EP2408840A1

EP2408840A1 - Copolycarbonates having improved properties

Info

Publication number: EP2408840A1
Application number: EP10709171A
Authority: EP
Inventors: Helmut-Werner Heuer; Rolf Wehrmann
Original assignee: Bayer MaterialScience AG
Current assignee: Bayer Intellectual Property GmbH
Priority date: 2009-03-18
Filing date: 2010-03-12
Publication date: 2012-01-25
Also published as: WO2010105769A1; SG174318A1; KR20110129395A; CN102356112A; US20120004375A1; JP2012520906A; DE102009013643A1

Abstract

The present invention relates to copolycarbonates having improved surface hardness, to methods for the production thereof and to the use thereof for the production of blends, moldings and extrudates, films (film layers), film laminates and cards.

Description

Copolycarbonates with improved properties

The present invention relates to molded parts and extrudates, films and laminates, with improved mechanical properties, with good heat resistance and chemical resistance, and to processes for their preparation and their use, in particular in the electrical / electronics (E / E) sector and in medical technology.

Aromatic polycarbonates belong to the group of engineering thermoplastics. They are characterized by the combination of the technologically important properties of transparency, heat resistance and toughness.

JP-A 09-183838 describes polycarbonates by the melt process in which the aromatic dihydroxy components have a content of at least 80 mol% of a mixture of 1,1-bis (4-hydroxyphenyl) -3,3,5- trimethylcyclohexane (TMC) and 2,2-bis (3-methyl-4-hydroxyphenyl) propane. The polycarbonates are due to their low birefringence particularly well suited for optical applications (discs, lenses, cards).

In JP-A 09-204053 are polycarbonates containing l, l-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 2,2-bis (3-methyl-4-hydroxyphenyl) propane as a binding component in an organic photoreceptor layer. However, these are applications in which only mixtures of copolycarbonates, the max. 50% TMC can be used with hydrazone derivatives. These applications are not the subject of this application.

WO 2008/008599 A2 discloses the use of polycarbonates which contain 2,2-bis (3-methyl-4-hydroxyphenyl) -propane and / or 1,1-bis (3-methyl-4-hydroxyphenyl) -cyclohexane can be described for the production of flame-retardant articles which have a good scratch resistance.

WO 2003/005354 A1 describes polycarbonates which may contain 1,1-bis (3-methyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane. Due to their good damping properties, these should be particularly suitable as materials for data carriers.

WO 2007/008390 A2 describes polycarbonates which contain 1,1-bis (3-methyl-4-hydroxyphenyl) -cyclohexane and optionally 2,2-bis (3-methyl-4-hydroxyphenyl) -propane. It is disclosed that windows and other articles of this copolycarbonate have good scratch resistance. It also reveals a good resistance to ammonia. JP-A 10-138649 discloses homo- and copolycarbonates containing various diphenols suitable for non-blocking sheets in thermal transfer applications. The specific combinations mentioned in the present application and their favorable properties are not described there.

The present invention ^' solves the problem, copolycarbonates available, which are composed of simple, unbridged monomer units and in comparison with known, constructed from simple, unbridged monomer building blocks copolycarbonates an improved combination of properties in terms of surface hardness, scratch resistance, heat resistance and chemical resistance. The present invention further solves the problems of providing processes for producing such copolycarbonates and such copolycarbonates for applications in which special demands are made on the stability of the surface and / or on the chemical resistance and / or on the heat resistance, without any additional protective layer would have to be applied. In particular, applications and products for medical technology, for the electrical / electronics sector (eg "soft keys"), lenses (eg infrared lenses), screen / display covers, frames and housing parts as well as foils, film laminates and cards should be mentioned.

Surprisingly, it has been found that copolycarbonates can be obtained by using a combination of in each case at least one compound of the general formula (Ia) and (Ib)

(1a)

(1b) in which R 1 is independently of one another C 1 -C ₄ -alkyl, preferably methyl, ethyl, n-propyl, isopropyl, t-butyl, very particularly preferably methyl,

n for 1, 2 or 3,

and R2 are independently H, linear or branched C _J -C _JO alkyl, preferably linear or branched C _r C ₆ alkyl, particularly preferably linear or branched C _r C ₄ alkyl, especially methyl, ethyl, n-propyl, i- Propyl, t-butyl, and most preferably methyl,

and in which R3 independently of one another represent linear or branched Ci-Ci ₀ alkyl, preferably linear or branched QC ₆ alkyl, particularly preferably linear or branched QC ₄ alkyl, very particularly preferably represent C alkyl, and

the _R ₄ independently of one another are H, linear or branched C ₁ -C 20 -alkyl, preferably linear or branched C ₁ -C ₆ -alkyl, particularly preferably linear or branched C ₁ -C ₄ -alkyl, in particular methyl, ethyl, n-propyl, isopropyl , t-butyl, and most preferably H or methyl,

solve this problem.

The copolycarbonates according to the invention thus contain diphenolate monomer units derived from

a) at least one compound selected from the group comprising the compounds having the general formula

da) in which the Rl, independently, C _r C ₄ alkyl, preferably methyl, ethyl, n-propyl, i-propyl, t-butyl, most preferably methyl,

n for 1, 2 or 3,

and _R ₂ independently of one another are 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, in particular methyl, ethyl, n-propyl, Propyl, t-butyl, and most preferably methyl, and b) at least one compound from the group containing the compounds having the general formula

(1b)

and in which the R 3 independently of one another are 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 -alkyl, and

the R ₄ independently of one another are 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, in particular methyl, ethyl, n-propyl, Propyl, t-butyl, and most preferably represent H or methyl.

The copolycarbonates particularly preferably contain combinations of one or more compounds of the general formulas (2a) and (2d), (2a) and (2b) and (2c) and (2b)

(2a) (2c)

(2b) (2d) in which n, Rl and R3 are the radicals described under the formulas (1).

Of the compounds (2a), (2b), (2c) and (2d), the compounds which are described by the formulas (3a), (3b), (3c) and (3d) are very particularly preferred.

(3a) (3c)

(3b) (3d)

The present invention therefore provides copolycarbonates comprising a combination of monomer units (4a) and (4b) derived from a combination of at least one compound of general formula (Ia) and at least one compound of general formula (Ib),

(4a) (4b) in which the R 1 independently of one another are C 1 -C ₄ -alkyl, preferably methyl, ethyl, n-propyl, isopropyl, t-butyl, very particularly preferably methyl,

n for 1, 2 or 3,

and R2 are independently H, linear or branched C] ₀ -C alkyl, preferably linear or branched Ci-C ₆ alkyl, particularly preferably linear or branched Ci-C ₄ alkyl, especially methyl, ethyl, n-propyl, i Propyl, t-butyl, and most preferably methyl,

and R3 are independently linear or branched Ci-Ci ₀ alkyl, preferably linear or branched Ci-C ₆ alkyl, particularly preferably linear or branched _Cj-C4-alkyl, very particularly preferably represent C alkyl, and

the R4 are each independently H, linear or branched Ci-Ci ₀ alkyl, preferably linear or branched QC ₆ alkyl, particularly preferably for linear or branched C _r C ₄ alkyl, in particular methyl, ethyl, n-propyl, i-propyl, t -Butyl, and most preferably represent H or methyl.

The monomer units are introduced via the corresponding diphenols of the general formulas (Ia) and (Ib).

Particular preference is given to the monomer units derived from diphenols of the general formula (2a) - (2d).

In each case, the combination of the compounds (2a) with (2b), (2b) with (2c) and (2a) with (2c) is particularly preferred. Most preferably, in these compounds n = 3, Rl and R3 = methyl.

This results in very particularly preferred copolymers according to the invention comprising combinations of the compounds

1, 1-bis (3-methyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (3a) and 2,2-bis (4-hydroxyphenyl) propane (3d) (bisphenol-A),

1, 1-bis (3-methyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (3a) and 2,2-bis (3-methyl-4-hydroxyphenyl) propane (3b) or

L, l-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (3c) (bisphenol TMC) and 2,2-bis (3-methyl-4-hydroxyphenyl) propane (3b) The total amount of diphenolic compounds (Ia) according to the invention in the copolycarbonate is 0.1-70 mol%, preferably 1-60 mol%, particularly preferably 5-50 mol% and very particularly preferably 5-35 mol% (based on the sum of the moles of diphenols used of the general formulas (Ia) and (Ib)). In other preferred embodiments, the total proportion of the compounds (Ia) is 40-90 mol%, 45-80 mol%, 50-75 mol% and 55-75 mol% based on the sum of the moles of diphenols used of the general formulas (Ia) and (Ib).

The copolycarbonates may be present as block and 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 polycarbonates or copolycarbonates can also be branched. For this purpose, certain small amounts, preferably amounts between 0.05 and 5 mol%, more preferably 0.1-3 MoI-%, most preferably 0.1-2 mol%, based on the moles of diphenols used, of trifunctional compounds such eg Isatin biscresol (IBK) or phloroglucinol, 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-hydroxy phenyl) -cyclohexyl] -propane; 2,4-bis (4-hydroxyphenylisopropyl) phenol; 2,6-bis- (2-hydroxy-5'-methyl-benzyl) -4-methyl phenol; 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) -propane; Hexa- (4- (4-hydroxyphenyl-isopropyl) -phenyl) -orthoterephthalate; Tetra (4-hydroxyphenyl) methane; Tetra- (4- (4-hydroxyphenyl-isopropyl) -phenoxy) -methane; Tris (4-hydroxyphenyl) -l, 3,5-triisopropylbenzene; 2,4-dihydroxybenzoic acid; trimesic; cyanuric chloride; 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole; 1,4-bis- (4 ', 4 "-dihydroxytriphenyl) -methyl) -benzene and in particular; l, l, l-tri- (4-hydroxyphenyl) -ethane and bis- (3-methyl-4-hydroxyphenyl) 2-oxo-2,3-dihydroindole are used as so-called branching agents, isatin biscresol and also l, l, l-tri- (4-hydroxyphenyl) -ethane and bis- (3-methyl-4-hydroxyphenyl) - 2-oxo-2,3-dihydroindole used as branching.

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 copolycarbonates according to the invention may additionally contain 2 to 20 parts of diphenols of the formula (5a)

(5a) contained in which

R is hydrogen, CpCig alkyl, C ³ and R ^{4 are} independently | -C ₈ -alkoxy, halogen, in each case optionally substituted aryl or aralkyl, are provided, and

X represents a single bond, -SO ₂ -, -CO-, -O-, -S- Q to C _£ _-A1kylen; C ₂ - to C ₅ -alkylidene or C ₅ - to C ₆ -cycloalkylidene which may be substituted by C ₁ - to C ₆ -alkyl, to C _6- C ₂ -arylene, which may optionally be condensed with further heteroatom-containing aromatic rings can, stands.

The structure (5a) is particularly preferably 2,2-bis (4-hydroxyphenyl) -propane (bisphenol A or BPA).

To obtain high molecular weight polycarbonates 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 such. As phenol or tert-butylphenol can be controlled. In these reactions arise almost exclusively linear polymers. This can be demonstrated by end group analysis. Through the targeted use of so-called branching agents, generally polyhydroxylated compounds, branched polycarbonates are also obtained.

The present invention furthermore relates to a process for the preparation of the copolycarbonates according to the invention comprising diphenolate units derived from diphenols of the formulas (1), (2) and (3), characterized in that the diphenols and any branching agents are dissolved in aqueous alkaline solution and treated with a optionally dissolved in a solvent carbonate source such as phosgene in a two-phase mixture of an aqueous alkaline solution, an organic solvent and a catalyst, preferably an amine compound, are reacted. The reaction can also be carried out in several stages.

Such processes for producing polycarbonate are basically two-phase interfacial processes, e.g. from H. Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York 1964 p. 33 et seq., and to Polymer Reviews, Vol. 10, "Condensation Polymers by Interfacial and Solution Methods", Paul W Morgan, Interscience Publishers, New York 1965, ch. VIII, p. 325 and the basic conditions are therefore familiar to the person skilled in the art.

The concentration of diphenols in the aqueous alkaline solution is from 2 to 25% by weight, preferably from 2 to 20% by weight, more preferably from 2 to 18% by weight and very particularly preferably from 3 to 15% by weight. The aqueous alkaline solution consists of water in which hydroxides of alkali or alkaline earth metals are dissolved. Preference is given to sodium and potassium hydroxides. When phosgene is used as the carbonate source, the volume ratio of aqueous alkaline solution to organic solvent is 5:95 to 95: 5, preferably 20:80 to 80:20, more preferably 30:70 to 70:30, and most preferably 40:60 to 60 : 40th The molar ratio of diphenol to phosgene is less than 1:10, preferably less than 1: 6, more preferably less than 1: 4 and most preferably less than 1: 3. The concentration of the branched polycarbonates and copolycarbonates according to the invention in the organic phase is 1.0 to 25% by weight, preferably 2 to 20% by weight, more preferably 2 to 18% by weight and most preferably 3 to 15% by weight.

The concentration of the amine compound, based on the amount of diphenol used, is 0.1 to 10 mol%, preferably 0.2 to 8 mol%, particularly preferably 0.3 to 6 mol%, and very particularly preferably 0.4 to 5 mol%.

Diphenols are to be understood as meaning diphenol mixtures selected from the abovementioned compounds with proportions of the abovementioned branching agents. The carbonate source is phosgene, diphosgene or triphosgene, preferably phosgene. In the event that phosgene is used, it may be possible to dispense with a solvent and the phosgene be introduced directly into the reaction mixture.

The catalyst used can be tertiary amines, such as triethylamine or N-alkylpiperidines. Suitable catalysts are trialkylamines and 4- (dimethylamino) pyridine. Particularly suitable are triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutylamine, N-methylpiperidine, N-ethylpiperidine, and N-propylpiperidine.

Suitable organic solvents are halogenated hydrocarbons such as methylene chloride, chlorobenzene, dichlorobenzene, trichlorobenzene or mixtures thereof or aromatic hydrocarbons such as toluene or xylenes. The reaction temperature may be from -5 ⁰ C to 100 ⁰ C, preferably 0 ⁰ C to 80 ⁰ C, more preferably 10 ⁰ C to 70 ⁰ C and most preferably 10 ⁰ C to 60 ⁰ C.

Also possible is the preparation of the polycarbonates by the melt transesterification process, in which the diphenols are reacted with diaryl carbonates, usually diphenyl carbonate, in the presence of catalysts, such as alkali salts, ammonium or phosphonium compounds, in the melt.

The melt transesterification process is described, for example, in the Encyclopedia of Polymer Science, Vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, Vol. 9, John Wiley and Sons, Inc. (1964) and DE-C 10 31 512 described.

In the melt transesterification process, the aromatic dihydroxy compounds already described in the phase boundary process 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 (6) and (7)

in which

R, R 'and R "are independently H, optionally branched Ci-C ₃₄ -alkyl / cycloalkyl, C ₇ -C ₃₄ - ₃₄ may represent -ATyI alkaryl or C ₆ -C

for example

diphenyl carbonate,

Butyl phenyl phenyl carbonate, di-butyl phenyl carbonate,

Isobutylphenyl-phenylcarbonate, di-isobutylphenylcarbonate, tert-butylphenyl-phenylcarbonate, di-tert-butylphenylcarbonate, n-pentylphenyl-phenylcarbonate, di (n-pentylphenyl) carbonate, n-hexylphenyl-phenylcarbonate, di (n-hexylphenyl) carbonate,

Cyclohexylphenyl phenyl carbonate, di-cyclohexylphenyl carbonate,

Phenylphenol-phenylcarbonate, di-phenylphenolcarbonate,

Isooctylphenyl-phenylcarbonate, diisooctylphenylcarbonate, n-nonylphenyl-phenylcarbonate, di (n-nonylphenyl) carbonate, cumylphenyl-phenylcarbonate, di-cumylphenylcarbonate,

Naphthyl phenyl phenyl carbonate, di-naphthyl phenyl carbonate,

Di-tert-butylphenyl-phenyl carbonate, di- (di-tert-butylphenyl) carbonate,

Dicumylphenyl phenyl carbonate, di- (dicumylphenyl) carbonate,

4-phenoxyphenyl-phenyl carbonate, di- (4-phenoxyphenyl) carbonate, 3-pentadecylphenyl phenyl carbonate, di- (3-pentadecylphenyl) carbonate trityl phenyl phenyl carbonate, di-trityl phenyl carbonate,

prefers

Diphenyl carbonate, tert-butylphenyl-phenylcarbonate, di-tert-butylphenylcarbonate, phenylphenol-phenylcarbonate, di-phenylphenolcarbonate, cumylphenyl-phenylcarbonate, di-cumylphenylcarbonate,

particularly preferably diphenyl carbonate.

It is also possible to use mixtures of the said carbonic diesters.

The proportion of carbonic acid ester is 100 to 130 mol%, preferably 103 to 120 mol%, particularly preferably 103 to 109 mol%, based on the dihydroxy compound.

As catalysts in the context of the invention, basic catalysts such as, for example, alkali metal and alkaline earth metal hydroxides and oxides but also ammonium or phosphonium salts, referred to below as onium salts, are used in the melt transesterification process as described in the cited literature. 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 (8)

(8th)

in which

R ^M have the same or different Ci-Ci _O alkyls, C ₆ -C ₀ aryls, C ₇ -C ₀ aralkyls or C ₅ -C ₆ - can be cycloalkyls, preferably methyl or C ₄ -C ₆ aryls, especially preferably methyl or phenyl, and

X ^"is an anion such as hydroxide, sulfate, hydrogen sulfate, hydrogen carbonate, carbonate, a halide, preferably-Θhlorid; may or an alcoholate of the formula OR, wherein R is C ₆ -Q ₄ -ATyI or C ₇ -C ₂ - aralkyl, preferably phenyl , which may be preferred catalysts tetraphenylphosphonium,

tetraphenylphosphonium,

Tetraphenylphosphonium phenolate, more preferably tetraphenylphosphonium phenolate.

The catalysts are preferably used in amounts of from θ ^' to θ ^{' 3} mol, based on one ripole diphenol, more preferably in amounts of from 10 ^'7 to 10 ^"4 mol.

Other 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 transesterification reaction of the aromatic dihydroxy compound and the carbonic diester in the melt is preferably carried out in two stages. In the first stage, the melting of the aromatic dihydroxy compound and the carbonic diester at temperatures of 80 - ^•

250 ⁰ C, preferably from 100 to 230 ⁰ C, particularly preferably 120 to 190 ⁰ C under normal pressure in 0-5

Hours, preferably 0.25 - 3 hours instead. After addition of the catalyst is by applying

Vacuum (up to 2 mm Hg) and increasing the temperature (up to 260 ⁰ C) by distilling off the monophenol the oligocarbonate from the aromatic dihydroxy compound and the

Carbonic acid diester produced. In this case, the majority of vapors from the process accrue. The oligocarbonate thus prepared has an average weight molecular weight M _w (determined by measuring the rel.

Solution viscosity in dichloromethane or in mixtures of equal amounts by weight of phenol / o-dichlorobenzene calibrated by light scattering) in the range from 2000 g / mol to 18 000 g / mol, preferably from 4000 g / mol to 15 000 g / mol.

In the second stage, the polycarbonate is produced in the polycondensation by further increasing the temperature to 250-320 ⁰ C, preferably 270-295 ⁰ C and a pressure of <2 mm Hg. The remainder of the vapors are removed from the process.

The catalysts can also be used in combination (two or more) with each other.

When using alkali / alkaline earth metal catalysts, it may be advantageous to add the alkali / alkaline earth metal catalysts at a later time (eg, after the oligocarbonate synthesis in the second stage polycondensation). The reaction of the aromatic dihydroxy compound and the carbonic acid diester to form the polycarbonate can be carried out batchwise or preferably continuously, for example in stirred vessels, thin-film evaporators, falling-film evaporators, stirred tank cascades, extruders, kneaders, simple disk reactors and high-viscosity disk reactors.

Analogous to the phase boundary process, branched poly- or copolycarbonates can be prepared by using polyfunctional compounds.

The relative solution viscosity of the copolycarbonates according to the invention, determined in accordance with DIN 51562, is preferably in the range from 1.15 to 1.35.

Preferred, particularly preferred or very particularly preferred are embodiments which make use of the parameters, compounds, definitions and explanations mentioned under preferred, particularly preferred or very particularly preferred or, preferably, etc.

However, the general or preferred definitions, parameters, compounds and explanations given in the description can also be combined with one another as desired, ie between the respective ranges and preferred ranges.

The copolycarbonates according to the invention can be worked up in a known manner and processed to give any shaped bodies, for example by extension, injection molding or extrusion blow molding.

The copolycarbonates according to the invention may also be blended with other aromatic polycarbonates and / or other aromatic polyester carbonates and / or other aromatic polyesters in a known manner, for example by compounding.

The copolycarbonates according to the invention can also be added in conventional amounts of the additives customary for these thermoplastics, such as mold release agents or gamma ray stabilizers. They can also contain shares of another plastic (blend).

The copolycarbonates according to the invention, optionally in admixture with other thermoplastics and / or customary additives, can be used to form any shaped articles / extrudates used wherever already known polycarbonates, polyestercarbonates and polyesters are used. Due to their property profile, they are particularly suitable as materials for injection molding of larger moldings, such as car windows. Due to the low water absorption and the associated improved dimensional stability but are also particularly suitable as substrate materials for optical data storage such as CD, CD-R, DVD, DVD-R, Blu-ray Disc or Advanced Optical Disc (AOD), but are also for example as films in the electrical sector as Moldings used in vehicle construction and as panels for covers in the security area. Further possible applications of the polycarbonates according to the invention are:

• Safety windows, which are known to be required in many areas of buildings, vehicles and aircraft, as well as shields of helmets.

• Production of films, in particular ski films.

Production of blown bodies (see for example US Pat. No. 2,964,794), for example 1 to 5 gallons of water bottles.

• Production of translucent panels, in particular of cellular panels, for example for covering buildings such as railway stations, greenhouses and lighting installations.

• Manufacture of optical data storage.

• For the production of traffic light housings or traffic signs.

For the production of foams (see, for example, DE-B 1 031 507).

For the production of threads and wires (see for example DE-B 1 137 167 and DE-A 1 785 137).

• As translucent plastics containing glass fibers for lighting purposes (see, for example, DE-A 1 554 020).

• As translucent plastics containing barium sulfate, titanium dioxide and / or zirconium oxide or organic polymeric acrylate rubbers (EP-A 634 445, EP-A 269 324) for the production of light-transmitting and light-scattering molded parts.

• For making precision injection molded parts, such as lens mounts. For this purpose, one uses polycarbonates with a content of glass fibers, which optionally additionally about 1-10 wt .-% MoS ₂ , based on total weight.

For the production of optical device parts, in particular lenses for photo and film cameras (see for example DE-A 2 701 173).

As light transmission carrier, in particular as optical fiber cable (see, for example, EP-A 0 089 801). • As electrical insulating material for electrical conductors and for connector housings and connectors.

• Manufacture of mobile phone cases with improved resistance to perfume, aftershave and skin sweat.

• Network interface devices

• For the production of lights, eg. B. headlamps, as so-called "head-lamps", scattered light lenses or inner lenses, and linear luminaires.

• For food applications, such as: As bottles, dishes and chocolate molds.

• For applications in the automotive sector, where contact with fuels and lubricants may occur, such as bumpers possibly in the form of suitable blends with ABS or suitable rubbers.

• For sporting goods, such as Slalom poles or ski boot buckles.

• For household items, such as B. kitchen sinks and letterbox housing.

• For housings, such as B. Electric distribution cabinets.

• Housing for electric toothbrushes and hair dryer housing

• Transparent washing machines - portholes with improved resistance to washing.

• goggles, visors or optical corrective goggles.

• Lamp covers for kitchen equipment with improved resistance to kitchen fumes, especially oil vapors.

• Packaging films for pharmaceuticals.

• Chip boxes and chip carriers

• For other applications, such as: B. stable mast doors or Tierkäfϊge.

• protective helmets

Particular preference is given to applications of the copolycarbonates according to the invention in medical technology, in particular products for • medical applications, eg oxygenators, dialyzers (hollow fiber dialyzers), dialysis modules or hemofilters (transparent housing parts of this "artificial kidney")

• cardiotomy reservoirs (for use during the suctioned blood collection operation)

• blood heat exchanger

• Hose connector

• 3 way taps

• blood filter

• Injection systems (for direct contact with blood and intravenous fluids)

• inhalers (for asthma and respiratory treatment)

• Centrifuge systems in medical technology (blood centrifuge in combination with a cardiotomy reservoir)

Ampoules (eg for a needle-free injection system)

• foils, for example, for use in blood glucose meters

• Patient terminal (eg call systems for nursing staff)

• Operating boxes for scalpels in surgery

• Suction devices for emergency medicine

• Lamp housing for baby incubators

• Ventilation assistance, eg B. Resuscitation bag in the rescue service

• Laparoscope for microsurgery

• Packaging films for pharmaceuticals

Also particularly preferred are products for electrical / electronic (E / E) applications, such as

• "soft keys", keyboards ("keypads") • Touch screen

• Housing, housing parts and frame

• lenses (eg infrared lenses)

• Screen / Display Covers

• Diffuser sheets

A preferred field of application are portable multimedia devices such as MP3 players, mobile phones, computers and digital cameras, as well as flat screens.

Also very particularly preferred are films and film laminates as well as films and film laminates containing coextrusion or laminate layers of the polymers according to the invention, and their use in the abovementioned applications.

The following examples are intended to illustrate the invention without, however, limiting it.

Examples

example 1

Synthesis of the Monomer Building Unit ljl-BisC-S-methyl-hydroxypheny O-S, S-trimethylcyclohexane (3a) (HCl method):

In a multi-necked round bottom flask, the amount of 42.07 g (0.3 mol) of 3,3,5-trimethylcyclohexanone, 324.42 g (3.0 mol) of freshly distilled o-cresol with a purity of> 99% and 0.812 g ( 0.004 mol) of dodecylmercaptan as a cocatalyst under nitrogen at about 36 ° C.

Subsequently, 10 g of hydrogen chloride gas from the compressed gas cylinder are introduced into the colorless transparent solution within 30 minutes.

The reaction is slightly exothermic and the total solution is heated to about 42 ^° C.

After the initiator, the batch is heated to 60 ^° C. within 10 minutes and left at this temperature for 25 minutes.

After the end of the reaction, the excess HCl is removed in a water jet vacuum at 80 ⁰ C. The residue is then carefully distilled under high vacuum to remove the excess of o-cresol and catalyst.

The residue is taken up in methylene chloride, washed several times with water and dried. The residue obtained is a white solid which can be phosgenated without further purification (see Example 4). Example 2 (Comparative Example ^* )

Synthesis of a copolycarbonate from bisphenol A (BPA) and bisphenol TMC:

middle mixture p-tert-B

To a nitrogen inertized solution of 47.94 g (0.21 mol) of bisphenol A (BPA), 27.94 g (0.09 mol) of bisphenol TMC, 1.352 g (0.009 mol, 3.0 mol% of. Bisphenols) p-tert-butylphenol (BUP) as a chain terminator and 27.60 g (0.69 mol) of sodium hydroxide in 568.4 ml of water are added to 568.4 ml of methylene chloride. At a pH of 12.5 - 13.5 and 20 ⁰ C is passed a 47.47 g (0.48 mol) of phosgene. In order not to drop the pH below 12.5, 30% sodium hydroxide solution was added during the phosgenation. After completion of the phosgenation and flushing with nitrogen, stirring is continued for a further 5 minutes and then 0.411 ml (0.003 mol, 1 mol% with respect to bisphenols) of N-ethylpiperidine as catalyst are added and stirring is continued for 1 hour. The organic phase is acidified after separating the aqueous phase with phosphoric acid and washed neutral with distilled water and salt-free. The org. Phase is separated, concentrated in a water-jet vacuum at 80 ⁰ C and dried at 130 ⁰ C in a water jet vacuum to constant mass.

This gives transparent polycarbonate. Example 3 (according to the invention)

Synthesis of a copolycarbonate of 2,2-bis (3-methyl-4-hydroxyphenyl) propane (3b) ("dimethyl bisphenol A") and bisphenol TMC:

O

NaOH

CI CI ^

Water Solvent mixture p-tert-butylphenol

To a nitrogen inertized solution of 1281.75 g (5.0 mol) of dimethyl bisphenol A, 1552.1 g (5.0 mol) of bisphenol TMC, 57.08 g (0.380 mol, 3.8 mol%). for bisphenols) p-tert-butylphenol (BUP) as chain terminator and 929.29 g (23.00 mol) of sodium hydroxide in 15.763 1 of water are added 7.171 1 of methylene chloride and 8.591 1 of chlorobenzene. At a pH of 12.5 - 13.5 and 20 ⁰ C is passed 1285.7 g (13.0 mol) of phosgene. In order not to drop the pH below 12.5, 30% sodium hydroxide solution was added during the phosgenation. After completion of the phosgenation and rinsing with nitrogen, the mixture is stirred for a further 5 minutes and then 11.31 g (0.10 mol, 1 mol% with respect to bisphenols) of N-ethylpiperidine as catalyst and stirred for 1 hour. The organic phase is acidified after separating the aqueous phase with phosphoric acid and washed neutral with distilled water and salt-free. After solvent exchange against chlorobenzene, the product is extruded at 270 ⁰ C via a Ausdampffextruder and granulated through a granulator. This gives transparent polycarbonate granules. The molecular weight of the polycarbonate resin is Mn = 8921 g / mol (number average molecular weight determined at room temperature ^{"Gelpermeatfons} chromatography GPG calibrated-on-BPA polycarbonate with refractive index detector) and Mw = 21537 g / mol (weight average) and polydispersity D = 2.41 The relative solution viscosity in methylene chloride (0.5 g / 100 ml solution) is 1.170. Example 4 (according to the invention):

Synthesis of a copolycarbonate from bisphenol A and 1,1-bis (3-methyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (3a) from Example 1

medium mixture

6.16 g (0.154 mol) of sodium hydroxide in 306 g of water are placed in an inertized phosgenation apparatus and dissolved. To the solution are added 11.19 g (0.05 mol) of bisphenol A (BPA), 7.1058 g (0.021 mol) of dimethyl TMC bisphenol from Example 1. Subsequently, the solution of 0.32 g (0.0021 mol, 3.0 mol% with respect to bisphenols) of p-tert-butylphenol (BUP) as a chain terminator and 306 ml of methylene chloride is added and stirred for 10 minutes at a moderate stirrer speed. At a pH of 12.5 - 13.5 and 20 ⁰ C is passed 13.851 g (0.14 mol) of phosgene. In order not to drop the pH below 12.5, conc. Sodium hydroxide solution added. After completion of the phosgenation and rinsing with nitrogen, the mixture is stirred for a further 5 minutes and then 0.096 ml (0.007 mol, 1 mol% with respect to bisphenols) of N-ethylpiperidine as catalyst and stirred for 1 hour. The organic phase is acidified after separating the aqueous phase with phosphoric acid and washed neutral with distilled water and salt-free. The org. Phase is then dried over sodium sulfate and evaporated overnight. The residue is then dried again for 8 hours in a water-jet vacuum at 80 ^° C.

The relative solution viscosity is 1.218. The glass transition temperature was determined by DSC to be 157 ° C. Example 5 (Comparative Example)

Lexan DMX 2415 from Sabic

Example 6 (Comparative Example): Makrolon 2600 (aromatic, linear polycarbonate based on BPA from Bayer MaterialScience AG)

Example 7 (Comparative Example): APEC 2000 (aromatic, linear copolycarbonate based on bisphenol TMC and BPA from Bayer Material Science AG)

Example 8 (Comparative Example): Makrolon 3103 (aromatic, linear polycarbonate based on BPA from Bayer MaterialScience AG)

Example 9 (Comparative Example): APEC 1895 (aromatic, linear copolycarbonate based on bisphenol TMC and BPA from Bayer Material Science AG)

Testing:

Test of Copolvcarbonates from Example 4 against an ammoniacal test solution:

This test solution is representative of pharmaceutical active ingredients (for example intravenously administered anesthetics, calcium antagonists, anticonvulsants, antiarrhythmics, calcineurin inhibitors for transplantation medicine or generally lipid-containing emulsions), which have amine groups / NH functionalities in the molecule and in contact with polymeric assemblies in the Come medical technology. For the ammonia resistance test, 2-step platelets of the polycarbonate with a layer thickness of 4 mm are completely immersed in an aqueous-ammoniacal solution (10% by weight). After different times (see Table 1) of the action of the test solution, a test specimen is removed in each case, washed off with water and, after drying, the turbidity is measured.

The Haze is determined according to ASTM D 1003-00 via Weitwinkei light scattering. The data are given in% Haze (H), where low values represent low turbidity and are therefore desirable.

Tab. 1

Compared to the comparative samples, the optical measurements on the sample moldings of copolycarbonate according to the invention show a significantly more stable behavior with regard to cloudiness after different exposure times of the sample medium Measurement of surface hardness:

The copolycarbonates are pre-dried overnight at 120 ⁰ C in a drying cabinet. The polymers were then dissolved in methylene chloride and poured into small 5 cm diameter dishes. The solvent was evaporated and the remaining polymer body again annealed at 120 ⁰ C in a vacuum oven. After removal of the polymer from the small dish, circular test disks having a diameter of 5 cm and a thickness of about 1 to 1.5 mm are obtained.

The surface hardness is measured on small platelets by means of an Atomic Force Microscope AFM (Digital Instruments Nanoscope), whereby the impression force of a diamond tip in a nanoindent measuring head (Hysitron) in the polymer surface (80 μN), the scanning speed of the tip ( 1 Hz) and the measuring field size (30 × 30 μm, scanned in 256 lines), the volume (depression in the material) mechanically removed from the sample surface by the scanning is obtained in μm ³ as a measured variable and thus as a unit of measure for the surface hardness. The larger the volume, the softer the material surface of the respective copolycarbonate. Smaller volume values thus indicate improved surface hardness. Table 2 shows measured values of copolycarbonates according to the invention and of the comparative example.

Table 2

The inventive example of a copolycarbonate of bisphenol-TMC and dimethyl-BPA (Example 4) shows a significantly lower volume value than for the comparative example (Example 5). Thus, the surface hardness of the copolycarbonate according to the invention over the prior art is significantly improved.

abrasion:

By friction wheel method (DIN 53 754) the wear resistance (Äbrieb) is determined by the increase of the scattered light. A Taber abrasion device Model 5151 with CS-10F Calibrase was used

Friction wheels (type FV) with 500 g weight per wheel. The Haze values according to the in the Table 3, with low values indicating good abrasion resistance.

Tab. 3

Also in the tab test, the copolycarbonate according to the invention (Example 4) is superior to both the homopolycarbonate based on bisphenol A (Example 8) and the copolycarbonate based on bisphenol A / bisphenol TMC.

Claims

claims

1. Copolycarbonate containing a combination of diphenol compounds selected from

a) at least one compound from the group containing the compounds with the general Forrnε!

(1a)

in which the R 1 independently of one another are C 1 -C ₄ -alkyl, preferably methyl, ethyl, n-propyl, isopropyl, t-butyl, very particularly preferably methyl,

n for 1, 2 or 3,

and R 2 independently of one another are 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, in particular methyl, ethyl, n-propyl, isopropyl, t-butyl, and most preferably methyl, and

b) at least one compound from the group containing the compounds having the general formula

(1 b)

in which the R 3 independently of one another represent linear or branched _{Ci-C) 0} alkyl, preferably linear or branched C ₁ -C ₆ AIlCyI, particularly preferably linear or branched Ci-C ₄ alkyl, "very particularly preferably represent Q- alkyl, and

the R4 are each independently H, linear or branched Ci-Ci ₀ alkyl, preferably linear or branched QC ₆ alkyl, particularly preferably linear or branched QC ₄ alkyl stand.

2. copolycarbonate according to claim 1, containing 0.1 - 80 mol% (based on the amount of diphenols used) diphenol selected from diphenols of the general formula (Ia).

3. copolycarbonate according to claim 1 or 2, containing 5-75 mol% (based on the amount of diphenols used) diphenols selected from diphenols of the general formula (Ia).

4. Copolycarbonate according to one of claims 1 to 3, wherein the diphenols of the general formula (Ia) are diphenols of the general formula (2a).

(2a)

5. copolycarbonate according to any one of claims 1 to 4, wherein the diphenols of the general formula (Ib) diphenols of the general formula (2b).

(2 B)

6. copolycarbonate according to claim 1, additionally containing diphenols of the formula (5a)

in which

R, ³ and R ⁴ are independently hydrogen, C ₁ -C ₈ -AIlCyI-, C ₁ -C ₁₈ -alkoxy, halogen, in each case optionally aryl substituiertet ocler aralkyl, and ^~

X represents a single bond, -SO ₂ -, -CO-, -O-, -S-, C ₁ - to C ₆ -alkylene, C ₂ - to C ₅ -

Alkylidene or C ₅ - to C ₆ - cycloalkylidene which is substituted by C ₁ - to C ₆ -alkyl may be, for C ₆ -C ₂ -arylene, which may optionally be condensed with further heteroatom-containing aromatic rings is.

Copolycarbonate according to Claim 6, characterized in that the diphenol of the formula (5a) is 2,2-bis (4-hydroxyphenyl) -propane (bisphenol-A).

8. copolycarbonates according to claim 1, characterized in that they have a solution viscosity η _rel = 1.10 - 1.35.

9. Use of copolycarbonates according to any one of claims 1-7 for the production of moldings, extrudates, films, film laminates and coextrusion layers.

10. Moldings, extrudates, films and film laminates, obtainable from copolycarbonates according to one of claims 1-8.

11. Extrudates, in particular cards and films containing one or more coextrusion layers obtainable from copolycarbonates according to one of claims 1-8.

12. blends of copolycarbonates according to any one of claims 1-8 with thermoplastic polymers.

13. A process for the preparation of copolycarbonates according to any one of claims 1-8 by the interfacial process or melt transesterification process, characterized in that a combination of compounds selected from one or more compounds of formulas (Ia) and from one or more compounds of the formulas (Ib) be used as diphenols.

14. Cards, keyboards in electrical and electronic equipment, lenses, screen / display covers, portable multimedia devices, flat screens and housings, housing parts and frames containing moldings, extrudates, films or film laminates according to claim 10 or 11.

15. Articles for medical applications or products in medical technology containing moldings, extrudates, films or film laminates according to claim 10 or 11.