EP3174933A1 - Compositions de copolycarbonate comportant des structures de ramification et des oligomères cycliques et présentant des propriétés rhéologiques améliorées - Google Patents

Compositions de copolycarbonate comportant des structures de ramification et des oligomères cycliques et présentant des propriétés rhéologiques améliorées

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Publication number
EP3174933A1
EP3174933A1 EP15745461.2A EP15745461A EP3174933A1 EP 3174933 A1 EP3174933 A1 EP 3174933A1 EP 15745461 A EP15745461 A EP 15745461A EP 3174933 A1 EP3174933 A1 EP 3174933A1
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EP
European Patent Office
Prior art keywords
copolycarbonate
alkyl
component
formula
composition according
Prior art date
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EP15745461.2A
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German (de)
English (en)
Inventor
Rolf Wehrmann
Helmut Werner Heuer
Anke Boumans
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Covestro Intellectual Property GmbH and Co KG
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Covestro Deutschland AG
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Publication of EP3174933A1 publication Critical patent/EP3174933A1/fr
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • Copolycarbonate compositions having branching structures and cyclic oligomers and improved rheological properties
  • This invention relates to copolycarbonate compositions having branching structures and cyclic oligomers which have improved flow properties, their use for the preparation of blends, moldings and moldings obtainable therefrom.
  • Copolycarbonates belong to the group of engineering thermoplastics. You will find versatile applications in the electrical and electronics sector, as housing material of luminaires and in applications where special thermal and mechanical properties are required, such as hair driers, automotive applications, plastic covers, diffusers or light guides and lamp covers or bezels. These copolycarbonates can be used as blend partners for other thermoplastics.
  • EP 2 333 012 discloses compositions comprising a copolycarbonate based on bisphenol A and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC).
  • DE 102004020673 describes copolycarbonates with improved flowability based on bisphenols having an ether or thioether linkage.
  • EP 0 953 605 describes linear polycarbonate compositions with improved flow behavior, characterized in that cyclic oligocarbonates in large quantities, for. B. 0.5% to 4% are added and homogenized by means of a twin-screw extruder in the matrix of a linear BPA polycarbonate at 285 ° C. The fluidity decreases with rising "
  • compositions comprising aromatic polycarbonate compositions which have an improved flowability with constant heat resistance.
  • compositions of special (high-Tg) copolycarbonates (component A, T g : glass transition temperature) with a further (co) polycarbonate (component B) always have improved flowability when special oligomeric structures and certain Branched structures are contained in small amounts in component B or in both components.
  • the heat resistance (Vicat temperature) remains virtually unchanged.
  • copolycarbonate compositions or blends are mixtures of at least one copolycarbonate and at least one further copolycarbonate or polycarbonate, which may optionally be provided with additives (component C).
  • the present invention therefore provides copolycarbonate compositions containing as a component
  • R 1 is hydrogen or C 1 -C 10 -alkyl, preferably hydrogen
  • R is C 1 -C 4 -alkyl, preferably methyl, n is 0, 1, 2 or 3, preferably 3; as a component
  • R 3 is H, linear or branched C 1 -C 10 -alkyl, preferably linear or branched C 1 -C 6 -alkyl, particularly preferably for linear or branched C 1 -C 4 -alkyl, very particularly preferably for H or C 1-6 -alkyl (methyl) stands; and in which R 4 is linear or branched C 1 -C 10 -alkyl, preferably linear or branched C 1 -C 6 -alkyl, particularly preferably linear or branched C 1 -C 4 -alkyl, very particularly preferably C 1-alkyl (methyl), Co) polycarbonate of component B) has no monomer units of formula (1) and the sum of the wt .-% of components A and B in the composition 100% by weight results; characterized in that component B contains at least one cyclic oligomer of general formula (I) in a total amount of less than 0.90% by weight, based on the weight of component B,
  • n is an integer from 2 to 6 and Z is a radical of the formula (Ia)
  • R 5 and R 6 are each independently H, Ci-Cs-alkyl, preferably H or Ci alkyl, particularly preferably hydrogen or methyl, and X is a single bond, C 1 - to C 6 -alkylene, C 2 - to C 6 -alkylidene or C 5 - to C 6 -cycloalkylidene which may be substituted by C 1 - to C 6 -alkyl, preferably methyl or ethyl, preferably a single bond or Isopropylidene, stands; and component B has one or more structures of the general formulas (II) to (V),
  • phenyl rings independently of one another may be monosubstituted or disubstituted by C 1 -C 5 -alkyl, halogen, such as chlorine or bromine, preferably C 1 -C 1 -alkyl, especially methyl
  • X is a single bond, C 1 - to C 6 -alkylene, C 2 - to C 6 -alkylidene or C 5 - to C 6 -cycloalkylidene which may be substituted by C 1 - to C 6 -alkyl, preferably methyl or ethyl, preferably a single bond or Isopropylidene, stands; wherein the amount of structures (I) can be determined by precipitation and subsequent quantitative HPLC and wherein the presence of the structures of formulas (II) to (V) in component B after total saponification of the copolycarbonate composition is determined by HPLC.
  • C 1 -C 4 -alkyl is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, C 1 -C 6 -alkyl, moreover, for example, n- Pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neo-pentyl, 1-ethylpropyl, cyclohexyl, cyclopentyl, n-hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1, 2-dimethylpropyl, 1 - Methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbut
  • alkyl radicals in the corresponding hydroxyalkyl or aralkyl or alkylaryl radicals are, for example, the alkylene radicals corresponding to the preceding alkyl radicals.
  • Aryl represents a carbocyclic aromatic radical having 6 to 34 skeleton carbon atoms.
  • aromatic part of an arylalkyl radical also called aralkyl radical
  • aryl constituents of more complex groups such as e.g. Arylcarbonyl.
  • C6-C3-Ar1 examples include phenyl, 0-, p-, m-tolyl, naphthyl, phenanthrenyl, anthracenyl or fluorenyl.
  • Arylalkyl or aralkyl in each case independently denotes a straight-chain, cyclic, branched or unbranched alkyl radical as defined above which may be monosubstituted, polysubstituted or completely substituted by aryl radicals as defined above.
  • the amount of the cyclic oligomers of the general formula (I) can be determined as follows: a sample of the polycarbonate composition is dissolved in methylene chloride. By adding acetone, the majority of the polymer is precipitated. The undissolved portions are filtered off, the filtrate is concentrated to dryness. The dry residue is dissolved with THF and the oligomers are determined by HPLC (High Pressure Liquid Chromatography) with UV detection.
  • HPLC High Pressure Liquid Chromatography
  • the cyclic oligomers of the general formula (I) are in a total amount of less than 0.90 wt .-%, preferably 0.2 wt .-% to 0.85 wt .-%, particularly preferably 0.2 wt .-% to 0.80 wt .-% and most preferably 0.3 wt .-% to 0.75 wt .-% in the component B (based on the total weight of component B and determined by precipitation and subsequent quantitative HPLC).
  • the above-defined structures (II) to (V) occur in different amounts and ratios to each other. Their amount can be determined by total saponification of the polycarbonate composition.
  • the low molecular weight degradation products of the formulas (IIa) to (Va) characteristic of the respective structure exemplified by bisphenol A as diphenol, i. X is isopropylidene, formed, the amount of which is determined by HPLC.
  • the determination of the defect structures (II) to (V) can thus be carried out as follows: a sample of the polycarbonate composition is saponified with sodium methylate under reflux. The saponification solution is acidified and concentrated to dryness. The dry residue is dissolved with acetonitrile and the phenolic compounds (IIa) to (Va) are fractionated by HPLC with UV-
  • the amount of compound of formula (II) or (IIa) released thereby is 50 to 800 ppm, preferably from 60 to 750 ppm, more preferably from 70 to 700 ppm and most preferably from 75 to 650 ppm, based on component B.
  • the amount of the compound of the formula (III) or (IIIa) released here (below the detection limit of ⁇ 5 ppm) is up to 120 ppm, preferably from 5 to 100 ppm, more preferably from 5 to 95 ppm, and very particularly preferably from 8 to 90 ppm, based on the component B.
  • the amount of compound of formula (IV) or (IVa) released thereby is 0 (below the detection limit of ⁇ 5 ppm) up to 85 ppm, preferably from 0 to 75 ppm, more preferably from 5 to 70 ppm, and most preferably from 5 to 65 ppm, based on the component B.
  • the amount of the compound of the formula (V) or (Va) 0 released (below the detection limit of ⁇ 5 ppm) is especially up to 300 ppm, preferably from 5 to 290 ppm preferably from 5 to 285 ppm and most preferably from 10 to 280 ppm, based on the component B.
  • Component A may likewise comprise one or more cyclic oligomers of general formula (I).
  • Component A may also contain one or more structures of general formulas (II) to (V).
  • the copolycarbonate composition according to the invention contains from 5 to 99% by weight, preferably from 10 to 95% by weight, and more preferably from 15 to 90% by weight (based on the sum of parts by weight of components A and B) of component A.
  • the monomer unit (s) of the general formula (1) are introduced via one or more corresponding diphenols of the general formula (Ia):
  • R 1 is hydrogen or C 1 -C 4 -alkyl, preferably hydrogen
  • R 2 is C 1 -C 4 -alkyl, preferably methyl, and n is 0, 1, 2 or 3, preferably 3.
  • one or more monomer units of formula (4) may be contained in component A:
  • R 7 and R 8 independently of one another are H, C 1 -C 6 -alkyl, C 1 -C 8 -alkoxy, halogen, such as Cl or Br, or in each case optionally substituted aryl or aralkyl, preferably H or C 1 -C 12 -alkyl, especially preferably represents H or C 1 -C 5 -alkyl and very particularly preferably represents H or methyl, and Y represents a single bond, -SO 2 -, -CO-, -O-, -S-, C 1 -C 6 -alkylene or C 2 -C 5 alkylidene, further for C 6 -C 12 -arylene, which may optionally be condensed with further heteroatom-containing aromatic rings is.
  • the monomer unit (s) of the general formula (4) are introduced via one or more corresponding diphenols of the general formula (4a):
  • R 7 , R 8 and Y each have the already mentioned in connection with the formula (4) meaning.
  • Preferred diphenols of the formula (4a) are, for example, 4,4'-dihydroxybiphenyl (DOD), 4,4'-dihydroxybiphenyl ether (DOD ether), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2 , 4-Bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis [2- (4-hydroxyphenyl) -2-propyl] - benzene, 1,3-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 (3,5-dimethyl-4-hydroxyphenyl) -methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) -propane, bis -
  • 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, 1,1-bis (4 -hydroxyphenyl) -1-phenylethane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) -propane.
  • bisphenol A 4,4'-dihydroxybiphenyl
  • DOD ether 4,4'-dihydroxybiphenyl ether
  • R 1 1 is H, linear or branched Ci-Cio alkyl, preferably linear or branched CI-C ⁇ alkyl, particularly preferably linear or branched Ci-C4 alkyl, most preferably (H or C-alkyl is methyl ) and in which R 12 is linear or branched C 1 -C 10 -alkyl, preferably linear or branched C 1 -C 6 -alkyl, particularly preferably linear or branched C 1 -C 4 -alkyl, very particularly preferably C 1 -C 4 -alkyl (methyl) stands.
  • the diphenol (4c) is very particularly preferred.
  • the diphenols of the general formulas (4a) can be used both alone and in admixture with one another.
  • the diphenols are known from the literature or can be prepared by methods known from the literature (see, for example, H.J. Buysch et al., Ullmann's Encyclopedia of Industrial Chemistry, VCH, New York 1991, 5th Ed., Vol. 19, pp. 348).
  • the proportion of the monomer units of the formula (1) in the copolycarbonate is preferably 0.1-88 mol%, particularly preferably 1-86 mol%, very particularly preferably 5-84 mol% and in particular 10-82 mol% (relative to on the sum of the moles of diphenols used).
  • the preferred diphenolate units of the copolycarbonates according to component A are derived from monomers having the general structures of the formulas (Ia) and (4a) described above, the combination of bisphenols (Ib) and (4c) being particularly preferred.
  • copolycarbonate component of the copolycarbonate compositions may be present as a block and random copolycarbonate. Particularly preferred are random copolycarbonates.
  • the ratio of the frequency of the diphenolate monomer units in the copolycarbonate results from the molar ratio of the diphenols used.
  • the copolycarbonate composition according to the invention contains from 95 to 1% by weight, preferably from 90 to 5% by weight, and particularly preferably from 85 to 10% by weight (based on the sum of the parts by weight of components A, B and C) of the component B.
  • Component B is a polycarbonate or a copolycarbonate.
  • (Co) polycarbonates in the context of the present invention are both homopolycarbonates and copolycarbonates,
  • the monomer unit (s) of the general formula (2) are introduced via one or more corresponding diphenols of the general formula (2a): in which R is H, linear or branched C 1 -C 10 -alkyl, preferably linear or branched C 1 -C 6 -alkyl, particularly preferably linear or branched C 1 -C 4 -alkyl, very particularly preferably H or C 1-6 -alkyl (methyl) in which R 4 is linear or branched C 1 -C 10 -alkyl, preferably linear or branched C 1 -C 6 -alkyl, particularly preferably linear or branched C 1 -C 18 -alkyl, very particularly preferably C 1 -C 4 -alkyl (methyl ) stands.
  • the diphenol (4c) is very particularly preferred.
  • one or more monomer units of the formula (4) may be present, as already described for component A.
  • the copolycarbonate composition contains 95 to 10 wt .-%, preferably 90 to 20 wt .-%, particularly preferably 80 to 49 wt .-% (based on the sum of parts by weight of components A and B) of the component B.
  • component B is based solely on the bisphenol (4c).
  • copolycarbonate compositions according to the invention have a lower melt viscosity and thus an improved processing behavior in the injection molding of the copolycarbonate compositions thus obtained, given specific ratios of the components A and B.
  • Preferred methods of preparation of the (co) polycarbonates which are preferably used in the composition according to the invention as component A and B, including the (co) polyester carbonates, are the interfacial process and the melt transesterification process, preferably at least one of the components A and B after the melt transesterification process will be produced.
  • the preparation of the component A takes place after the melt transesterification process.
  • the preparation of the component B is preferably carried out by the interfacial process.
  • the alkali metal salts of diphenols are reacted with phosgene in the two-phase mixture.
  • the molecular weight can be determined by the amount of monophenols which act as chain terminators, such as. For example, phenol, tert-butylphenol or cumylphenol, particularly preferably phenol, tert-butylphenol. In these reactions arise almost exclusively linear polymers. This can be demonstrated by end group analysis.
  • branching agents generally polyhydroxylated compounds, branched polycarbonates are also obtained.
  • Branches may be small amounts, preferably amounts between 0.05 and 5 mol%, particularly preferably 0.1-3 mol%, very particularly preferably 0.1-2 mol%, based on the moles of diphenols used, of trifunctional Compounds such as isatin biscresol (IBK) or phlogoglucin, 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-tris (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 (2-hydroxy-5'-methylbenzyl) -4-methyl
  • Isatin biscresol and 1,1,1-tris (4-hydroxyphenyl) ethane (THPE) and bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole are preferably used as branching agents.
  • the use of these branching agents results in branched structures.
  • the resulting long chain branching usually leads to rheological properties of the resulting polycarbonates, which manifests itself in an intrinsic viscosity in comparison to linear types.
  • the amount of chain terminator to be used is preferably 0.5 mol% to 10 mol%, preferably 1 mol% to 8 mol%, particularly preferably 2 mol% to 6 mol%, based on mols of diphenols used in each case.
  • the addition of the chain terminators can be carried out before, during or after the phosgenation, preferably as a solution in a solvent mixture of methylene chloride and chlorobenzene (8-15 wt .-% -).
  • diphenols are reacted with carbonic acid diesters, usually diphenyl carbonate, in the presence of catalysts, such as alkali salts, ammonium or phosphonium compounds, in the melt.
  • catalysts such as alkali salts, ammonium or phosphonium compounds
  • 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 described.
  • diphenols of the formulas (2a) and optionally (Ia) are transesterified in the melt with carbonic acid diesters with the aid of suitable catalysts and optionally further additives.
  • Carbonic acid diesters according to the invention are those of the formulas (5) and (6)
  • R, R 'and R "independently of one another may represent H, optionally branched C 1 -C 4 -alkyl / cycloalkyl, C 1 -C 4 -alkaryl or C 6 -C 34 -aryl, for example
  • the proportion of carbonic acid esters is 100 to 130 mol%, preferably 103 to 120 mol%, particularly preferably 103 to 109 mol%, based on the one or more diphenols.
  • Catalysts used in the melt transesterification process are basic catalysts, for example alkali metal and alkaline earth metal hydroxides and oxides, but also ammonium or phosphonium salts, referred to below as onium salts.
  • Onium salts, particularly preferably phosphonium salts, are preferably used here.
  • Phosphonium salts in the context of the invention are those of the following general formula (7)
  • R 13 "16, the same or different Ci-Cio-alkyl, C6-Cio-aryl, C7-Cio-aralkyls or C5-C6 cycloalkyls may be, preferably methyl or C6-Ci 4 aryls, particularly preferably methyl or phenyl, and ⁇ ' " an anion such as hydroxide, sulfate, hydrogen sulfate, bicarbonate, carbonate, a halide, preferably chloride, or an alkoxide of the formula OR 17 may be, wherein R 17 C ⁇ -CM-aryl or C7-Ci2-aralkyl, preferred Preferred catalysts are tetraphenylphosphonium chloride, tetraphenylphosphonium hydroxide, tetraphenylphosphonium phenolate, particularly preferably tetraphenylphosphonium phenolate.
  • the catalysts are preferably used in amounts of from 10.sup.- 8 to 10.sup.- 3 mol, based on one mol of diphenol, particularly preferably in amounts of 10.sup.- 7 to 10.sup.- 4 mol.
  • 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 sodium hydroxide, alkoxide or aryloxide salts. Most preferred are sodium hydroxide and sodium phenolate.
  • the amounts of cocatalyst can range from 1 to 200 ppb, preferably from 5 to 150 ppb, and most preferably from 10 to 125 ppb, each calculated as sodium.
  • the addition of the catalysts is carried out in solution in order to avoid harmful excess concentrations during the metering.
  • the solvents are systemic and process inherent compounds such as diphenol, carbonic acid diesters or monohydroxyaryl compounds. Particular preference is given to monohydroxyaryl compounds, because it is known to the person skilled in the art that the diphenols and carbonic diesters readily change and decompose at already slightly elevated temperatures, in particular under the action of a catalyst.
  • These are the polycarbonate grades. In the technically significant transesterification process for the production of polycarbonate, the preferred compound is phenol. Phenol is also an obvious choice because the catalyst used, preferably tetraphenylphosphonium phenolate, is isolated as a mixed crystal with phenol during production.
  • the process for the preparation of the (co) polycarbonates contained in the composition according to the invention by the transesterification process can be carried out batchwise or else continuously.
  • the reaction is started in the presence of the catalyst.
  • the conversion or molecular weight is increased with increasing temperatures and falling pressures in suitable apparatus and devices by discharging the cleaving Monohydroxyarylharm until the desired final state is reached.
  • the ratio of diphenol to carbonic acid diester and the rate of loss of the carbon given by the choice of the method or plant for producing the polycarbonate.
  • the end groups are imprinted in type and concentration.
  • temperatures, pressures and catalysts used to perform the melt transesterification reaction between the diphenol and the carbonic acid diester optionally also other added reactants.
  • Each condition is possible as long as the selected temperatures, pressures and catalysts allow a melt transesterification with correspondingly rapid removal of the cleaved Monohydroxyarylharm.
  • the temperatures over the entire process are generally 180 to 330 ° C at pressures of 15 bar, absolute to 0.01 mbar, absolute.
  • the continuous process for the preparation of polycarbonates is characterized in that one or more diphenols with the carbonic acid diester, optionally also other added reactants using the catalysts, after a precondensation without separating the Monohydroxyarylharm formed in then then following several reaction Evaporator stages at gradually increasing temperatures and gradually falling pressures, the molecular weight is built up to the desired level.
  • the apparatus, apparatus and reactors suitable for the individual reaction-evaporator stages are, according to the process course, heat exchangers, expansion apparatuses, separators, columns, evaporators, stirred vessels and reactors or other commercially available apparatus which provide the necessary residence time at selected temperatures and pressures.
  • the chosen devices must provide the necessary heat input and be designed to meet the ever-increasing melt viscosities.
  • the reactants can either be melted together or else the solid diphenol in the carbonic acid diester melt or the solid carbonic acid diester can be dissolved in the melt of the diphenol or both raw materials are brought together as a melt, preferably directly from the preparation.
  • the residence times of the separate melts of the raw materials, in particular those of the melt of the diphenol, are set as short as possible.
  • the melt mixture can linger longer due to the reduced melting point of the raw material mixture compared to the individual raw materials at correspondingly lower temperatures without sacrificing quality.
  • the catalyst preferably dissolved in phenol, admixed and the melt is heated to the reaction temperature.
  • This is at the beginning of the technically significant process for the production of polycarbonate from 2,2-bis (4-hydroxyphenyl) propane and diphenyl carbonate 180 to 220 ° C, preferably 190 to 210 ° C, most preferably 190 ° C.
  • the reaction equilibrium is adjusted without the hydroxyaryl compound formed being removed.
  • the reaction can be run at atmospheric pressure, but for technical reasons even at overpressure.
  • the preferred pressure in technical systems is 2 to 15 bar absolute.
  • the melt mixture is in a first vacuum chamber, the pressure of 100 to 400 mbar, preferably adjusted to 150 to 300 mbar, relaxed and then directly heated in a suitable device at the same pressure back to the inlet temperature. In the relaxation process, the resulting hydroxyaryl compound is evaporated with remaining monomers.
  • the reaction mixture is in a second vacuum chamber whose pressure is 50 to 200 mbar, preferably 80 to 150 mbar, relaxed and then directly in a suitable Device at the same pressure to a temperature of 190 to 250 ° C, preferably 210 to 240 ° C, more preferably 210 to 230 ° C, heated.
  • the resulting Hydroxyarylharm is evaporated with remaining monomers.
  • the reaction mixture in a third vacuum chamber whose pressure is 30 to 150 mbar, preferably 50 to 120 mbar, relaxed and directly afterwards in a suitable device at the same pressure to a temperature of 220 to 280 ° C, preferably 240 to 270 ° C, more preferably 240 to 260 ° C, heated.
  • the resulting HydroxyarylENS is evaporated with remaining monomers.
  • the reaction mixture is in a further vacuum chamber whose pressure at 5 to 100 mbar, preferably 15 to 100 mbar, particularly preferably 20 to 80 mbar is relaxed and directly 2Q after in a suitable device at the same pressure to a temperature of 250 to 300 ° C, preferably 260 to 290 ° C, more preferably 260 to 280 ° C, heated.
  • a suitable device at the same pressure to a temperature of 250 to 300 ° C, preferably 260 to 290 ° C, more preferably 260 to 280 ° C, heated.
  • Viscosity of the oligomeric carbonate is between 1.04 and 1.20, preferably between 1.05 and 1.15, particularly preferably between 1.06 and 1.10.
  • the oligocarbonate thus produced is after a residence time of 5 to 20 min in a sump template possibly pumped with the same pressure and same temperature as in the last flash / evaporator stage in a disk or basket reactor and at 250 to 310 ° C, preferably 250 to 290 ° C, more preferably 250 to 280 ° C, at pressures of 1 to 15 mbar, preferably 2 to 10 mbar, at residence times of 30 to 90 minutes, preferably 30 to 60 minutes, further condensed.
  • the product reaches a rel. Viscosity of 1.12 to 1.28, preferably 1.13 to 1.26, more preferably 1.13 to 1.24.
  • the melt leaving this reactor is brought to the desired final viscosity or the final molecular weight in a further disk or basket reactor.
  • the temperatures are 270 to 330 ° C, preferably 280 to 320 ° C, more preferably 280 to 310 ° C, the pressure 0.01 to 3 mbar, preferably 0.2 to 2 mbar, with residence times of 60 to 180 minutes, preferably 75 to 150 min.
  • the rel. Viscosities are adjusted to the level required for the intended application and are from 1.18 to 1.40, preferably 1.18 to 1.36, particularly preferably 1.18 to 1.34.
  • the function of the two basket reactors or disk reactors can also be summarized in a basket reactor or disk reactor.
  • the monohydroxyaryl compound can be used directly for the preparation of a diphenol or a carbonic acid diester.
  • the disk or basket reactors are characterized by the fact that they provide a very large, constantly renewing surface on a vacuum at high residence times.
  • the disk or basket reactors are geometrically formed according to the melt viscosities of the products. Suitable examples are reactors, as described in DE 44 47 422 C2 and EP A 1 253 163, or two-shaft reactors, as described in WO A 99/28 370.
  • the oligocarbonates, even very low molecular weight, and the finished polycarbonates are usually promoted by gear pumps, screws of various designs or positive displacement pumps special design.
  • polyfunctional compounds can be used as branching agents.
  • the weight average molecular weights in the poly- or copolycarbonates of the invention are preferably from 15,000 to 40,000 g / mol, more preferably from 17,000 to 36,000 g / mol, and most preferably from 17,000 to 34,000 g / mol, and are determined by GPC against polycarbonate calibration certainly.
  • copolycarbonate compositions in which component B or component A and component B contain, at least in part, as end group, a structural unit of the formula (3a) and / or a structural unit of the formula (3b).
  • the present invention furthermore relates to compositions comprising components A and B and optionally as component C at least one additive, preferably selected from the group of customary for these thermoplastics additives such as fillers, carbon black, UV stabilizers, IR stabilizers, heat stabilizers, antistatic agents and Pigments, colorants in the usual amounts; if necessary, the demolding behavior, the flow behavior, and / or the flame retardancy can be improved by the addition of external mold release agents, flow agents, and / or flame retardants such as sulfonic acid salts, PTFE polymers or PTFE copolymers, brominated oligocarbonates, or oligophosphates and phosphazenes (z B.
  • additives preferably selected from the group of customary for these thermoplastics additives such as fillers, carbon black, UV stabilizers, IR stabilizers, heat stabilizers, antistatic agents and Pigments, colorants in the usual amounts; if necessary, the demolding behavior, the flow behavior, and / or
  • alkyl and aryl phosphites alkyl and aryl phosphites, phosphates, phosphanes, -niedermoleculare carboxylic acid esters, halogen compounds, salts, chalk, talc, silicates, boron nitride, thermally or electrically conductive carbon blacks or graphites, quartz / quartz powder, glass and carbon fibers, pigments or also additives for the reduction of the linear thermal expansion coefficient (CLTE) and their combination.
  • CLTE linear thermal expansion coefficient
  • the composition generally contains 0 to 5.0 wt .-%, preferably 0 to 2.50 wt .-%, particularly preferably 0 to 1.60 wt .-%, most preferably 0.03 to 1.50 wt. %, in particular very particularly preferably 0.02 to 1.0% by weight (based on the total composition) of additives.
  • the total amount of organic and inorganic additives may be up to 30% by weight (based on the total composition).
  • the mold release agents optionally added to the compositions according to the invention are preferably selected from the group consisting of pentaerythritol tetrastearate, glycerol monostearate and long-chain fatty acid esters, for example stearyl stearate and propanediol stearate, and mixtures thereof.
  • the mold release agents are preferably used in amounts of 0.05% by weight to 2.00% by weight, preferably in amounts of 0.1% by weight to 1.0% by weight, particularly preferably in amounts of 0 , 15 wt .-% to 0.60 wt .-% and most preferably in amounts of 0.20 wt .-% to 0.50 wt .-%, based on the total weight of the components A, B and C.
  • Suitable additives are described, for example, in “Additives for Plastics Handbook, John Murphy, Elsevier, Oxford 1999", in the “Plastics Additives Handbook, Hans Zweifel, Hanser, Kunststoff 2001”.
  • Suitable antioxidants or thermal stabilizers are, for example:
  • Tris (2,4-di-tert-butylphenyl) phosphite (Irgafos 168), tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4 "-diylbisphosphonite are preferably suitable as heat stabilizers , Triisoctyl phosphate (TOF), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox 1076), bis (2,4-dicumyl-phenyl) pentaerythritol diphosphite (Doverphos S-9228), Bis ( 2,6-di-tert-butyl-4-methylphenyl) -pentaerythritol diphosphite (ADK STAB PEP-36) and triphenylphosphine (TPP) ""
  • Thermostabilizers are preferably used in amounts of 0.005 wt .-% to 2.00 wt .-%, preferably in amounts of 0.01 wt .-% to 1.0 wt .-%, particularly preferably in amounts of 0.015 wt .-%. % to 0.60 wt .-% and most preferably in amounts of 0.02 wt .-% to 0.50 wt .-%, based on the total weight of the components A, B and C.
  • Suitable complexing agents for heavy metals and for the neutralization of alkali traces 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) -1,3 , 5-triazines or substituted hydroxyalkoxyphenyl, 1,3,5-triazoles, preferred are substituted benzotriazoles such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy -3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-tert-butylpheny
  • Suitable UV stabilizers are furthermore suitably selected from the group consisting of benzotriazoles (for example Tinuvine from BASF), triazine Tinuvin 1600 from BASF), benzophenones (Uvinule from Fa.
  • benzotriazoles for example Tinuvine from BASF
  • benzophenones Uvinule from Fa.
  • the UV stabilizers are used in amounts of from 0.01% by weight to 2.0% by weight, based on the molding composition, preferably in amounts of from 0.05% by weight to 1.00% by weight, especially preferably in amounts of 0.08 wt .-% to 0.5 wt .-% and most preferably in amounts of 0.1 wt .-% to 0.4 wt .-% based on the total composition.
  • Polypropylene glycols alone or in combination with z can be used against damage by gamma rays.
  • stabilizers may be used singly or in combinations and added to the polymer in the above-mentioned forms.
  • Suitable flame retardant additives are phosphate esters, ie triphenyl phosphate, resorcinol diphosphoric acid esters, bromine-containing compounds such as brominated phosphoric acid esters, brominated oligocarbonates and polycarbonates, and preferably salts of fluorinated organic sulfonic acids.
  • Suitable impact modifiers are butadiene rubber grafted with styrene-acrylonitrile or methyl methacrylate, ethylene-propylene rubbers grafted with maleic anhydride, ethyl and Butylacrylatkautschuke with grafted methyl methacrylate or styrene-acrylonitrile, interpenetrating siloxane and acrylate networks with grafted methyl methacrylate or styrene-acrylonitrile.
  • the composition according to the invention contains at least one additive selected from the group consisting of the heat stabilizers, the mold release agents and the UV absorbers, preferably in a total amount of 0.2 wt.% To 2.0 wt.%, Based on the total amount of components A, B and C. Particularly preferred are thermal stabilizers.
  • the coolycarbonate compositions of the invention are prepared on conventional machines such as multi-screw extruder by compounding optionally with the addition of additives and other additives at temperatures between 280 ° C and 360 ° C.
  • the (co) polycarbonates and copolycarbonate compositions according to the invention can be processed in conventional manner on customary machines, for example on extruders or injection molding machines, to give any desired shaped bodies or shaped parts into films or sheets or bottles.
  • copolycarbonate compositions according to the invention can be used to form any molded articles / extrudates used wherever already known polycarbonates, polyestercarbonates and polyesters are used:
  • Safety discs which are known to be required in many areas of buildings, vehicles and aircraft, as well as shields of helmets.
  • Automotive headlamps, bezels, turn signals, reflectors 4.
  • translucent plastics containing glass fibers for lighting purposes As translucent plastics containing barium sulfate, titanium dioxide and or zirconium oxide or high-reflectance opaque compositions (high reflectance) and components made therefrom.
  • medical devices e.g. Oxygenators, dialyzers (hollow fiber dialyzers), 3-way valves, hose connectors, blood filters, injection systems, inhalers, ampoules
  • LED applications (pedestal, reflectors, heat sinks),
  • the compounds, blends, moldings, extrudates, films and film laminates of the copolycarbonate compositions according to the invention are likewise subject matter of this application, as are moldings, extrudates and films containing coextrusion layers of the copolycarbonate compositions according to the invention.
  • PC 1 is a polycarbonate based on bisphenol A, phenol as a chain terminator with a melt volume flow rate (MVR) of 12.5 cm 710 min (300 ° C / 1.2 kg) and a content of cyclic oligomers of the formula (I) of 1.39 wt .-%, wherein no proportions of branching and defect structures are detectable.
  • MVR melt volume flow rate
  • the individual amounts of the respective branching and defect structures (II) to (V) are: 521 ppm for (II), 73 ppm (III), 46 ppm (IV) and 203 ppm (V).
  • the segments of the formulas (II) to (IV) act as a branching element.
  • PC I is thus the polycarbonate, which has no branching and defect structures, while these are significantly present in PC 2.
  • CoPC is a commercially available copolycarbonate based on bisphenol A and bisphenol TMC, phenol as chain terminator with an MVR of 17 crriVIO min (330 ° C / 2.16 kg) (Apec 1745 from Bayer MaterialScience AG).
  • the polycarbonate PC2 was prepared in a melt process as follows:
  • the average residence time is 50 minutes.
  • the melt is then passed through an expansion valve in a below 200 mbar separator.
  • the effluent melt is reheated to 190 ° C. in a falling-film evaporator, which is also under 200 mbar, and collected in a receiver.
  • the melt is pumped into the next three, similarly constructed stages.
  • the conditions in the 2nd / 3rd / 4th stages are 100/74/40 mbar; 220 ° / 225 ° / 273 ° C and 20/10/10 minutes.
  • the resulting oligomer has a rel. Viscosity of 1.08. All vapors are pressurized into a vacuum "
  • the oligomer is condensed in a subsequent disc reactor at 280 ° C and 3.0 mbar at a residence time of 45 minutes to a higher molecular weight product.
  • the rel. Viscosity is 1.195.
  • the vapors are condensed. From the melt stream, which is passed into another basket reactor, a partial flow of 150 kg melt / h is branched off by means of a gear pump, mixed with 150 g of a 5% solution of the quencher of formula 6 in phenol / h, via a static mixer with a Length-to-diameter ratio of 20 out and returned to the main melt stream.
  • the added quencher is homogeneously distributed throughout the melt stream by means of another static mixer.
  • the melt thus treated is further exposed in a further disc reactor at 290 ° C, 0.7 mbar and at a mean residence time of 120 minutes the process conditions, discharged and granulated.
  • the vapors are condensed in the vacuum system and behind it.
  • the polycarbonate PCI was prepared in a phase interface process as follows:
  • the copolycarbonate CoPC was prepared analogously to the PCI in a phase boundary process.
  • the BP-TMC to BPA ratio is chosen so that a VICAT B temperature of 170 ° C is reached.
  • the copolycarbonate compositions of Examples 1 -6 based on the raw materials PCI and PC2 and CoPC (Apec 1745) are mixed on a twin-screw extruder at 300 ° C. in the formulations listed in Tables 1 and 2.
  • the polymer compositions thus obtained by compounding are granulated and are available for polymer physical characterizations.
  • Determination of the content of cyclic oligomers The sample is dissolved with methylene chloride. By adding acetone, the majority of the polymer is precipitated. The undissolved portions are filtered off, the filtrate is concentrated to dryness. The dry residue is dissolved with THF and the oligomers are determined by HPLC with UV detection.
  • Determination of Defective Structures (II to V): The sample is saponified with sodium methylate under reflux. The saponification solution is acidified and concentrated to dryness. The dry residue is dissolved with acetonitrile and the phenolic compounds (IIa to Va) are determined by HPLC with UV detection. Characterization of the novel molding materials (test methods): The determination of the melt volume flow rate (MVR) was carried out according to ISO 1133 (at a test temperature of 330 ° C., mass 2.16 kg) with the device Zwick 4106 from Roell.
  • MVR melt volume flow rate
  • the Vicat softening temperature VST / B50 or B120 as a measure of the heat resistance was according to ISO 306 on test specimens of dimension 80 x 10 x 4 mm with a stamping load of 50 N and a heating rate of 50 ° C / h or 120 ° C / h with the Coesfeld Eco 2920 device from Coesfeld Materialtest.
  • Examples 4 to 6 according to the invention have significantly higher MVR values at approximately the same Vicat temperatures, demonstrating improved flowability of the melts, and although there is a significant proportion of branching and mismatching which normally results in an increase in viscosity ,
  • Examples 4-6 of the present invention show significantly lower levels of melt viscosities over both the entire shear range and at different temperatures, and although there is a significant level of branching and mismatching which normally results in an increase in viscosity.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne des compositions de copolycarbonate comportant des structures de ramification et des oligomères cycliques et présentant des propriétés d'écoulement améliorées, ainsi que leur utilisation pour la fabrication de mélanges et de pièces moulées et les pièces moulées ainsi obtenues.
EP15745461.2A 2014-08-01 2015-07-31 Compositions de copolycarbonate comportant des structures de ramification et des oligomères cycliques et présentant des propriétés rhéologiques améliorées Withdrawn EP3174933A1 (fr)

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EP3174936A1 (fr) * 2014-08-01 2017-06-07 Covestro Deutschland AG Compositions de copolycarbonate comportant des structures de ramification et des oligomères linéaires et présentant des propriétés rhéologiques améliorées
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