EP1325056A1 - Use of copolycarbonates - Google Patents

Use of copolycarbonates

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Publication number
EP1325056A1
EP1325056A1 EP01972054A EP01972054A EP1325056A1 EP 1325056 A1 EP1325056 A1 EP 1325056A1 EP 01972054 A EP01972054 A EP 01972054A EP 01972054 A EP01972054 A EP 01972054A EP 1325056 A1 EP1325056 A1 EP 1325056A1
Authority
EP
European Patent Office
Prior art keywords
mol
copolycarbonates
polycarbonates
formula
copolycarbonates according
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Withdrawn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
EP01972054A
Other languages
German (de)
French (fr)
Inventor
Silke Kratschmer
Klaus Horn
Annett KÖNIG
Rolf Wehrmann
Steffen Kühling
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 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
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP1325056A1 publication Critical patent/EP1325056A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31507—Of polycarbonate

Definitions

  • the present invention relates to the use of stress-crack-resistant, impact-resistant copolycarbonates with particularly good low-temperature properties and good aging stability, for applications in which particularly good low-temperature properties and / or high aging stability are required, e.g. for automotive or outdoor applications, as well as new copolycarbonates themselves.
  • Polycarbonates typically become brittle at low temperatures, i.e. they tend to break and lose their impact strength.
  • polycarbonates After storage at temperatures below the glass transition temperature, polycarbonates also show an aging effect that is dependent on the storage time and temperature, which significantly reduces the high energy level in the impact strength (Bottenbruch et al., Engineering Thermoplastics Polycarbonates, Polyacetals, Polyesters, Cellulose Esters, Carl Hanser Verlag Kunststoff, Vienna, New York, 1996,
  • Copolycarbonates based on 4,4'-dihydroxydiphenyl and 2,2-bis (4-hydroxy ⁇ henyl) propane have now been known from JP 5 117 382 and in EP-AI 0 544407, US 5 470 938, US 5 532 324 and No. 5,401,826 is described as particularly chemical-resistant, heat-resistant and flame-retardant, with, in comparison to commercially available polycarbonate made from pure bisphenol, the same mechanical properties and transparency.
  • these copolycarbonates have particularly good low-temperature properties, let alone that these polycarbonates have a particular aging stability.
  • the task was therefore to find a transparent polycarbonate which, on the one hand, shows improved low-temperature toughness compared to polycarbonate made from pure 2,2-bis (4-hydroxyphenyl) propane, and on the other hand has increased aging stability with improved stress cracking behavior.
  • the copolycarbonate according to the invention shows no aging effect which is dependent on the storage time and temperature when stored below the glass transition temperature of the copolycarbonate, so that the high energy level in the impact strength is maintained and the polycarbonates do not become brittle.
  • the copolycarbonate according to the invention thus provides a material which has very good notched impact strength at low low temperatures, but which also does not lose this property again due to aging effects due to storage at temperatures below the glass transition temperature.
  • the present invention therefore relates to the use of copolycarbonates which, from 0.1 mol% to 46 mol%, preferably from 11 mol% to 34 mol% and in particular from 26 mol% to 34 mol%, of compounds of the formula (I),
  • R 1 to R 4 independently of one another are H, C 1 -C 4 -alkyl, phenyl, substituted phenyl or halogen, preferably H, C 1 -C 4 -alkyl or halogen and particularly preferably all the same radical, in particular H or tert-butyl stand, and complementary amounts, ie 99.9 mol% to 54 mol%, preferably 89 mol% to 66 mol% and in particular 74 mol% to 66 mol% of compounds of the formula (II)
  • R 5 - R 8 are independently H, CH 3, Cl or Br, and X is C ⁇ -C 5 alkylene, C 2 -C 5 alkylidene, C 5 -C 6 cycloalkylene, C 5 -C ⁇ 0 cycloalkylidene is , are built up as monomers, as materials in areas where particularly good low-temperature properties and thermal stability are required.
  • Copolycarbonates composed of 34-26 mol%, especially 33-27 mol%, in particular 32-28 mol%, very particularly 31-29 mol% and particularly highlighted 30 mol% of monomer of formula (I) are very particularly preferred and even subject matter of the invention. , each supplemented by a complementary content of monomer of formula (II).
  • the percentages of the bisphenol monomers relate to the total content of bisphenols defined in the polycarbonates at 100%.
  • a pure bisphenol A polycarbonate would then consist of 100% bisphenol A.
  • the carbonate content from carbonic acid esters or halides is not taken into account.
  • Preferred, particularly preferred or very particularly preferred are polycarbonates which have the compositions mentioned under preferred, particularly preferred or very particularly preferred.
  • copolycarbonates on the one hand have particularly good low-temperature properties and on the other hand also have particularly good aging properties. They can therefore be used as moldings wherever the properties of the polycarbonates known hitherto are insufficient, in particular, for. B. in the electrical sector and in the construction sector, for covers or glazing, in particular in the automotive sector as films, plates, fittings or housing parts, but also in the optical field as lenses and data storage as well as consumer goods, when increased heat resistance or chemical resistance with good low-temperature properties and / or aging stability at the same time. In addition, they can also replace other materials in which ordinary polycarbonates have not been able to be used because of their insufficient low-temperature properties.
  • Good low-temperature properties are to be understood according to the invention as good, but not restrictive, good low-temperature toughness, since ordinary polycarbonates break brittle at low temperatures in the impact test.
  • low temperatures are understood to mean temperatures below -10 ° C, particularly preferably below -20 ° C, particularly preferably below -30 ° C, very particularly preferably below -40 ° C, in particular below -50 ° C.
  • good thermal stability and aging stability is to be understood, by way of example, but not restrictively, to mean good notched impact strength after annealing, since ordinary polycarbonates become brittle after annealing and thus tend to break and crack.
  • Glass transition temperature of 155 ° C to understand preferably the temperature is range from 40 ° C to 140 ° C, particularly preferably from 60 ° C to 140 ° C and very particularly preferably from 80 ° C to 140 ° C.
  • Preferred compounds of formula (I) are 4,4'-dihydroxydiphenyl (DOD) and 4,4'-dihydroxy-3,3 ', 5,5'tetra (tert-butyl) diphenyl, 4,4'-dihydroxy- 3,3 ', 5,5'tetra (n-butyl) diphenyl and 4,4'-dihydroxy-3,3', 5,5'tetra (methyl) diphenyl, 4,4'-dihydroxydiphenyl is particularly preferred.
  • DOD 4,4'-dihydroxydiphenyl
  • DOD 4,4'-dihydroxy-3,3 ', 5,5'tetra (tert-butyl) diphenyl
  • 4,4'-dihydroxy- 3,3 ', 5,5'tetra (n-butyl) diphenyl 4,4'-dihydroxy-3,3', 5,5'tetra (methyl) diphenyl
  • 4,4'-dihydroxydiphenyl is particularly preferred.
  • Preferred compounds of the formula (II) are 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 1,3-bis [2- (4- hydroxyphenyl) -2-propyl] benzene, 1,1-bis (4-hydroxyphenyl) -1-phenyl ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, in particular 2,2-bis (4-hydroxyphenyl) propane (Bisphenol A) and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC), very particularly preferably 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).
  • both a compound of the formula (II), with formation of binary copolycarbonates, and also a plurality of compounds of the formula (II) can be used.
  • the starting materials of the formula (I) and (II) can of course contain impurities due to the synthesis.
  • a high level of purity is desirable and desirable, which is why these educts are used with the highest possible level of purity.
  • polycarbonates and copolycarbonates are generally known in the literature and is also carried out accordingly in the cases according to the invention: According to DE-OS 2 119 779, the production of polycarbonates with the participation of monomers of the formula (I) is preferably carried out in solution, specifically by the phase interface process and the process in homogeneous phase.
  • melt transesterification process acetate processes and phenyl ester processes
  • transesterification processes acetate processes and phenyl ester processes
  • the copolycarbonates can have molecular weights between Mw (weight average
  • Molecular weight 10,000 to 60,000, preferably Mw 20,000 to 55,000, 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.
  • the polycarbonates according to the invention can be processed thermoplastically in the usual manner at temperatures of 240 ° C. to 380 ° C., preferably 260 ° C. to 360 ° C. Any shaped bodies and foils can be produced in a known manner by injection molding or via extrusion. Moldings and extrudates from the copolycarbonates according to the invention are also the subject of the present application.
  • the polycarbonates according to the invention are readily soluble in solvents such as chlorinated hydrocarbons, for example methylene chloride, and can thus be processed, for example, to give cast films in a known manner.
  • Safety windows 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 1-10% 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-OS 2 701 173).
  • Headlight lamps so-called “head lamps” or scattered light discs.
  • dialyzers For medical applications, e.g. Oxygenators, dialyzers.
  • films can be made from the high molecular weight aromatic polycarbonates of the invention.
  • the films have preferred thicknesses between 1 and 1500 ⁇ m, in particular preferred thicknesses between 10 and 900 ⁇ m.
  • the films obtained can be stretched monoaxially or biaxially in a manner known per se, preferably in a ratio of 1: 1.5 to 1: 5.
  • the films can be produced by the known processes for film production, for example by extrusion of a polymer melt through a slot die, by blowing on a film blowing machine, by deep drawing or casting. It is possible that the foils are used on their own. They can of course also be used to produce composite films with other plastic films using the conventional methods, with all known films in principle being suitable as partners, depending on the desired application and the end property of the composite film. A composite of two or more foils can be created.
  • the copolycarbonates according to the invention can also be used in other layer systems, for example in coextruded sheets.
  • the polycarbonates according to the invention can contain different end groups. These are introduced by chain breakers. Chain terminators in the sense of the invention are those of the formula (III)
  • R, R 'and R independently of one another H, optionally branched Cj-C 4 -
  • the polycarbonates can contain small amounts of 0.02 to 3.6 mol% (based on the
  • Suitable branching agents are the compounds with three or more functional groups suitable for polycarbonate production, preferably those with three or more than three phenolic OH groups, for example branching agents, as mentioned in EP-A 708 130, p. 4, preferably 1 , 1,1-tri- (4-hydroxyphenyl) ethane and isatin biscresol.
  • auxiliaries and reinforcing materials can be added to the polycarbonates according to the invention.
  • thermal and UV stabilizers flow aids, mold release agents, flame retardants, pigments, finely divided minerals, fiber materials, e.g. Alkyl and
  • Such compounds are described, for example, in WO 99/55772, pp. 15-25, and in "Plastics Additives", R. Gumbleter and H. Müller, Hanser Publishers 1983.
  • polystyrene can also be mixed into the polycarbonates according to the invention, e.g. Polyolefins, polyurethanes, polyesters, acrylonitrile butadiene styrene and polystyrene.
  • These substances are preferably added to the finished polycarbonate in conventional units, but, depending on the requirements, can also be carried out at a different stage in the production process.
  • the impact test according to ISO 180 / 4A was used to determine the impact strength.
  • a polycarbonate with 30 mol% dihydroxydiphenyl (DOD) and 70 mol% bisphenol A was produced in the phase interface process.
  • Tert-butylphenol was used as the chain terminator.
  • the granules have a relative solution viscosity of
  • a polycarbonate with 30 mol% DOD and 70 mol% bisphenol A was produced in the melt transesterification process.
  • the product has a relative solution viscosity of 1.28.
  • a polycarbonate with 35 mol% DOD and 65 mol% bisphenol A was produced in the melt transesterification process.
  • the product has a relative solution viscosity of 1.295.
  • the product has a relative solution viscosity of 1.295.
  • a polycarbonate with 20 mol% DOD and 80 mol% bisphenol A was produced in the melt transesterification process.
  • the product has a relative solution viscosity of 1.295.
  • Table 2 shows the superior low-temperature toughness of the inventive copolycarbonates of Examples 1-3 at -60 ° C.
  • the property profile of the copolycarbonate according to the invention also changed significantly after aging.
  • polycarbonate from pure bisphenol A shows brittle fracture behavior, while the tough behavior of the copolycarbonate can still be observed after 7 days.
  • the copolymer shows tough fracture behavior at a high level even after storage at 150 ° C. and subsequent impact test.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Saccharide Compounds (AREA)

Abstract

The invention relates to the use of copolycarbonates which are impact-resistant and resistant to tension cracking, with particularly good low temperature properties and high ageing stability, in applications where particularly good low temperature properties and/or high ageing stability is required, for example, in automobile construction and external applications and novel copolycarbonates themselves.

Description

Verwendung von CopolycarbonatenUse of copolycarbonates
Gegenstand der vorliegenden Erfindung ist die Verwendung spannungsrissbeständiger, schlagzäher Copolycarbonate mit besonders guten Tieftemperatureigenschaften und gute Alterungsstabilitat, für Anwendungen, in denen besonders gute Tieftemperatureigenschaften und/oder eine hohe Alterungsstabilitat gefragt sind, z.B. für den Automobilbau oder Außenanwendungen, sowie neue Copolycarbonate selbst.The present invention relates to the use of stress-crack-resistant, impact-resistant copolycarbonates with particularly good low-temperature properties and good aging stability, for applications in which particularly good low-temperature properties and / or high aging stability are required, e.g. for automotive or outdoor applications, as well as new copolycarbonates themselves.
Für den Automobilbau und andere Außenanwendungen werden seit langem möglichst chemikalienresistente und vorzugsweise transparente Polycarbonate gesucht, die einerseits tieftemperaturbeständig sind, andererseits eine hohe Alterungsstabilitat aufweisen.For the automotive industry and other outdoor applications, chemical-resistant and preferably transparent polycarbonates have been sought for a long time, which on the one hand are resistant to low temperatures and on the other hand have a high aging stability.
Polycarbonate werden typischerweise bei tiefen Temperaturen spröde, d.h. sie neigen dazu zu brechen und ihre Kerbschlagzähigkeit zu verlieren.Polycarbonates typically become brittle at low temperatures, i.e. they tend to break and lose their impact strength.
Polycarbonate zeigen zudem nach Lagerung bei Temperaturen unterhalb der Glasübergangstemperatur einen von der Lagerzeit und Temperatur abhängigen Alterungseffekt, durch den das hohe Energieniveau bei der Kerbschlagzähigkeit deutlich gesenkt wird (Bottenbruch et al., Engineering Thermoplastics Polycarbonates, Polyacetals, Poly- esters, Cellulose Esters, Carl Hanser Verlag München, Wien, New York, 1996,After storage at temperatures below the glass transition temperature, polycarbonates also show an aging effect that is dependent on the storage time and temperature, which significantly reduces the high energy level in the impact strength (Bottenbruch et al., Engineering Thermoplastics Polycarbonates, Polyacetals, Polyesters, Cellulose Esters, Carl Hanser Verlag Munich, Vienna, New York, 1996,
S. 183 f), d.h. auch dadurch werden Polycarbonate spröde.P. 183 f), i.e. this also makes polycarbonates brittle.
Es wurden nun bereits Copolycarbonate auf Basis von 4,4'-Dihydroxydiphenyl und 2,2- Bis(4-hydroxyρhenyl)propan aus JP 5 117 382 bekannt und in EP-AI 0 544407, US 5 470 938, US 5 532 324 und US 5 401 826 als besonders chemikalienresistent, hitzebeständig und schwer entflammbar beschrieben, bei, im Vergleich zu handelsüblichem Polycarbonat aus reinem Bisphenol, gleichen mechanischen Eigenschaften und Transparenz. Es findet sich im Stand der Technik jedoch keinerlei Hinweis darauf, dass diese Copolycarbonate besonders gute Tieftemperatureigenschaften besitzen, geschweige denn dass diese Polycarbonate eine besondere Alterungsstabilitat aufweisen. Die Aufgabe bestand daher darin, ein transparentes Polycarbonat zu finden, das einerseits verbesserte Tieftemperaturzähigkeit im Vergleich zu Polycarbonat aus reinem 2,2-Bis(4-hydroxyphenyl)propan zeigt, andererseits eine erhöhte Alterungsstabilitat aufweist, bei verbessertem Spannungsrissverhalten.Copolycarbonates based on 4,4'-dihydroxydiphenyl and 2,2-bis (4-hydroxyρhenyl) propane have now been known from JP 5 117 382 and in EP-AI 0 544407, US 5 470 938, US 5 532 324 and No. 5,401,826 is described as particularly chemical-resistant, heat-resistant and flame-retardant, with, in comparison to commercially available polycarbonate made from pure bisphenol, the same mechanical properties and transparency. However, there is no indication in the prior art that these copolycarbonates have particularly good low-temperature properties, let alone that these polycarbonates have a particular aging stability. The task was therefore to find a transparent polycarbonate which, on the one hand, shows improved low-temperature toughness compared to polycarbonate made from pure 2,2-bis (4-hydroxyphenyl) propane, and on the other hand has increased aging stability with improved stress cracking behavior.
Überraschenderweise wurde nun gefunden, dass das erfindungsgemäße Copoly- carbonat bei Lagerung unterhalb der Glasübergangstemperatur des Copolycarbonats keinen von der Lagerzeit und Temperatur abhängigen Alterungseffekt zeigt, so dass das hohe Energieniveau bei der Kerbschlagzähigkeit beibehalten wird, die Polycarbonate werden nicht spröde.Surprisingly, it has now been found that the copolycarbonate according to the invention shows no aging effect which is dependent on the storage time and temperature when stored below the glass transition temperature of the copolycarbonate, so that the high energy level in the impact strength is maintained and the polycarbonates do not become brittle.
Dieses unerwartete Alterungsverhalten des erfindungsgemäßen Copolycarbonats ist fiir die Praxisanwendung von großer Bedeutung. Viele Anwendungen unterliegen ständig wechselnden thermischen Belastungen. Mit dem erfindungsgemäßen Copolycarbonat wird somit ein Werkstoff bereit gestellt, der über eine sehr gute Kerbschlagzähigkeit bei tiefen Tieftemperatur verfügt, der jedoch auch diese Eigenschaft nicht durch Lagerung bei Temperaturen unterhalb der Glasübergangstemperatur auf Grund von Alterungseffekten wieder verliert.This unexpected aging behavior of the copolycarbonate according to the invention is of great importance for practical use. Many applications are subject to constantly changing thermal loads. The copolycarbonate according to the invention thus provides a material which has very good notched impact strength at low low temperatures, but which also does not lose this property again due to aging effects due to storage at temperatures below the glass transition temperature.
Die vorliegende Erfindung betrifft daher die Verwendung von Copolycarbonaten, die aus 0,1 mol % bis 46 mol %, vorzugsweise aus 11 mol % bis 34 mol % und insbesondere aus 26 mol % bis 34 mol % Verbindungen der Formel (I),The present invention therefore relates to the use of copolycarbonates which, from 0.1 mol% to 46 mol%, preferably from 11 mol% to 34 mol% and in particular from 26 mol% to 34 mol%, of compounds of the formula (I),
worin R1 bis R4 unabhängig voneinander für H, Cι-C4-Alkyl, Phenyl, substituiertes Phenyl oder Halogen stehen, bevorzugt für H, Cι-C -Alkyl oder Halogen stehen und besonders bevorzugt alle für den gleichen Rest, insbesondere für H oder tert.-Butyl stehen, und komplementären Mengen, also 99,9 mol % bis 54 mol %, vorzugsweise 89 mol % bis 66 mol % und insbesondere 74 mol % bis 66 mol % an Verbindungen der Formel (II)wherein R 1 to R 4 independently of one another are H, C 1 -C 4 -alkyl, phenyl, substituted phenyl or halogen, preferably H, C 1 -C 4 -alkyl or halogen and particularly preferably all the same radical, in particular H or tert-butyl stand, and complementary amounts, ie 99.9 mol% to 54 mol%, preferably 89 mol% to 66 mol% and in particular 74 mol% to 66 mol% of compounds of the formula (II)
worin R5 - R8 unabhängig voneinander H, CH3, Cl oder Br sind und X Cι-C5-Alkylen, C2-C5-Alkyliden, C5-C6-Cycloalkylen, C5-Cι0-Cycloalkyliden ist, als Monomere aufgebaut sind, als Werkstoffe in Bereichen in denen besonders gute Tieftemperatureigen- schatten und thermische Stabilität gefragt sind.wherein R 5 - R 8 are independently H, CH 3, Cl or Br, and X is Cι-C 5 alkylene, C 2 -C 5 alkylidene, C 5 -C 6 cycloalkylene, C 5 -Cι 0 cycloalkylidene is , are built up as monomers, as materials in areas where particularly good low-temperature properties and thermal stability are required.
Ganz besonders bevorzugt und selbst Erfindungsgegenstand sind Copolycarbonate aufgebaut aus 34-26 mol %, speziell 33-27 mol %, insbesondere 32-28 mol %, ganz speziell 31-29 mol % und besonders herausgehoben 30 mol % an Monomer der Formel (I), jeweils durch einen komplementären Gehalt an Monomer der Formel (II) ergänzt.Copolycarbonates composed of 34-26 mol%, especially 33-27 mol%, in particular 32-28 mol%, very particularly 31-29 mol% and particularly highlighted 30 mol% of monomer of formula (I) are very particularly preferred and even subject matter of the invention. , each supplemented by a complementary content of monomer of formula (II).
Die Prozentangaben der Bisphenol-Monomere beziehen sich auf den auf 100 % definierten Gesamtgehalt der Polycarbonate an Bisphenolen. Ein reines Bisphenol A Polycarbonat bestünde dann aus 100 % Bisphenol A. Der Carbonatanteil aus Kohlen- säureestern oder - Halogeniden wird dabei nicht mit berücksichtigt.The percentages of the bisphenol monomers relate to the total content of bisphenols defined in the polycarbonates at 100%. A pure bisphenol A polycarbonate would then consist of 100% bisphenol A. The carbonate content from carbonic acid esters or halides is not taken into account.
Bevorzugt, besonders bevorzugt oder ganz besonders bevorzugt sind Polycarbonate, welche die unter bevorzugt, besonders bevorzugt oder ganz besonders bevorzugt genannten Zusammensetzungen aufweisen .Preferred, particularly preferred or very particularly preferred are polycarbonates which have the compositions mentioned under preferred, particularly preferred or very particularly preferred.
Die oben aufgeführten allgemeinen oder in Vorzugsbereichen aufgeführten Definitionen, Mengenverhältnisse bzw. Erläuterungen können jedoch auch untereinander, also zwischen den jeweiligen Bereichen und Vorzugsbereichen beliebig kombiniert werden. Sie gelten für die Endprodukte sowie für die Vor- und Zwischenprodukte entsprechend.However, the general definitions, quantitative ratios or explanations given above or in preferred areas can also be combined with one another, that is, between the respective areas and preferred areas become. They apply accordingly to the end products as well as to the preliminary and intermediate products.
Es hat sich nun überraschenderweise gezeigt, dass solche Copolycarbonate einerseits besonders gute Tieftemperatureigenschaften, andererseits auch besonders gute Alterungseigenschaften aufweisen. Sie sind daher als Formkörper überall dort einsetzbar, wo die bislang bekannten Polycarbonate in ihrem Eigenschaftsbild nicht ausreichend sind, insbesondere z. B. im Elektrosektor sowie im Bausektor, für Abdeckungen oder Verglasungen, insbesondere im Kraftfahrzeugbereich als Folien, Platten, Armaturen- teile oder Gehäuseteile, aber auch im optischen Bereich als Linsen und Datenspeicher sowie als Gebrauchsartikel, und zwar dann, wenn erhöhte Wärmeform- oder Chemikalienbeständigkeit bei gleichzeitig guten Tieftemperatureigenschaften und/oder Alterungsstabilitat verlangt werden. Daneben können sie auch andere Werkstoffe ersetzen, in denen gewöhnliche Polycarbonate auf Grund ihrer dafür nicht ausreichenden Tief- temperatureigenschaften bislang nicht eingesetzt werden konnten.Surprisingly, it has now been shown that such copolycarbonates on the one hand have particularly good low-temperature properties and on the other hand also have particularly good aging properties. They can therefore be used as moldings wherever the properties of the polycarbonates known hitherto are insufficient, in particular, for. B. in the electrical sector and in the construction sector, for covers or glazing, in particular in the automotive sector as films, plates, fittings or housing parts, but also in the optical field as lenses and data storage as well as consumer goods, when increased heat resistance or chemical resistance with good low-temperature properties and / or aging stability at the same time. In addition, they can also replace other materials in which ordinary polycarbonates have not been able to be used because of their insufficient low-temperature properties.
Unter guten Tieftemperatureigenschaften ist erfindungsgemäß beispielhaft aber nicht einschränkend eine gute Tieftemperaturzähigkeit zu verstehen, da gewöhnliche Polycarbonate bei tiefen Temperaturen bei der Kerbschlagprüfung spröde brechen.Good low-temperature properties are to be understood according to the invention as good, but not restrictive, good low-temperature toughness, since ordinary polycarbonates break brittle at low temperatures in the impact test.
Unter tiefen Temperaturen sind erfindungsgemäß Temperaturen unterhalb -10°C, besonders bevorzugt unterhalb -20°C, besonders bevorzugt unterhalb -30°C, ganz besonders bevorzugt unterhalb -40°C, insbesondere unterhalb -50°C zu verstehen.According to the invention, low temperatures are understood to mean temperatures below -10 ° C, particularly preferably below -20 ° C, particularly preferably below -30 ° C, very particularly preferably below -40 ° C, in particular below -50 ° C.
Unter guter thermischer Stabilität und Alterungsstabilitat ist erfindungsgemäß beispielhaft aber nicht einschränkend eine gute Kerbschlagzähigkeit nach Temperung zu verstehen, da gewöhnliche Polycarbonate nach Temperung spröde werden, und damit zum Brechen und Reißen neigen.According to the invention, good thermal stability and aging stability is to be understood, by way of example, but not restrictively, to mean good notched impact strength after annealing, since ordinary polycarbonates become brittle after annealing and thus tend to break and crack.
Unter Temperung ist erfindungsgemäß eine Lagerung bei Temperaturen unterhalb derAccording to the invention, under tempering, storage at temperatures below the
Glasübergangstemperatur von 155°C zu verstehen, bevorzugt ist der Temperaturbe- reich von 40°C bis 140°C, besonders bevorzugt von 60°C bis 140°C und ganz besonders bevorzugt von 80°C bis 140°C.Glass transition temperature of 155 ° C to understand, preferably the temperature is range from 40 ° C to 140 ° C, particularly preferably from 60 ° C to 140 ° C and very particularly preferably from 80 ° C to 140 ° C.
Bevorzugte Verbindungen der Formel (I) sind 4,4'-Dihydroxydiphenyl (DOD) und 4,4'-Dihydroxy-3,3',5,5'tetra(tert.-Butyl)diphenyl, 4,4'-Dihydroxy-3,3 ',5,5'tetra(n- butyl)diphenyl und 4,4'-Dihydroxy-3,3',5,5'tetra(methyl)diphenyl, besonders bevorzugt ist 4,4'- Dihydroxydiphenyl.Preferred compounds of formula (I) are 4,4'-dihydroxydiphenyl (DOD) and 4,4'-dihydroxy-3,3 ', 5,5'tetra (tert-butyl) diphenyl, 4,4'-dihydroxy- 3,3 ', 5,5'tetra (n-butyl) diphenyl and 4,4'-dihydroxy-3,3', 5,5'tetra (methyl) diphenyl, 4,4'-dihydroxydiphenyl is particularly preferred.
Bevorzugte Verbindungen der Formel (II) sind 2,2-Bis(4-hydroxyphenyl)propan, 1,1- Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexan und l,3-Bis[2-(4-hydroxyphenyl)-2- propyl]benzol, 1 , 1 -Bis(4-hydroxyphenyl)- 1 -phenyl ethan, 1 , 1 -Bis(4-hydroxyphenyl)- cyclohexan, insbesondere 2,2-Bis(4-hydroxyphenyl)propan (Bisphenol A) und 1,1- Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexan (Bisphenol TMC), ganz besonders bevorzugt 2,2-Bis(4-hydroxyphenyl)propan (Bisphenol A).Preferred compounds of the formula (II) are 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 1,3-bis [2- (4- hydroxyphenyl) -2-propyl] benzene, 1,1-bis (4-hydroxyphenyl) -1-phenyl ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, in particular 2,2-bis (4-hydroxyphenyl) propane (Bisphenol A) and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC), very particularly preferably 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).
Es können sowohl eine Verbindung der Formel (I), unter Bildung binärer Copolycarbonate, als auch mehrere Verbindungen der Formel (I) verwendet werden.Both a compound of the formula (I), with the formation of binary copolycarbonates, and several compounds of the formula (I) can be used.
Ebenso können sowohl eine Verbindung der Formel (II), unter Bildung binärer Co- polycarbonate, als auch mehrere Verbindungen der Formel (II) verwendet werden.Likewise, both a compound of the formula (II), with formation of binary copolycarbonates, and also a plurality of compounds of the formula (II) can be used.
Die Edukte der Formel (I) und (II) können selbstverständlich Verunreinigungen, bedingt durch die Synthese, enthalten. Eine hohe Reinheit ist aber wünschenswert und anzustreben, daher werden diese Edukte mit der höchst möglichen Reinheit eingesetzt.The starting materials of the formula (I) and (II) can of course contain impurities due to the synthesis. A high level of purity is desirable and desirable, which is why these educts are used with the highest possible level of purity.
Die Herstellung von Polycarbonaten und Copolycarbonaten ist in der Literatur allgemein bekannt, und wird auch in den erfindungsgemäßen Fällen entsprechend durchgeführt: Gemäß DE-OS 2 119 779 erfolgt die Herstellung von Polycarbonaten unter Beteiligung von Monomeren der Formel (I) vorzugsweise in Lösung, und zwar nach dem Phasengrenzflächenverfahren und dem Verfahren in homogener Phase.The production of polycarbonates and copolycarbonates is generally known in the literature and is also carried out accordingly in the cases according to the invention: According to DE-OS 2 119 779, the production of polycarbonates with the participation of monomers of the formula (I) is preferably carried out in solution, specifically by the phase interface process and the process in homogeneous phase.
Zur Herstellung von Polycarbonaten nach dem Phasengrenzflächenverfahren sei beispielhaft auf "Schnell", Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York, London, Sydney 1964 und auf Polymer Reviews, Volume 10, "Condensation Polymers by Interfacial and Solution Methods", Paul W. Morgan, Interscience Publishers, New York 1965, Kap. VHI, S. 325 und EP 971790 verwiesen.For the production of polycarbonates by the phase interface process, examples include "Schnell", Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York, London, Sydney 1964 and Polymer Reviews, Volume 10, "Condensation Polymers by Interfacial and Solution Methods ", Paul W. Morgan, Interscience Publishers, New York 1965, chap. VHI, p. 325 and EP 971790 referenced.
Daneben ist die Herstellung auch nach dem bekannten Polycarbonatherstellungs- verfahren in der Schmelze (sogenanntes Schmelzeumesterungsverfahren) möglich, das z.B. in DE-OS 19 64 6401 oder in DE-OS 1 42 38 123 beschrieben ist. Daneben werden Umesterungsverfahren (Acetatverfahren und Phenylesterverfahren) beispielsweise in den US-PS 3 494 885, 4 386 186, 4 661 580, 4 680 371, und 4 680 372, in den EP-A 26120, 26121, 26684, 28030, 39845, 91602, 97970, 79075, 146887, 156103, 234913 und 240301 sowie in den DE-A 1 495 626 und 2232 977 beschrieben.In addition, production is also possible in the melt using the known polycarbonate production process (so-called melt transesterification process), which, for example, is described in DE-OS 19 64 6401 or in DE-OS 1 42 38 123. In addition, transesterification processes (acetate processes and phenyl ester processes) are described, for example, in US Pat. Nos. 3,494,885, 4,386,186, 4,661,580, 4,680,371 and 4,680,372, in EP-A 26120, 26121, 26684, 28030, 39845, 91602, 97970, 79075, 146887, 156103, 234913 and 240301 and in DE-A 1 495 626 and 2232 977.
Die Copolycarbonate können Molekulargewichte zwischen Mw (gewichtsgemitteltesThe copolycarbonates can have molecular weights between Mw (weight average
Molekulargewicht) 10.000 bis 60.000 aufweisen, bevorzugt Mw 20.000 bis 55.000, ermittelt durch Messung der relativen Lösungsviskosität in Dichlormethan oder in Mischungen gleicher Gewichtsmengen Phenol/o-Dichlorbenzol, geeicht durch Lichtstreuung.Molecular weight) 10,000 to 60,000, preferably Mw 20,000 to 55,000, 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.
Die erfindungsgemäßen Polycarbonate sind bei Temperaturen von 240°C bis 380°C, vorzugsweise 260°C bis 360°C in üblicher Weise thermoplastisch verarbeitbar. Durch Spritzguss oder via Extrusion können beliebige Formkörper und Folien in bekannter Weise hergestellt werden. Formkörper und Extrudate aus den erfindungs- gemäßen Copolycarbonaten sind ebenfalls Gegenstand der vorliegenden Anmeldung. Die erfindungsgemäßen Polycarbonate sind in Lösungsmitteln wie chlorierten Kohlenwasserstoffen, z.B. Methylenchlorid, gut löslich und können somit beispielsweise in bekannter Weise zu Gießfolien verarbeitet werden.The polycarbonates according to the invention can be processed thermoplastically in the usual manner at temperatures of 240 ° C. to 380 ° C., preferably 260 ° C. to 360 ° C. Any shaped bodies and foils can be produced in a known manner by injection molding or via extrusion. Moldings and extrudates from the copolycarbonates according to the invention are also the subject of the present application. The polycarbonates according to the invention are readily soluble in solvents such as chlorinated hydrocarbons, for example methylene chloride, and can thus be processed, for example, to give cast films in a known manner.
Die Kombination von Eigenschaften wie Wärmeformbeständigkeit, gute Tieftemperatureigenschaften, Alterungsstabilitat und Chemikalienbeständigkeit ermöglicht einen breiten Einsatz der erfindungsgemäßen Copolymere. Mögliche Anwendungen der erfindungsgemäßen Polycarbonate sindThe combination of properties such as heat resistance, good low-temperature properties, aging stability and chemical resistance enables the copolymers according to the invention to be used widely. Possible uses of the polycarbonates according to the invention are
1. Sicherheitsscheiben, die bekanntlich in vielen Bereichen von Gebäuden, Fahrzeugen und Flugzeugen erforderlich sind, sowie als Schilde von Helmen.1. Safety windows, which are known to be required in many areas of buildings, vehicles and aircraft, and as shields for helmets.
2. Herstellung von Folien, insbesondere Skifolien.2. Production of foils, especially ski foils.
3. Herstellung von Blaskörpern (siehe beispielsweise US-Patent 2 964794).3. Manufacture of bladders (see, for example, US Patent 2 964 794).
4. Herstellung von lichtdurchlässigen Platten, insbesondere von Hohlkarnmerplatten, beispielsweise zum Abdecken von Gebäuden wie Bahnhöfen, Gewächshäusern und4. Production of translucent panels, in particular hollow panels, for example for covering buildings such as train stations, greenhouses and
Beleuchtungsanlagen.Lighting systems.
5. Zur Herstellung von Ampelgehäusen oder Verkehrsschildern.5. For the production of traffic light housings or traffic signs.
6. Zur Herstellung von Schaumstoffen (siehe beispielsweise DE- AS 1 031 507).6. For the production of foams (see for example DE-AS 1 031 507).
7. Zur Herstellung von Fäden und Drähten (siehe beispielsweise DE- AS 1 137 167 und DE-OS 1 785 137).7. For the production of threads and wires (see for example DE-AS 1 137 167 and DE-OS 1 785 137).
8. Als transluzente Kunststoffe mit einem Gehalt an Glasfasern für lichttechnische Zwecke (siehe beispielsweise DE-OS 1 554020).8. As translucent plastics containing glass fibers for lighting purposes (see for example DE-OS 1 554020).
9. Zur Herstellung von Präzisionsspritzgussteilchen, wie beispielsweise Linsen- halterungen. Hierzu verwendet man Polycarbonate mit einem Gehalt an Glasfasern, die gegebenenfalls zusätzlich etwa 1 - 10 Gew.-% MoS2, bezogen auf das Gesamtgewicht, enthalten.9. For the production of precision injection molded particles, such as lens holders. For this purpose, polycarbonates with a glass fiber content are used, which may additionally contain about 1-10% by weight of MoS 2 , based on the total weight.
10. Zur Herstellung optischer Geräteteile, insbesondere Linsen für Foto- und Filmkameras (siehe beispielsweise DE-OS 2 701 173).10. For the production of optical device parts, in particular lenses for photo and film cameras (see for example DE-OS 2 701 173).
11. Als Lichtübertragungsträger, insbesondere als Lichtleiterkabel (siehe beispielsweise EP-AI 0 089 801). 12. Als Elektroisolierstoffe für elektrische Leiter und für Steckergehäuse sowie Steckverbinder.11. As a light transmission carrier, in particular as an optical fiber cable (see for example EP-AI 0 089 801). 12. As electrical insulating materials for electrical conductors and for connector housings and connectors.
13. Als Trägermaterial für organische Fotoleiter.13. As a carrier material for organic photoconductors.
14. Zur Herstellung von Leuchten, z.B. Scheinwerferlampen, als sogenannte "head- lamps" oder Streulichtscheiben.14. For the manufacture of lights, e.g. Headlight lamps, so-called "head lamps" or scattered light discs.
15. Für medizinische Anwendungen, z.B. Oxygenatoren, Dialysatoren.15. For medical applications, e.g. Oxygenators, dialyzers.
16. Für Lebensmittelanwendungen, wie z.B. Flaschen, Geschirr und Schokoladenformen.16. For food applications such as Bottles, dishes and chocolate molds.
17. Für Anwendungen im Automobilbereich, wo Kontakt zu Kraftstoffen und Schmier- mittein auftreten kann.17. For applications in the automotive sector, where contact with fuels and lubricants can occur.
18. Für Sportartikel, wie z.B. Slalomstangen.18. For sporting goods such as Slalom poles.
19. Für Haushaltsartikel, wie z.B. Küchenspülen und Briefkastengehäuse.19. For household items such as Kitchen sinks and mailbox housings.
20. Für Gehäuse, wie z.B. Elektroverteilerschränke20. For housings such as Electrical distribution cabinets
21. Für sonstige Anwendungen, wie z.B. Stallmasttüren oder Tierkäfige.21. For other applications, such as Barn doors or animal cages.
Insbesondere können aus den hochmolekularen aromatischen Polycarbonaten der Erfindung Folien hergestellt werden. Die Folien haben bevorzugte Dicken zwischen 1 und 1500 μm, insbesondere bevorzugte Dicken zwischen 10 und 900 μm.In particular, films can be made from the high molecular weight aromatic polycarbonates of the invention. The films have preferred thicknesses between 1 and 1500 μm, in particular preferred thicknesses between 10 and 900 μm.
Die erhaltenen Folien können in an sich bekannter Weise monoaxial oder biaxial gereckt werden, bevorzugt im Verhältnis 1 : 1,5 bis 1 : 5.The films obtained can be stretched monoaxially or biaxially in a manner known per se, preferably in a ratio of 1: 1.5 to 1: 5.
Die Folien können nach den bekannten Verfahren zur Folienerzeugung hergestellt werden, z.B. durch Extrusion einer Polymerschmelze durch eine Breitschlitzdüse, durch Blasen auf einer Folienblasmaschine, durch Tiefziehen oder Gießen. Dabei ist es möglich, dass die Folien für sich allein verwendet werden. Man kann mit ihnen natürlich auch nach den herkömmlichen Verfahren Verbundfolien mit anderen Kunststoff- Folien herstellen, wobei prinzipiell, je nach gewünschter Anwendung und Endeigenschaft der Verbundfolie, alle bekannten Folien als Partner in Frage kommen. Es kann ein Verbund aus zwei oder mehr Folien erzeugt werden. Daneben können die erfindungsgemäßen Copolycarbonate auch in anderen Schichtsystemen Anwendung finden, wie z.B. in coextrudierten Platten.The films can be produced by the known processes for film production, for example by extrusion of a polymer melt through a slot die, by blowing on a film blowing machine, by deep drawing or casting. It is possible that the foils are used on their own. They can of course also be used to produce composite films with other plastic films using the conventional methods, with all known films in principle being suitable as partners, depending on the desired application and the end property of the composite film. A composite of two or more foils can be created. In addition, the copolycarbonates according to the invention can also be used in other layer systems, for example in coextruded sheets.
Die erfindungsgemäßen Polycarbonate können verschiedene Endgruppen enthalten. Diese werden durch Kettenabbrecher eingeführt. Kettenabbrecher im Sinne der Erfindung sind solche der Formel (III)The polycarbonates according to the invention can contain different end groups. These are introduced by chain breakers. Chain terminators in the sense of the invention are those of the formula (III)
wobei R, R' und R" unabhängig voneinander H, gegebenenfalls verzweigte Cj-C 4-where R, R 'and R "independently of one another H, optionally branched Cj-C 4 -
Alkyl/Cycloalkyl, C7-C 4-Alkaryl oder C6-C34-Aryl darstellen können, beispielsweise Butylphenol, Tritylphenol, Cumylphenol, Phenol, Octylphenol, bevorzugt Butyl- phenol oder Phenol.Can represent alkyl / cycloalkyl, C 7 -C 4 alkaryl or C 6 -C 34 aryl, for example butylphenol, tritylphenol, cumylphenol, phenol, octylphenol, preferably butylphenol or phenol.
Die Polycarbonate können geringe Mengen von 0,02 bis 3,6 mol % (bezogen auf dieThe polycarbonates can contain small amounts of 0.02 to 3.6 mol% (based on the
Dihydroxyverbindung) an Verzweigern enthalten. Geeignete Verzweiger sind die für die Polycarbonatherstellung geeigneten Verbindungen mit drei und mehr funktioneilen Gruppen, vorzugsweise solche mit drei oder mehr als drei phenolischen OH-Gruppen, beispielsweise Verzweiger, wie in EP-A 708 130, S. 4, genannt, bevor- zugt 1,1,1 -Tri-(4-hydroxyphenyl)ethan und Isatinbiskresol.Dihydroxy compound) contained on branching. Suitable branching agents are the compounds with three or more functional groups suitable for polycarbonate production, preferably those with three or more than three phenolic OH groups, for example branching agents, as mentioned in EP-A 708 130, p. 4, preferably 1 , 1,1-tri- (4-hydroxyphenyl) ethane and isatin biscresol.
Zur Änderung der Eigenschaften können den erfindungsgemäßen Polycarbonaten Hilfs- und Verstärkungsstoffe zugemischt werden. Als solche sind u.a. in Betracht zu ziehen: Thermo- und UV-Stabilisatoren, Fließhilfsmittel, Entformungsmittel, Flammschutzmittel, Pigmente, fein zerteilte Mineralien, Faserstoffe, z.B. Alkyl- undTo change the properties, auxiliaries and reinforcing materials can be added to the polycarbonates according to the invention. As such, To consider: thermal and UV stabilizers, flow aids, mold release agents, flame retardants, pigments, finely divided minerals, fiber materials, e.g. Alkyl and
Arylphosphite, -phosphate, -phosphane, niedermolekulare Carbonsäureester, Halogenverbindungen, Salze, Kreide, Quarzmehl, Glas- und Kohlenstofffasern, Pigmente und deren Kombination. Solche Verbindungen werden z.B. in WO 99/55772, S. 15 - 25, und in "Plastics Additives", R. Gächter und H. Müller, Hanser Publishers 1983, beschrieben.Aryl phosphites, phosphates, phosphines, low molecular weight carboxylic acid esters, halogen compounds, salts, chalk, quartz powder, glass and carbon fibers, pigments and their combinations. Such compounds are described, for example, in WO 99/55772, pp. 15-25, and in "Plastics Additives", R. Gächter and H. Müller, Hanser Publishers 1983.
Weiterhin kömien den erfindungsmäßen Polycarbonaten auch andere Polymere zu- gemischt werden, z.B. Polyolefine, Polyurethane, Polyester, Acrylnitrilbutadienstyrol und Polystyrol.Furthermore, other polymers can also be mixed into the polycarbonates according to the invention, e.g. Polyolefins, polyurethanes, polyesters, acrylonitrile butadiene styrene and polystyrene.
Der Zusatz dieser Stoffe erfolgt vorzugsweise auf herkömmlichen Aggregaten zum fertigen Polycarbonat, kann jedoch, je nach den Erfordernissen, auch auf einer anderen Stufe des Herstellverfahrens erfolgen.These substances are preferably added to the finished polycarbonate in conventional units, but, depending on the requirements, can also be carried out at a different stage in the production process.
Die nachfolgenden Beispiele sollen die vorliegende Erfindung illustrieren, ohne sie jedoch einzuschränken: The following examples are intended to illustrate the present invention without, however, restricting it:
BeispieleExamples
Nach den bekannten Herstellverfahren in der Schmelze, wie beispielsweise in DEAccording to the known manufacturing processes in the melt, such as in DE
4238 123 beschrieben, und über die Phasengrenzfläche, wie zum Beispiel in "Schnell", Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9,4238 123, and about the phase interface, as for example in "Schnell", Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9,
Interscience Publishers, New York, London, Sydney 1964 beschrieben, wurden verschiedene Polycarbonate synthetisiert und mit handelsüblichem Makrolon mit vergleichbarer Viskosität verglichen.Interscience Publishers, New York, London, Sydney 1964 described, various polycarbonates were synthesized and compared with commercially available Makrolon with comparable viscosity.
Die relative Lösungsviskosität wurde in Dichlormethan bei einer Konzentration vonThe relative solution viscosity was determined in dichloromethane at a concentration of
5 g/1 bei 25°C bestimmt, geeicht durch Lichtstreuung.5 g / 1 determined at 25 ° C, calibrated by light scattering.
Zur Ermittlung der Schlagzähigkeit wurde der Schlagbiegeversuch nach ISO 180/4A verwendet.The impact test according to ISO 180 / 4A was used to determine the impact strength.
Beispiel 1example 1
Im Phasengrenzflächenverfahren wurde ein Polycarbonat mit 30 mol % Dihydroxy- diphenyl (DOD) und 70 mol % Bisphenol A hergestellt. Als Kettenabbrecher wurde tert-Butylphenol verwendet. Das Granulat weist eine relative Lösungsviskosität vonA polycarbonate with 30 mol% dihydroxydiphenyl (DOD) and 70 mol% bisphenol A was produced in the phase interface process. Tert-butylphenol was used as the chain terminator. The granules have a relative solution viscosity of
1,298 auf.1,298.
Beispiel 2Example 2
Im Phasengrenzflächenverfahren wurde ein Polycarbonat mit 30 mol % DOD undA polycarbonate with 30 mol% DOD and
70 mol % Bisphenol A hergestellt. Als Kettenabbrecher wurde tert-Butylphenol verwendet. Das Granulat weist eine relative Lösungsviskosität von 1,341 auf. Beispiel 370 mol% bisphenol A. Tert-butylphenol was used as the chain terminator. The granules have a relative solution viscosity of 1.341. Example 3
Im Schmelzeumesterungsverfahren wurde ein Polycarbonat mit 30 mol % DOD und 70 mol % Bisphenol A hergestellt. Das Produkt weist eine relative Lösungsviskosität von 1,28 auf.A polycarbonate with 30 mol% DOD and 70 mol% bisphenol A was produced in the melt transesterification process. The product has a relative solution viscosity of 1.28.
Vergleichsbeispiel 1Comparative Example 1
Im Schmelzeumesterungsverfahren wurde ein Polycarbonat mit 35 mol % DOD und 65 mol % Bisphenol A hergestellt. Das Produkt weist eine relative Lösungsviskosität von 1,295 auf.A polycarbonate with 35 mol% DOD and 65 mol% bisphenol A was produced in the melt transesterification process. The product has a relative solution viscosity of 1.295.
Vergleichsbeispiel 2Comparative Example 2
Im Schmelzeumesterungsverfahren wurde ein Polycarbonat mit 25 mol % DOD undIn the melt transesterification process, a polycarbonate with 25 mol% DOD and
75 mol % Bisphenol A hergestellt. Das Produkt weist eine relative Lösungsviskosität von 1,295 auf.75 mol% bisphenol A produced. The product has a relative solution viscosity of 1.295.
Vergleichsbeispiel 3Comparative Example 3
Im Schmelzeumesterungsverfahren wurde ein Polycarbonat mit 20 mol % DOD und 80 mol % Bisphenol A hergestellt. Das Produkt weist eine relative Lösungsviskosität von 1,295 auf.A polycarbonate with 20 mol% DOD and 80 mol% bisphenol A was produced in the melt transesterification process. The product has a relative solution viscosity of 1.295.
Einen Vergleich mit handelsüblichem Makrolon zeigen Tabellen 1-2. A comparison with commercially available Makrolon is shown in Tables 1-2.
Tabelle 1: Vergleich der LösungsviskositätenTable 1: Comparison of the solution viscosities
Tabelle 2: Vergleich der Kerbschlagzähigkeit und der Erweichungstemperatur s = spröd gebrochen z = zäh gebrochenTable 2: Comparison of notched impact strength and softening temperature s = brittle broken z = tough broken
Die Tabelle 2 zeigt die überlegene Tieftemperaturzähigkeit der erfindungsgemäßen Copolycarbonate der Beispiele 1-3 bei -60 °C. Table 2 shows the superior low-temperature toughness of the inventive copolycarbonates of Examples 1-3 at -60 ° C.
Tabelle 3: Vergleich der Kerbschlagzähigkeiten nach ISO 180/4A in [kJ/m ] s = spröd gebrochen z = zäh gebrochenTable 3: Comparison of the impact strength according to ISO 180 / 4A in [kJ / m] s = brittle broken z = tough broken
Wie in der Tabelle 3 dargestellt, zeigt sich ein deutlich verändertes Eigenschaftsprofil bei dem erfindungsgemäßen Copolycarbonat auch nach Alterung. Bereits nach einer Lagerungszeit von 46 h bei 135° zeigt Polycarbonat aus reinem Bisphenol A ein Spröd- bruchverhalten, während das zähe Verhalten des Copolycarbonats auch nach 7 Tagen noch zu beobachten ist. Darüber hinaus zeigt das Copolymer auch bei Lagerung bei 150°C und anschließender Kerbschlagzähigkeitsprüfung noch ein zähes Bruchverhalten auf hohem Niveau. As shown in Table 3, the property profile of the copolycarbonate according to the invention also changed significantly after aging. Already after a storage time of 46 h at 135 °, polycarbonate from pure bisphenol A shows brittle fracture behavior, while the tough behavior of the copolycarbonate can still be observed after 7 days. In addition, the copolymer shows tough fracture behavior at a high level even after storage at 150 ° C. and subsequent impact test.

Claims

Patentansprü ch e Claims e
1. Verwendung von thermoplastischen Copolycarbonaten, aufgebaut aus 0,1 mol % bis 46 mol %, vorzugsweise aus 11 mol % bis 34 mol % und insbesondere aus 26 mol % bis 34 mol % Verbindungen der Formel (I),1. Use of thermoplastic copolycarbonates, built up from 0.1 mol% to 46 mol%, preferably from 11 mol% to 34 mol% and in particular from 26 mol% to 34 mol%, of compounds of the formula (I),
worin R1 bis R4 unabhängig voneinander für H, Cι-C4-Alkyl, Phenyl, substituiertes Phenyl oder Halogen stehen, bevorzugt für H, Cι-C4-Alkyl oder Halogen stehen und besonders bevorzugt alle für den gleichen Rest, insbesondere für H oder tert.-Butyl stehen, und komplementäre Mengen, also 99,9 mol % bis 54 mol %, vorzugsweise 89 mol % bis 66 mol % und insbesondere 74 mol % bis 66 mol % an Verbindungen der Formel (11)wherein R 1 to R 4 independently of one another are H, -CC 4 -alkyl, phenyl, substituted phenyl or halogen, preferably H, -CC 4 -alkyl or halogen and particularly preferably all for the same radical, in particular for H or tert-butyl, and complementary amounts, ie 99.9 mol% to 54 mol%, preferably 89 mol% to 66 mol% and in particular 74 mol% to 66 mol%, of compounds of the formula (11)
worin R5 - R8 unabhängig voneinander H, CH3, Cl oder Br sind und X C1-C5- Alkylen, C2-C5-Alkyliden, C5-C6-Cycloalkylen, C5-Cι0-Cycloalkyliden ist, alswherein R 5 - R 8 are independently H, CH 3 , Cl or Br and XC 1 -C 5 alkylene, C 2 -C 5 alkylidene, C 5 -C 6 cycloalkylene, C 5 -Cι 0 cycloalkylidene , as
Monomere aufgebaut sind, als Werkstoffe in Bereichen in denen besonders gute Tieftemperatureigenschaften und/oder Alterungsstabilitat gefragt sind.Monomers are built up as materials in areas in which particularly good low-temperature properties and / or aging stability are required.
2. Verwendung der Copolycarbonate gemäß Anspruch 1 für Außenan- Wendungen. 2. Use of the copolycarbonates according to claim 1 for external applications.
3. Verwendung der Copolycarbonate gemäß Anspruch 1 für Folien.3. Use of the copolycarbonates according to claim 1 for films.
4. Verwendung der Copolycarbonate gemäß Anspruch 1 für optische Anwen- düngen.4. Use of the copolycarbonates according to claim 1 for optical applications.
5. Verwendung der Copolycarbonate gemäß Anspruch 1 für medizinische und Lebensmittelanwendungen.5. Use of the copolycarbonates according to claim 1 for medical and food applications.
6. Verwendung der Copolycarbonate gemäß Anspruch 1 im Automobilbereich.6. Use of the copolycarbonates according to claim 1 in the automotive field.
7. Verwendung der Copolycarbonate gemäß Anspruch 1 im Elektrobereich.7. Use of the copolycarbonates according to claim 1 in the electrical field.
8. Copolycarbonate gemäß Anspruch 1, dadurch gekennzeichnet, daß sie aus 34- 26 mol % an Monomer der Formel (I), sowie einem komplementären Gehalt an Monomer der Formel (II) aufgebaut sind. 8. Copolycarbonates according to claim 1, characterized in that they are made up of 34-26 mol% of monomer of formula (I) and a complementary content of monomer of formula (II).
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