis of the bisphenols according to the invention is preferably carried out as a condensation reaction of corresponding phenols of the formulas A and B.
  • R ⁇ to R ⁇ 2 have the meanings given above, but not necessarily in the presence of a sulfur-containing compound, preferably with the aid of an acid catalyst, particularly preferably an acidic ion exchanger or hydrochloric acid at temperatures preferably between 0 and 100 ° C with a stoichiometric ratio of Phenol derivative to ketone derivative from 15 to 1 to 2 to 1.
  • a sulfur-containing compound preferably with the aid of an acid catalyst, particularly preferably an acidic ion exchanger or hydrochloric acid at temperatures preferably between 0 and 100 ° C with a stoichiometric ratio of Phenol derivative to ketone derivative from 15 to 1 to 2 to 1.
  • the phenols of the formulas A and B are known or can be prepared by processes known from the literature, for example by alkylation according to Friedel Crafts (organic, basic organic chemistry internship, corrected reprint of the 20th edition, Wiley-VCH, Weinheim, p. 355, 1999). Many phenols are also commercially available (suppliers e.g. Aldrich, Fluka, Acros, etc.).
  • ketones of the formula C are likewise known or can be prepared by processes known from the literature, for example by oxidation of the corresponding alcohols (see also: Cesare Ferri, reactions in organic synthesis, technical and preparative preparation and conversion processes, Georg Thieme Verlag Stuttgart , P.407 ff, 1978.). A great many ketones are also commercially available (suppliers e.g. Aldrich, Fluka, Acros, Alfa, Avocado etc.).
  • the very particularly preferred compound 4- (2,2,6-trimethylcyclohexyl) -2-butanone of the formula C can be obtained, for example, from Avocado, from Alfa (A Johnson Matthey Company, Düsseldorf, Germany), ChemSampCo, Inc. Trenton, NJ, USA or from Pfaltz & Bauer, Inc. Waterbury, CT, USA.
  • the condensation is very particularly preferably carried out using hydrochloric acid as the acid catalyst at temperatures between 0 and 60 ° C. with a stoichiometric ratio of phenol derivative to ketone derivative of 10 to 1, with a mercapto or thiocarboxylic acid compound (eg dodecyl mercaptan, mercaptopropionic acid or thioacetic acid), is present, preferably only in about 0.01 to 25% based on the ketone compound.
  • the hydrochloric acid is very particularly preferably introduced as an HCl gas.
  • the condensation can be carried out in bulk or in solution.
  • Inert solvents such as chlorinated hydrocarbons such as methylene chloride, dichloroethane or toluene, xylenes or chlorobenzenes are used.
  • the reaction is particularly preferably carried out in bulk with an excess of phenol.
  • the present invention also relates to polycarbonates or copolycarbonates which have been produced using the bisphenols according to the invention and the corresponding production processes.
  • the polycarbonates or copolycarbonates prepared using the bisphenols according to the invention and containing the structural units -O-D-O- derived from the compounds of the formulas 1 to 3 are exemplified but not exclusively by the general formulas (4a) and (4b),
  • the OEO radical stands for any diphenolate radicals in which -E- is, independently of one another, an aromatic radical with 6 to 40 C atoms, which may contain one or more aromatic or condensed aromatic nuclei, optionally containing heteroatoms, and optionally with C ⁇ - Ci2-alkyl radicals or halogen is substituted and aliphatic radicals
  • cycloaliphatic may contain cal residues, aromatic nuclei or heteroatoms as bridge members, and in which k is an integer between 1 and 1000, preferably between 1 and 800, particularly preferably between 1 and 600 and very particularly preferably between 1 and 500 and particularly preferably between 1 and 300 stands for, and m stands for a fractional number z / k and n stands for a fractional number (kz) / k where z stands for numbers between 1 and k.
  • Preferred diphenolate units of the copolycarbonates according to the invention are derived from general structures of the formula (5)
  • R 2 ⁇ and R 2 ⁇ independently of one another for H, linear or branched C 8 alkyl or alkoxy radicals, halogen such as Cl or Br or for an optionally substituted aryl or aralkyl radical, preferably for H or linear or branched C 1 -C 2 alkyl, particularly preferably H or C 8 alkyl radicals and very particularly preferably H or methyl,
  • R3 and R4 stand for linear or branched C ⁇ -Ci Q alkyl
  • X for a single bond, -SO 2 -, -CO-, -O-, -S-, a C - to Cg-alkylene, C2- to C5-alkylidene, C5 to Cg-cycloalkylidene radical, which with C1 - to Cg-alkyl, preferably methyl or ethyl radicals, or a Cg to Ci2-arylene radical, which may optionally be fused with further heteroatoms containing aromatic rings, and
  • o stands for an integer between 1 and 1000, preferably between 1 and 800, particularly preferably between 1 and 600 and very particularly preferably between 1 and 500 and particularly preferably between 1 and 300, and p for a fractional number z / o and q stands for a fraction (oz) / o where z stands for numbers between 1 and o and
  • n and m have the meaning given above.
  • the diphenolate residues OEO in formula (4b) and the general diphenolate residues in formula (5) are particularly preferably derived from the suitable diphenols mentioned below.
  • diphenols which, in addition to the bisphenols according to the invention are based on the general formulas (4) and (5), are hydroquinone, resorcinol, dihydroxybiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, ⁇ , ⁇ '-bis (hydroxyphenyl) diisopropylbenzenes, and their nuclear alkylated and nuclear halogenated compounds, and also called ⁇ , ⁇ -bis (hydroxyphenyl) polysiloxanes.
  • Preferred diphenols are, for example, 4,4'-dihydroxybiphenyl (DOD), 4,4'-dihydroxybiphenyl ether (DOD ether), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), l, l- Bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC), l, l-bis (4-hydroxyphenyl) cyclohexane, 2,4-bis (4-hydroxyphenyl) -2- methylbutane, l, l-bis (4-hydroxyphenyl) -l-phenylethane, 1,1- bis [2- (4-hydroxyphenyl) -2-propyl] benzene, l, 3-bis [2- (4- hydroxyphenyl) -2-propyl] benzene (bisphenol M), 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, Bis (3,
  • diphenols are, for example, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 4,4'-dihydroxybiphenyl (DOD), 4,4'-dihydroxybiphenyl ether (DOD ether), 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene (bisphenol M), 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, l, l-bis (4-hydroxyphenyl ) -l-phenylethane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, l, l- Bis (4-hydroxyphenyl) cyclohexane and l, l-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC).
  • bisphenol A 2,2-bis (4-hydroxyphenyl) propane
  • DOD 4,4'-
  • the diphenols can be used both alone and in a mixture with one another; both homopolycarbonates and copolycarbonates are included.
  • the diphenols are known from the literature or can be prepared by processes known from the literature (see, for example, HJ Buysch et al., Ullmann's Encyclopedia of Industrial Chemistry, VCH, New York 1991, 5th Ed., Vol. 19, p. 348).
  • the polycarbonates or copolycarbonates can also be branched.
  • certain small amounts preferably amounts between 0.05 and 5 mol%, particularly preferably 0.1 to 3 mol%, very particularly preferably 0.1 to 2 mol%, based on the moles of diphenols used, of trifunctional compounds such as eg isatin biscresol (EBK) or phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2; 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) heptane; l, 3,5-tri- (4-hydroxy ⁇ henyl) benzene; l, l, l-tri- (4-hydroxyphenyl) ethane (THPE); Tri- (4-hydroxyphenyl) phenylmethane; 2,2-bis [4,4-bis (4-hydroxyphenyl) -cyclohexyl] -propane; 2,4-bis (4-hydroxyphenyl-isopropyl) phenol; 2,6-bis-bis-
  • the present invention further relates to a process for the preparation of the polycarbonates and copolycarbonates of the formulas (4a), (4b) and (5) according to the invention, characterized in that bisphenols and any branching agents are dissolved in aqueous alkaline solution and, if appropriate, in a solvent dissolved carbonate source such as phosgene in a two-phase mixture of an aqueous alkaline solution, an organic solvent and a catalyst, preferably an amine compound.
  • the reaction can also be carried out in several stages.
  • Such processes for the production of polycarbonate are basically two-phase interface processes e.g. from H. Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York 1964 pp. 33 ff. and on Polymer Reviews, Vol. 10, "Condensation Polymers by Interfacial and Solution Methods", Paul W Morgan, Interscience Publishers, New York 1965, chap. VLI, p. 325 known and therefore the basic conditions familiar to the expert.
  • the concentration of the bisphenols in the aqueous alkaline solution is 2 to 25% by weight, preferably 2 to 20% by weight, particularly preferably 2 to 18% by weight and very particularly preferably 3 to 15% by weight.
  • the aqueous alkaline solution consists of water in which hydroxides of alkali or alkaline earth metals are dissolved. Sodium and potassium hydroxides are preferred.
  • the volume ratio of aqueous alkaline solution to organic solvent is 5:95 to 95: 5, preferably 20:80 to 80:20, particularly preferably 30:70 to 70:30 and very particularly preferably 40:60 to 60 : 40th
  • the molar ratio of bisphenol to phosgene is less than 1:10, preferably less than 1: 6, particularly preferably less than 1: 4 and very particularly preferably less than 1: 3.
  • the concentration of the branched polycarbonates and copolycarbonates according to the invention in the organic phase is 1.0 to 25% by weight, preferably 2 to 20% by weight, particularly preferably 2 to 18% by weight and very particularly preferably 3 to 15% by weight. %.
  • the concentration of the amine compound based on the amount of bisphenol used is 0.1 to 10 mol%, preferably 0.2 to 8 mol%, particularly preferably 0.3 to 6 mol% and very particularly preferably 0.4 to 5 mol%.
  • the carbonate source is phosgene, diphosgene or triphosgene, preferably phosgene.
  • phosgene diphosgene or triphosgene, preferably phosgene.
  • a solvent can optionally be dispensed with and the phosgene can be introduced directly into the reaction mixture.
  • Tertiary amines such as triethylamine or N-alkylpiperidines can be used as the catalyst.
  • Trialkylamines and 4- (dimethylamino) pyridine are suitable as catalysts.
  • Triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutylamine, N-methylpiperidine, N-ethylpiperidine and N-propylpiperidine are particularly suitable.
  • Halogenated hydrocarbons such as methylene chloride and / or chlorobenzene, dichlorobenzene, trichlorobenzene or mixtures thereof or aromatic hydrocarbons such as e.g. Toluene or xylenes in question.
  • the reaction temperature can be -5 ° C to 100 ° C, preferably 0 ° C to 80 ° C, particularly preferably 10 ° C to 70 ° C and very particularly preferably 10 ° C to 60 ° C.
  • the polycarbonates according to the invention can also be produced by the melt transesterification process.
  • the melt transesterification process is described, for example, in the Encyclopedia of Polymer Science, Vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, Vol. 9, John Wiley and Sons, Inc. (1964) and DE -C 10 31 512.
  • the aromatic dihydroxy compounds already described in the phase interface process are used, with carbonic acid diesters with the aid of suitable catalysts and
  • Carbonic acid diesters for the purposes of the invention are those of the formulas (6) and (7)
  • Diphenyl carbonate tert-butylphenylphenyl carbonate, di-tert-butylphenyl carbonate, phenylphenol phenyl carbonate, di-phenylphenol carbonate, cumylphenyl phenyl carbonate,
  • the proportion of carbonic acid ester is 100 to 130 mol%, preferably 103 to 120 mol%, particularly preferably 103 to 109 mol%, based on the dihydroxy compound.
  • onium salts As catalysts in the context of the invention, basic catalysts such as, for example, alkali metal and alkaline earth metal hydroxides and oxides, but also ammonium or phosphonium salts, hereinafter referred to as onium salts, are used in the melt transesterification process as described in the literature mentioned. Onium salts are preferably used, particularly preferably phosphonium salts. Phosphonium salts for the purposes of the invention are those of the formula (8)
  • R 1 '4 the same or different C ⁇ -C ⁇ 0 alkyls, C 6 -C ⁇ 0 aryls, C 7 -C ⁇ 0 aralkyls or C 5 -C 6 - Cycloalkyls can be, preferably methyl or C 6 -C ⁇ 4 aryls , particularly preferably methyl or phenyl, and
  • X can be an anion such as hydroxide, sulfate, hydrogen sulfate, hydrogen carbonate, carbonate, a halide, preferably chloride, or an alcoholate of the formula OR, where RC 6 -C ] 4 - aryl or C 7 -C ⁇ 2 aralkyl, preferably phenyl, preferred catalysts are
  • the catalysts are preferably used in amounts of 10 "8 to 10 " 3 mol, based on one mol of bisphenol, particularly preferably in amounts of 10 "7 to 10 " 4 mol.
  • Additional catalysts can be used alone or optionally in addition to the onium salt to increase the rate of polymerization.
  • These include salts of alkali metals and alkaline earth metals, such as hydroxides, alkoxides and aryloxides of lithium, sodium and potassium, preferably hydroxide, alkoxide or aryloxide salts of sodium. Most preferred are sodium hydroxide and sodium phenolate.
  • the amounts of the cocatalyst can range from 1 to 200 ppb, preferably 5 to 150 ppb and most preferably 10 to 125 ppb, each calculated as sodium.
  • the transesterification reaction of the aromatic dihydroxy compound and the carbonic acid diester in the melt is preferably carried out in two stages.
  • the aromatic dihydroxy compound and the carbonic acid diester are melted at temperatures of 80 to 250 ° C., preferably 100 to 230 ° C., particularly preferably 120 to 190 ° C. under normal pressure in 0 to 5 hours, preferably 0.25 to 3 hours instead.
  • the oligocarbonate is prepared from the aromatic dihydroxy compound and the carbonic acid diester by applying a vacuum (up to 2 mm Hg) and increasing the temperature (up to 260 ° C.) by distilling off the monophenol. The main amount of vapors is generated in the process.
  • the oligocarbonate thus produced has an average weight molar mass M w (determined by measuring the relative solution viscosity in dichloromethane or in mixtures of equal amounts by weight of phenol / o-dichlorobenzene calibrated by light scattering) in the range from 2000 g / mol to 18,000 g / mol from 4,000 g / mol to 15,000 g / mol.
  • the polycarbonate is produced in the polycondensation by further increasing the temperature to 250 to 320 ° C., preferably 270 to 295 ° C. and a pressure of ⁇ 2 mm Hg. This removes the rest of the vapors from the process.
  • the catalysts can also be used in combination (two or more) with one another.
  • alkali / alkaline earth metal catalysts When using alkali / alkaline earth metal catalysts, it may be advantageous to add the alkali / alkaline earth metal catalysts at a later point in time (for example after the oligocarbonate synthesis in the polycondensation in the second stage).
  • the reaction of the aromatic dihydroxy compound and the carbonic acid diester to form the polycarbonate can be carried out batchwise or preferably continuously in the sense of the process according to the invention, for example in stirred tanks, thin-film evaporators, falling film evaporators, stirred tank cascades, extruders, kneaders, simple disk reactors and high-viscosity disk reactors.
  • branched poly- or copolycarbonates can be produced by using multifunctional compounds.
  • the molecular weights Mw of the branched polycarbonates and copolycarbonates according to the invention are in the range from 6000 to 200000 g / mol, preferably between 6000 and 100000 g / mol, particularly preferably between 10,000 and 80,000 g / mol and very particularly preferably between 12000 and 70,000 g / mol (determined by means of GPC and polycarbonate calibration).
  • Preferred, particularly preferred or very particularly preferred are embodiments which make use of the parameters, compounds, definitions and explanations mentioned under preferred, particularly preferred or very particularly preferred or, preferably, etc.
  • polycarbonates and copolycarbonates according to the invention can be worked up in a known manner and processed into any shaped articles, for example by extrusion, injection molding or extrusion blow molding.
  • aromatic polycarbonates and / or other aromatic polyester carbonates and / or other aromatic polyesters can be mixed in a known manner with the polycarbonates and copolycarbonates according to the invention, for example by compounding.
  • thermoplastics such as fillers, UV stabilizers, thermal stabilizers, antistatic agents and pigments
  • additives customary for these thermoplastics can also be added to the polycarbonates and copolycarbonates according to the invention in the customary amounts; 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 (for example 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 the corresponding chapters of the "Plastics Additives Handbook", ed. Hans Doubt, 5 * Edition 2000, Hanser Publishers, Kunststoff.).
  • polycarbonates and copolycarbonates according to the invention can be processed into extrudates of any shape wherever known polycarbonates, polyester carbonates and polyesters are used. Due to their property profile, they are particularly suitable as materials for the injection molding of larger molded parts, for example car windows. Due to the low water absorption and the associated improved dimensions Onsstability are also particularly suitable as substrate materials for optical data storage such as CD, CD-R, DVD, DVD-R, Blu-ray Disc or Advanced Optical Disc (AOD), but are also for example as films in the electrical sector as molded parts in vehicle construction and Can be used as plates for covers in the security area. Further possible applications of the polycarbonates according to the invention are:
  • Safety panes which are known to be required in many areas of buildings, vehicles and aircraft, and as shields for helmets.
  • polycarbonates with a glass fiber content are used, which may additionally contain about 1 to 10% by weight of MoS 2 , based on the total weight.
  • optical device parts in particular lenses for photo and film cameras (see for example DE-A 2 701 173).
  • a light transmission carrier in particular as an optical fiber cable (see for example EP-A 0 089 801).
  • headlight lamps so-called “head-lamps”, flare lenses or inner lenses, and linear lights.
  • dialyzers For medical applications, e.g. Oxygenators, dialyzers.
  • Safety glasses, visors or optical corrective glasses are provided.
  • Chip boxes and chip carriers 31 are Chip boxes and chip carriers 31.
  • B. stable mast doors or animal cages are other applications, such as B. stable mast doors or animal cages.
  • the excess phenol was first in a water jet vacuum and finally at a max. Distilled temperature of 150 ° C in an oil pump vacuum with the rotary vane pump.
  • the crude product was finally taken up in methylene chloride and washed neutral with water. After concentrating the organic phase and drying the residue, 122 g of product were obtained, which was still contaminated.
  • the crude product was taken up in 150 ml of petroleum ether and boiled for 2 hours. The raw product brightened increasingly. After decanting, it was again twice with 150 ml of n-hexane for 30 min. boiled for a long time. After decanting, both products are obtained which have been dried in a drying cabinet at 50 ° C.
  • Example 2 The polycarbonate obtained in Example 2 is rheologically examined at 290 ° C. The following data is obtained: Shear cases s -1 ] Viscosity
  • the ratio of the GC-MS mass signals of the various (silylated) components is 0.600 (educt): 1.295 (monosubst. Product): 1.0 (disubst. Product).
  • the water content is determined after various storage times using quantitative Karl Fischer titration (coulometric titration).
  • Makrolon CD 2005 Bayer AG n.a. 0.32 - 0.34 2a) 0.12 / 0.15 0.15 / 0.16 5a) 0.12 / 0.14 0.12 / 0.13 9a) 0.21 / 0.23 0, 20 / 0.21

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  • Materials Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des polycarbonates et des copolycarbonates ayant une absorption d'eau réduite et une aptitude à l'écoulement améliorée, leur procédé de production et leur utilisation pour la production de produits déterminés ainsi que les produits ainsi obtenus. L'invention concerne également de nouveaux bisphénols et leur procédé de production et d'utilisation.
EP04764166A 2003-08-23 2004-08-16 Polycarbonates et copolycarbonates ayant une absorption d'eau reduite et une aptitude a l'ecoulement amelioree, leur production et leur utilisation Withdrawn EP1660425A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10338907A DE10338907A1 (de) 2003-08-23 2003-08-23 Polycarbonate und Copolycarbonate mit verminderter Wasseraufnahme und verbesserter Fließfähigkeit, ihre Herstellung und Verwendung
PCT/EP2004/009174 WO2005021478A1 (fr) 2003-08-23 2004-08-16 Polycarbonates et copolycarbonates ayant une absorption d'eau reduite et une aptitude a l'ecoulement amelioree, leur production et leur utilisation

Publications (1)

Publication Number Publication Date
EP1660425A1 true EP1660425A1 (fr) 2006-05-31

Family

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EP04764166A Withdrawn EP1660425A1 (fr) 2003-08-23 2004-08-16 Polycarbonates et copolycarbonates ayant une absorption d'eau reduite et une aptitude a l'ecoulement amelioree, leur production et leur utilisation

Country Status (8)

Country Link
US (1) US7132497B2 (fr)
EP (1) EP1660425A1 (fr)
JP (1) JP2007503408A (fr)
KR (1) KR20060132546A (fr)
CN (1) CN100393681C (fr)
DE (1) DE10338907A1 (fr)
TW (1) TW200526566A (fr)
WO (1) WO2005021478A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008023800A1 (de) * 2008-05-15 2009-11-19 Bayer Materialscience Ag Alkylphenol zur Einstellung des Molekulargewichtes und Copolycarbonat mit verbesserten Eigenschaften

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US2503196A (en) * 1949-03-30 1950-04-04 Dow Chemical Co Bis-phenols
US2602822A (en) * 1951-07-23 1952-07-08 Shell Dev Production of bis (hydroxyphenyl) compounds
US3220977A (en) * 1961-09-14 1965-11-30 Eastman Kodak Co Linear polyesters from 4,4'-(cyclohexylmethylene)diphenols
US4520187A (en) * 1982-12-17 1985-05-28 General Electric Company Polycarbonates and polyester carbonates exhibiting improved heat resistance
DE3343898A1 (de) * 1982-12-17 1984-06-20 General Electric Co., Schenectady, N.Y. Thermoplastische polymere zubereitungen mit verbesserter waermebestaendigkeit
DE4001932A1 (de) * 1990-01-24 1991-07-25 Bayer Ag 1,1-bicyclo-substituierte fluorhaltige cyclopentane und verfahren zu deren herstellung
JP3077855B2 (ja) * 1992-06-30 2000-08-21 キヤノン株式会社 電子写真感光体、およびそれを用いた電子写真装置およびファクシミリ
US5378570A (en) * 1993-01-05 1995-01-03 Fuji Xerox Co., Ltd. Electrophotographic photoreceptor
JPH11149166A (ja) * 1997-11-18 1999-06-02 Fuji Xerox Co Ltd 電子写真感光体及びそれを用いた電子写真装置
JPH11184101A (ja) * 1997-12-18 1999-07-09 Fuji Xerox Co Ltd 電子写真感光体及びそれを用いた電子写真装置
JP2000265075A (ja) * 1999-03-16 2000-09-26 Teijin Chem Ltd 制振性熱可塑性樹脂組成物
JP2003178489A (ja) * 2001-12-07 2003-06-27 Hitachi Maxell Ltd 情報記録媒体

Non-Patent Citations (1)

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Title
See references of WO2005021478A1 *

Also Published As

Publication number Publication date
JP2007503408A (ja) 2007-02-22
US20050054808A1 (en) 2005-03-10
WO2005021478A1 (fr) 2005-03-10
DE10338907A1 (de) 2005-03-17
CN100393681C (zh) 2008-06-11
CN1871198A (zh) 2006-11-29
US7132497B2 (en) 2006-11-07
KR20060132546A (ko) 2006-12-21
TW200526566A (en) 2005-08-16

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