Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
• • 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
  • C08G64/18—Block or graft polymers
  • C08G64/186—Block or graft polymers containing polysiloxane sequences
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polycarbonate sequences
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
  • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes

Definitions

• Siloxane-containing block copolymers with a small domain size Siloxane-containing block copolymers with a small domain size
• the present invention relates to polysiloxane-polycarbonate block co-condensates (hereinafter also referred to as SiCoPC) which have a small siloxane domain size.
• the block cocondensates are preferably produced in the melt transesterification process starting from special polycarbonates and hydroxyaryl-terminated polysiloxanes.
• the present invention relates to polysiloxane-polycarbonate block co-condensates with special compatibilizers.
• the invention also relates to the production of said block co-condensates by means of reactive extrusion.
• the polysiloxane block co-condensates according to the invention have a fine polysiloxane domain distribution and are distinguished by good mechanical properties and good melt stability.
• polysiloxane-polycarbonate block co-condensates have good properties in terms of low temperature impact strength or low temperature notched impact strength, chemical resistance and outdoor weathering resistance, and aging properties and flame resistance. They are partly in these properties. superior to conventional polycarbonates (for example homopolycarbonate based on bisphenol-A).
• cocondensates are usually produced industrially from the monomers using the phase boundary process with phosgene.
• the production of these polysiloxane-polycarbonate block co-condensates by the melt transesterification process using diphenyl carbonate is also known. These processes have the disadvantage that the industrial plants used for this purpose are used for the production of standard polycarbonate and therefore have a large plant size.
• the production of special block co-condensates in these systems is often not economically viable because of the lower volume of these products.
• the starting materials required for the production of the cocondensates such as e.g. Polydimethylsiloxane, impair the system, as they can lead to contamination of the system or the solvent circuits.
• starting materials such as phosgene are required for production or, as in the melt transesterification process, require a high level of energy.
• siloxane-polycarbonate block co-condensates by the melt transesterification process from bisphenol, diaryl carbonate, silanol-terminated polysiloxanes and catalyst is described in US Pat. No. 5,227,449.
• the siloxane compounds are polydiphenyl or polydimethylsiloxane telomers with silanol end groups are used. It is known, however, that such dimethylsiloxanes with silanol end groups in acidic or basic medium with decreasing chain length, in contrast to diphenylsiloxane with silanol end groups, increasingly tend to self-condensation, so that incorporation into the resulting copolymer is made more difficult.
• the cyclic siloxanes formed in the process remain in the polymer and have an extremely disruptive effect in electrical / electronic applications.
• No. 5,504,177 describes the production of a polysiloxane-polycarbonate block cocondensate by melt transesterification from a carbonate-terminated silicone with bisphenol and diaryl carbonate. Due to the high level of incompatibility of the siloxanes with bisphenol and diaryl carbonate, even incorporation of the siloxanes into the polycarbonate matrix via the melt transesterification process is difficult or impossible to achieve.
• the domain size in the phase boundary process is typically below 100 nm. This allows translucent or even transparent materials to be obtained, since there is hardly any light scattering due to the small domain size.
• siloxane-containing block cocondensates with a low degree of turbidity is known in principle.
• a precondensate is produced from an oligocarbonate and siloxane using the phase interface process and then further condensed in a second step with a bisphenol using the phase interface process.
• phase interface-active substances such as those used e.g. are described in DE 19523000, however, cannot be used in the process according to the invention, since they are not compatible with the high temperatures and relatively long residence times associated with the melt transesterification process.
• Other compatibilizers too, cannot usually be used due to the high temperatures, since they are degraded or lead to a product with poor melt stability.
• US20070238846 describes cloud-free siloxane block cocondensates based on siloxane blocks with a particularly low molecular weight. These block co-condensates are also produced using the phase boundary process.
• the melt transesterification process has the disadvantage that, in principle, it is not possible to work diluted and the reactants are always very concentrated.
• siloxane domains are formed with a size between 0.1 and 10 ⁇ m.
• a large domain size has a negative effect on the processing properties.
• Large domains can lead to segregation, which can be expressed by inhomogeneous surface structure and partly leads to flow lines and streaking. Since large domains are sensitive to shear, such materials are difficult to process in injection molding, so that only very small processing windows are possible. In some cases, it is necessary to work at very low injection speeds, which is often undesirable because it reduces the cycle time.
• the object was therefore to remedy at least one disadvantage of the prior art.
• the present invention was based on the object of developing a polysiloxane-polycarbonate block cocondensate with a small siloxane domain size, which at the same time has good mechanical properties.
• the block cocondensate should preferably be produced in the melt transesterification process.
• the domain size should achieve a D90 value of less than 120 nm, preferably less than 110 nm, and particularly preferably less than 100 nm.
• the proportion of particles with a diameter of less than 100 nm should preferably be greater than 70%, particularly preferably greater than 80% and very particularly preferably greater than 90%, based on the total number of siloxane domains.
• siloxane-based additive which contains both aromatic and aliphatic groups
• block co-condensates with low siloxane Domain size can be obtained.
• SiCoPCs with high melt stability were obtained.
• the simultaneous presence of aromatic groups and aliphatic groups in the siloxane-based additive seems to mediate between the different phases of the polycarbonate and the siloxane block. In particular in the case of a melt transesterification process, this leads to an improved siloxane domain distribution with a smaller size. This effect is better than with a siloxane-based additive that only has aromatic groups.
• the present invention thus relates, inter alia, to a process for the production of polysiloxane-polycarbonate block cocondensates, wherein
• s, si, S2 , S 3 and S4 is a natural number between 1 and 250,
• the process comprises a step of adding component C) to component A), to component B) and / or to a mixture of components A) and B).
• the present invention also relates to a polycarbonate composition containing
• Zi, Z2 and Z3 each independently represent methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, propenyl, butenyl, C5 to Cl 8 alkyl, methacryloxypropyl; 2,3-epoxypropyloxy, monodicarbinol, methoxy, ethoxy, propoxy, butoxy, epoxypropoxypropyl, phenylethyl, phenylisopropyl, 3-phenylpropyl or phenyl, hydroxy, hydrogen, chlorine, fluorine or CN which is optionally substituted by alkyl or alkoxy,
• Rs and R9 each independently represent an aliphatic or an aromatic group, with the proviso that in formula (I) or (Ia) at least one Rs stands for an aliphatic and at least one R9 for an aromatic group and
• s, si, S2 , S 3 and S4 is a natural number between 1 and 250, (iii) optionally at least one further polymer which is different from component (i), and
• Such a composition preferably results when the method according to the invention is used.
• a polysiloxane-polycarbonate block cocondensate is obtained, which thus preferably represents component (i) of the composition according to the invention. If the process according to the invention is carried out in the presence of component C), this remains at least in traces in the product, so that the direct process product can be the polycarbonate composition according to the invention.
• the method according to the invention preferably comprises or is particularly preferably a polycondensation method. It is further preferred that the process according to the invention is carried out in a melt transesterification process. Polycarbonate A) are preferably reacted with the hydroxyaryl-terminated (poly) siloxane B) and component C) in the melt on an extruder or high-viscosity reactor. Such processes are also known as reactive extrusion processes.
• melt replacement process and the reactive extrusion process are generally known (e.g. US 5,227,449, US 5,504,177 and the literature cited above).
• the extruder or melt reactor can be a single-shaft reactor, a double-shaft reactor, or a multi-shaft reactor, for example a planetary roller extruder or ring extruder. It can also be a high volume kneading reactor.
• the method can be performed on a single device - e.g. a twin screw extruder as well as two-stage, i.e. a reactor combination.
• the reactor combination preferably consists of a prereactor - such as a twin-screw extruder - and a high-viscosity reactor.
• the process is preferred at temperatures from 280 ° C. to 370 ° C., preferably from 290 ° C. to 360 ° C., more preferably from 300 ° C. to 350 ° C. and pressures from 0.001 mbar to 5 mbar, preferably 0.005 mbar to 4 mbar, in particular preferably 0.02 to 3 mbar and very particularly preferably 0.03 to 1 mbar, preferably carried out in the presence of a catalyst.
• the preferred reactor is a Single-screw or twin-screw extruder, particularly preferably a co-directional twin-screw extruder, is used.
• the twin-screw extruder is characterized by the fact that it comprises several vacuum zones.
• the processing temperature (melt temperature) when using a twin-screw extruder is preferably 280 ° C. to 400 ° C., preferably 290 to 380 ° C., and the pressure in the first stage is 500 to 0.01 mbar, preferably 200 to 0.1 mbar and in the following Vacuum levels 0.001 mbar to 50 mbar.
• the reactive extrusion process can be carried out in a two-stage process, the reactor combination preferably consisting of a twin or single-screw extruder and a high-viscosity reactor and the resulting low molecular weight cleavage products being removed by evaporation in a vacuum.
• the polycarbonate is melted on the twin-screw or single-screw extruder, as is the admixture of other starting materials such as silicone components and possibly catalysts, possibly in the form of masterbatches.
• the components are also mixed and pre-reacted here.
• the preliminary product is then fed to the high-viscosity reactor in which it reacts completely to form the polycondensation product with simultaneous supply of thermal and mechanical energy in a vacuum.
• the volatile low molecular weight cleavage products and other low molecular weight constituents can be withdrawn both in the prereactor (single or twin screw extruder) after the prereactor and / or in the high viscosity reactor.
• low molecular weight constituents are removed under vacuum in the prereactor. This is particularly preferably done in two vacuum stages, the first vacuum stage preferably being operated at an absolute pressure of 10 to 800 mbar and particularly preferably at an absolute pressure of 10 to 100 mbar, and the second vacuum stage preferably being operated at 0.1 to 100 mbar absolute pressure and especially preferably at 0.2 to 5 mbar absolute pressure.
• the reaction in the high-viscosity reactor is also carried out under vacuum.
• the vacuum is 0.001 mbar to 50 mbar, preferably 0.005 mbar to 40 mbar, particularly preferably 0.02 to 30 mbar and very particularly preferably 0.03 to 5 mbar absolute.
• the high-viscosity reactors used are apparatuses which are suitable for processing highly viscous masses, which provide a sufficient residence time with thorough mixing and which expose the melt to the vacuum required according to the invention.
• Numerous apparatuses are described in the patent literature which basically meet these requirements and which can be used according to the invention.
• reactors according to EP 460 466, EP 528 210, EP 638 354, EP 715 881, EP 715 882, EP 798 093 or those according to EP 329 092, according to EP 517 068, EP 1 436 073 or WO 20021114 and such can be used according to EP 222 599.
• This reactor / mixer is characterized in that all surfaces of the scrapers are kinematically cleaned, in particular with shafts rotating at the same speed in any radial section through the mixer, all outward-facing surfaces of the scrapers are a contraction concentric to the center of rotation if they are cleaned from the housing are, otherwise, however, have approximately the center distance as the radius of curvature and are convex and are cleaned by an adjacent weir or its scrapers, so that, in particular with rotors rotating at the same speed, all inwardly facing surfaces of the scrapers of a weir in any radial section through the mixer approximately the Have center distance as a radius of curvature and are concave and are cleaned by scrapers from another adjacent shaft.
• the melt can be passed over further mixing elements for better mixing.
• a static mixer can be used between the pre-reactor and the high-viscosity reactor.
• a single-shaft screw, a twin-shaft screw or a gear pump is used to discharge the fully reacted cocondensates from the high-viscosity reactor. If necessary, additives and / or aggregates are added and mixed in.
• the additives can be mixed in in the discharge unit or in a static mixer connected downstream.
• the melt is formed via one or more nozzles and comminuted with a granulating device according to the prior art.
• short reaction time means the reaction time that is required to produce the melted starting polycarbonate up to the target viscosity with the incorporation of the siloxane component.
• the reaction time is preferably less than 1/2 hour, particularly preferably less than 15 minutes and very particularly preferably less than 7.5 minutes. In a particularly preferred embodiment, the reaction time is less than 30, particularly preferably less than 20 minutes.
• the polycarbonate to be used according to the invention and the (poly) siloxane to be used according to the invention can be reacted by means of catalysts. Although the reaction can in principle also be carried out without a catalyst, higher temperatures and longer residence times may then have to be accepted.
• Catalysts suitable for the process according to the invention are, for example Ammonium catalysts, such as tetramethylammonium hydroxide,
• Phosphonium catalysts of the formula (K) are particularly suitable:
• Ra, Rb, Rc and Rd are the same or different CI -CIO-alkyls, C6-C14-aryls, C7-C15-aryl-alkyls or C5-C6-cycloalkyls, preferably methyl or C6-C14-aryls, particularly preferably methyl or phenyl and X- can be an anion such as hydroxide, sulfate, hydrogen sulfate, hydrogen carbonate, carbonate or a halide, preferably chloride or an alkylate or arylate of the formula -OR, where R is a C6-C14 aryl, C7-C 15 - Arylalkyl or C5-C6-cycloalkyl, preferably phenyl.
• catalysts are tetraphenylphosphonium chloride,
• the alkali metal salts or alkaline earth metal salts of these ammonium and / or phosphonium catalysts are particularly preferably used.
• the catalyst is preferably used in amounts from 0.0001 to 1.0% by weight, preferably from 0.001 to 0.5% by weight, particularly preferably from 0.005 to 0.3% by weight and very particularly preferably from 0.01 to 0.15% by weight based on the total composition.
• the catalyst can be used alone or as a catalyst mixture and added in bulk or as a solution, for example in water or in phenol (e.g. as mixed crystals with phenol).
• polycarbonate and the (poly) siloxane are reacted in the presence of an organic or inorganic salt of a weak acid with a pK A value in the range from 3 to 7 (25 °).
• This salt can also be referred to as a co-catalyst.
• Suitable weak acids include carboxylic acids, preferably C2-C22 carboxylic acids such as acetic acid, propanoic acid, oleic acid, stearic acid, lauric acid, benzoic acid, 4-methoxybenzoic acid, 3-methylbenzoic acid, 4-tert-butylbenzoic acid, p-toluene acetic acid, 4-hydroxybenzoic acid and salicylic acid, Partial esters of polycarboxylic acids, such as, for example, monoesters of succinic acid, partial esters of phosphoric acids, such as, for example, mono- or di-organic phosphoric acid esters, branched aliphatic carboxylic acids such as 2,2-dimethylpropionic acid, 2,2-dimethylbutanoic acid, 2,2-dimethylpentanoic acid and 2-ethylhexanoic acid.
• carboxylic acids preferably C2-C22 carboxylic acids such as acetic acid, propanoic acid, ole
• Suitable organic or inorganic salts are selected from or derived from hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium stearate, potassium stearate, lithium stearate, sodium oleate, potassium oleate, lithium oleate, sodium benzoate, potassium benzoate, lithium benzoate and dilithium salts of bisphenol A.
• the salts calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, the corresponding barium stearate, magnesium stearate, magnesium stearate.
• the salts can be used alone or in any mixtures.
• the salt is particularly preferably selected from the group consisting of alkali metal salts and phosphonium salts of carboxylic acids.
• the organic or inorganic salt is derived from a carboxylic acid.
• the organic or inorganic salts are preferably used in amounts from 0.5 to 1000 ppm, particularly preferably from 1 to 100 ppm and very particularly preferably from 1 to 10 ppm, based on the total weight of the siloxane and the organic or inorganic salt.
• the organic or inorganic salts are preferably used in an amount of 0.0005 to 5 mmol / kg, particularly preferably 0.001 to 1 mmol / kg and very particularly preferably 0.001 to 0.5 mmol / kg, based on the total weight of the siloxane, the polycarbonate and the organic or inorganic salt.
• the organic or inorganic salt is a sodium salt, preferably a sodium salt of a carboxylic acid.
• the sodium content in the resulting polysiloxane-polycarbonate block cocondensate is in the range from 0.1 ppm to 1000 ppm, preferably 0.2 to 100 ppm, particularly preferably 0.3 to 10 ppm and particularly preferably 0.4 to 5 ppm , are based on the total weight of the polysiloxane-polycarbonate block cocondesate that is to be formed.
• the sodium content of the cocondensate can be determined, for example, by atomic absorption spectroscopy.
• the organic or inorganic salt can be used alone or in any desired mixtures. It can be added as a solid or in solution. In a preferred embodiment, the organic or inorganic salt is added in the form of a mixture containing the siloxane and the organic or inorganic salt.
• Catalysts suitable for the process according to the invention are those mentioned above, which are either introduced into the reaction by means of a masterbatch with a suitable polycarbonate, in particular the polycarbonate according to the invention described above, or can be added separately or additionally.
• the catalysts can be used alone or in a mixture and can be added in bulk or as a solution, for example in water or in phenol.
• the catalyst is preferably added in pure form, as a mixture or in a masterbatch in the prereactor, preferably on a twin-screw extruder.
• polycarbonates are both homopolycarbonates and copolycarbonates and mixtures of polycarbonates.
• the polycarbonates can be linear or branched in a known manner.
• the polycarbonates can be produced in a known manner by the melt transesterification process or the phase boundary process.
• Polycarbonates with molecular weights from 8,000 to 28,000 g / mol, particularly preferably from 10,000 to 27,000 g / mol and particularly preferably from 12,000 to 26,500 g / mol are preferably used to produce the polysiloxane-polycarbonate block co-condensate.
• These polycarbonates preferably have a phenolic OH group content of 250 ppm to 2500 ppm, preferably 500 to 2000, and particularly preferably 1000 to 1800 ppm.
• the phenolic OH groups are preferably determined by means of IR spectroscopy.
• the method used for determining the molar masses specified for the polycarbonate, the siloxane component or the polysiloxane-polycarbonate block cocondensate in the context of the invention is method no. 2301-0257502-09D from Currenta GmbH & Co. OHG, which can be requested from Currenta at any time can be.
• polycarbonates with relative solution viscosities of 1.10 to 1.285 are used to produce the polysiloxane-polycarbonate block cocondensate according to the invention.
• the relative solution viscosity (rpel; also referred to as eta rel) is preferably determined in dichloromethane at a concentration of 5 g / l at 25 ° C. using an Ubbeloh viscometer.
• Preferred diphenols for producing the polycarbonates are 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) -! -phenyl-propane, 1,1-bis- (4-hydroxyphenyl) -phenyl-ethane, 2,2-bis- (4- hydroxyphenyl) propane, 2,2-bis (3-methyl, 4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,3-bis [2- (4- hydroxyphenyl) -2-propyl] benzene (bisphenol M), 2,2-bis- (3-methyl-4-hydroxyphenyl) -propane, bis- (3,5-dimethyl-4-hydroxyphenyl) -methane, 2,2 -Bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, bis- (3,5-dimethyl-4-hydroxyphenyl) -sulfone, 2,4-bis- (3,5-dimethyl-4-hydroxy
• diphenols are 2,2-bis (4-hydroxyphenyl) propane (BPA), hydroquinone, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 2,2-bis ( 3-methyl, 4-hydroxyphenyl) propane.
• BPA 2,2-bis (4-hydroxyphenyl) propane
• hydroquinone 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane
• 2,2-bis ( 3-methyl, 4-hydroxyphenyl) propane 2,2-bis (4-hydroxyphenyl) propane
• polycarbonates based on bisphenol A are used. These polycarbonates very particularly preferably contain phenol as an end group.
• Polycarbonates which are particularly suitable for producing the block cocondensates according to the invention are those which have been produced by the melt transesterification process.
• polycarbonates are used which contain certain rearrangement structures.
• the polycarbonates to be used in this embodiment contain at least one, preferably several of the following structures (4) to (7):
• the phenyl rings independently of one another, can be substituted once or twice with C1 - C8 alkyl, halogen, preferably C1 to C4 alkyl, particularly preferably with methyl, and X for a single bond, C1 to C6 alkylene, C2 to C5 alkylidene or C5 to C6 Cycloalkylidene, preferably a single bond or C1 to C4 alkylene and particularly preferably isopropylidene, the total amount of structural units (4) to (7) (determined after saponification) generally in the range from 50 to 1000 ppm, preferably in the range is from 80 to 850 ppm.
• the respective polycarbonate is subjected to total saponification and the corresponding degradation products of the formulas (4a) to (7a) are formed, the amount of which is determined with HPLC (this can be done, for example, as follows:
• the polycarbonate sample is Sodium methylate saponified under reflux.
• the corresponding solution is acidified and concentrated to dryness.
• the drying residue is dissolved in acetonitrile and the phenolic compounds of the formula (la) to (4a) are determined by means of HPLC with UV detection):
• the amount of the compound of the formula (4a) released is preferably from 20 to 800 ppm, particularly preferably from 25 to 700 ppm and particularly preferably from 30 to 500 ppm.
• the amount of the compound of the formula (5a) released is preferably 0 (i.e. below the detection limit of 10 ppm) to 100 ppm, particularly preferably 0 to 80 ppm and particularly preferably 0 to 50 ppm.
• the amount of the compound of the formula (6a) released is preferably 0 (i.e. below the detection limit of 10 ppm) to 800 ppm, more preferably 10 to 700 ppm and particularly preferably 20 to 600 ppm and very particularly preferably 30 to 350 ppm.
• the amount of the compound of the formula (7a) released is preferably 0 (i.e. below the detection limit of 10 ppm) to 300 ppm, preferably 5 to 250 ppm and particularly preferably 10 to 200 ppm.
• Component B is preferably a Flydroxy aryl-terminated (poly) siloxane of the formula (1)
• R 5 stands for hydrogen or C1 to C4 alkyl, C1 to C4 alkoxy, preferably hydrogen or methyl, methyloxy, particularly preferably hydrogen.
• R 6 and R 7 independently of one another represent aryl, preferably phenyl, C1 to C4 alkyl, preferably methyl, in particular methyl.
• Ci to C t -alkyl can, preferably for a single bond, -O-, isopropylidene or for a C5 to C 6 -cycloalkylidene radical which can be substituted one or more times by Ci to C t -alkyl, and in particular for isopropylidene.
• V stands for oxygen, C2-C6 alkylene or C3 to C6 alkylidene, preferably for oxygen or C3 alkylene.
• W is oxygen, C2 to C6-alkylene or C3- to C6-alkylidene, preferably oxygen or C3-alkylene.
• p or q each independently represent 0 or E.
• o stands for an average number of repeating units of 10 to 400, preferably 10 to 100, particularly preferably 15 to 50.
• m stands for an average number of repeating units of 1 to 10, preferably 1 to 6, particularly preferably 1.5 to 5.
• RI stands for hydrogen, C1-C4-alkyl, preferably for hydrogen or methyl and particularly preferably for hydrogen,
• R2 independently of one another for aryl or alkyl, preferably for methyl,
• X for a single bond, -S02-, -CO-, -O-, -S-, CI- to C6-alkylene, C2- to C5-alkylidene or for C6- to C12-arylene, which optionally contains aromatic with further heteroatoms
• Wrestling can be condensed, stands,
• X preferably represents a single bond, C1 to C5-alkylene, C2 to C5-alkylidene, C5 to O2-cycloalkylidene, -O-, -SO- -CO-, -S-, -SO2-, particularly preferably X represents a single bond , Isopropylidene, C5 to O2 cycloalkylidene or oxygen, and very particularly preferably isopropylidene,
• n is an average number from 10 to 400, preferably 10 and 100, particularly preferably 15 to 50 and
• m represents an average number from 1 to 10, preferably from 1 to 6 and particularly preferably from 1.5 to 5.
• the siloxane block can also preferably be derived from the following structure
• the molecular weight of the siloxane component is preferably 1,500 to 20,000 g / mol and particularly preferably 3500-15,000 g / mol.
• the molecular weight is preferably determined as described above under component A).
• the siloxane component of the formula (1), (2) or (3) or also (VII), (VIII) or (IX) are from 0.5 to 50% by weight, preferably from 1 to 40% by weight, particularly preferably from 2 to 20% and very particularly preferably from 2.5 to 10% by weight, based in each case on components A) and B).
• siloxane blocks are known in principle and can be produced by methods such as those described in US20130267665, for example.
• At least one siloxane of the general chemical formula (I), (Ia) or any mixtures thereof is used as component C),
• Zi, Z2 and Z3 each independently represent methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, propenyl, butenyl, C5 to C18 alkyl, methacryloxypropyl; Monodicarbinol, methoxy, ethoxy, propoxy, butoxy, epoxypropoxypropyl, phenylethyl, phenylisopropyl, 3-phenylpropyl or phenyl, hydroxy, hydrogen, chlorine, fluorine or CN, which is optionally substituted by alkyl or alkoxy, Rs and R each independently represent an aliphatic or an aromatic group, with the proviso that in formula (I) or (Ia) at least one Rs represents an aliphatic and at least one R represents an aromatic group and
• s, si, S , S and S each independently represent a natural number between 1 and 250, preferably 1 to 100, particularly preferably 1 to 75.
• This component C) according to the invention corresponds to the component (i) according to the invention in the polycarbonate composition according to the invention.
• the following description therefore relates independently of one another to both components according to the invention.
• component C) the presence of at least one aliphatic and at least one aromatic group in component C) in the process for producing a polysiloxane-polycarbonate block cocondensate leads to a significant reduction in the siloxane domain distribution and significantly more particles with a particle diameter smaller 100 nm can be obtained. According to the invention, this is brought about by the better mediation between components A) and B) through component C).
• Component C) or (ii) according to the invention is linear and / or has a comb-like and / or plug-like structure.
• Rs in the general chemical formula (I) or (Ia) each independently represent methyl, ethyl, propyl, butyl, isopropyl, vinyl, isobutyl, a C5 to C18 alkyl or an optionally substituted by alkyl or alkoxy Phenylethyl, phenylisopropyl, 3-phenylpropyl or phenyl and
• the optionally present substitution of phenylethyl, phenylisopropyl, 3-phenylpropyl or phenyl is a C1-C9 alkyl, a methoxy group or an ethoxy group. It is very particularly preferably phenylethyl, phenylisopropyl, 3-phenylpropyl or phenyl optionally substituted with alkyl or alkoxy in all embodiments of this invention to —CH 2 CH 2 CH 2 (C 6 R 5 ), - CH 2 CH 2 (C 6 R5),
• each R independently of one another can be H, alkyl or alkoxy, preferably C1 to C9 alkyl, a methoxy group or an ethoxy group . It is very particularly preferably -CH 2 CH 2 CH 2 (C 6 Hs), -CH 2 CH 2 (C 6 Hs), -CH 2 CH (CH 3 ) - (C 6 Hs) or -C 6 H 5 .
• Zi, Z 2 and Z 3 have the meanings given above.
• Preferably Zi, Z 2 and Z 3 each independently represent methyl, vinyl, phenyl or hydroxy.
• Rs in the general chemical formula (I) or (Ia) each independently represent methyl, ethyl, trimethylphenyl, -CH 2 -CH 2 -phenyl, -CH 2 -CH 2 -CH 2 -phenyl, - CH 2 - CH (CH 3 ) -phenyl, -CH 2 -CH 2 -CH 2 - (2-methoxy) phenyl or phenyl and R 9 in the general chemical formula (I) each independently represents methyl, ethyl, trimethylphenyl, -CH 2 -CH 2 -phenyl, -CH 2 - CH 2 -CH 2 -phenyl, -CH 2 -CH (CH 3) -phenyl, -CH 2 -CH 2 -CH 2 - (2-methoxy) phenyl, or Phenyl, with the proviso that at least one Rs stands for methyl or ethyl and at least one R 9 stands for a
• the groups Rs and R 9 are a group which form a “D” unit known to the person skilled in the art.
• Particularly preferred D units are selected from the following structures:
• Ph is each independently -CH 2 -CH 2 -phenyl, -CH 2 -CH 2 -CH 2 -phenyl, -CH 2 -CH (CH 3 ) -phenyl or phenyl and
• M units each independently stands for a C2 to Cl 8 alkyl and the number of repeat units s, si, s 2, S3 and S 4 are defined according to the invention, depending on whether the D unit belongs to structural formula (I) or (Ia) .
• the person skilled in the art is able to read these D units into structural formula (I) or (Ia).
• the last siloxane unit together with the end groups Zi, Z 2 or Z 3 form an “M” unit.
• M units preferred according to the invention are selected from the group consisting of
• the radical R 9 on this T unit is selected from the group consisting of a methyl group and a Ph group, where Ph each independently represents -Cth-Cth-phenyl, -CH 2 -CH 2 -CH 2 - Phenyl, -CH 2 -CH (CH 3 ) -phenyl or phenyl.
• the person skilled in the art is able to read these T units into structural formula (Ia).
• s, si, S 2, S3 and S 4 each independently represent a natural number between 3 and 50, preferably between 4 and 25, particularly preferably between 5 and 15, in the general formula (I) .
• These can be pure substances or oligomer mixtures. If it is a question of an oligomer mixture, s, si, S 2, S3 and S 4 therefore represent mean values of the distribution and thus an average number. In this case, s, si, S 2, S3 and S 4 can also be a decimal number.
• component C) is a mixture of at least one siloxane of the formula (I) and at least one siloxane of the formula (Ia). It is preferred that the at least one siloxane of the formula (Ia) is up to 10% by weight, preferably 1 to 5% by weight, very particularly preferably 2 to 4% by weight, based on the total weight of all siloxanes Formula (I) and (Ia) is included in the mixture.
• the at least one siloxane of component (ii) or component C) is represented by the general chemical formula (II), the general chemical formula (Ha), the general chemical formula (III) and / or the general chemical formula (IV)
• Zi, Z2 and Z3 each independently represent methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, propenyl, butenyl, C5 to C18 alkyl, methacryloxypropyl;, monodicarbinol, methoxy, ethoxy, propoxy, butoxy, epoxypropoxypropyl, a phenylethyl, phenylisopropyl, 3-phenylpropyl or phenyl, hydroxy, hydrogen, chlorine, fluorine or CN, preferably methyl, methoxy, ethoxy, hydrogen or hydroxyl, optionally substituted with alkyl or alkoxy,
• Rio each independently represents hydrogen, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, isooctyl, isononyl or isodecyl,
• Rn independently of one another, represents methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, propenyl, butenyl, C5 to Cl 8 alkyl, methacryloxypropyl; Monodicarbinol, methoxy, ethoxy, propoxy, butoxy, epoxypropoxypropyl, phenylethyl, phenylisopropyl, 3-phenylpropyl or phenyl, hydroxy, hydrogen, chlorine, fluorine or CN, which is optionally substituted by alkyl or alkoxy, r is a natural number between 0 and 3,
• s and t are each independently a natural number between 1 and 250, preferably 1 to 100, particularly preferably 1 to 75, very particularly preferably 1 to 50, also preferably between 4 and 25, particularly preferably between 5 and 15
• w and v are each independently a natural number between 1 and 250, preferably between 1 and 100, particularly preferably between 5 and 75 and
• Groups with the indices s, w, v, t and u can be statistically distributed in the siloxane of component (ii) or component C), preferably statistically distributed in the siloxane of component (ii) or component C).
• component (ii) or component C) is a mixture of at least one siloxane selected from the group consisting of the general chemical formula (II), (Ha) and (III) and up to 5% by weight of a siloxane of the formula (Ia), preferably of the formula (IV). .
• Zi, Z 2 and Z 3 each independently represent methyl, vinyl, methoxy, ethoxy, hydrogen or flydroxy, preferably methyl, hydroxy or a mixture of methoxy and ethoxy,
• Rn each independently represents methyl, phenyl, vinyl, methoxy, ethoxy, hydrogen or hydroxy, preferably methyl or phenyl,
• r is a natural number between 0 and 3, particularly preferably 0,
• s is a natural number between 1 and 100, preferably 5 and 75, particularly preferably between 5 and 15
• t is a natural number between 1 and 75
• w is a natural number between 5 and 75
• v is a natural number between 1 and 75 and
• u is a natural number between 1 and 10. It is preferred according to the invention that the expression “a natural number between” a range of numbers includes the explicitly disclosed limit values of the range.
• Rn each independently represent methyl or phenyl
• s is a natural number between 1 and 100, preferably 5 and 75, particularly preferably between 5 and 15
• t is a natural number between 1 and 75
• w is a natural number between 5 and 75
• v is a natural number between 1 and 75 and
• reaction melt component C) is preferably 0.01 to 20 wt .-%, particularly preferably 0.01 to 10 wt .-%, particularly preferably 0.05 to 2.5 wt .-% %, further preferably 0.1 to 2.0, very particularly preferably 0.20 to 1.0%, based on the total composition (sum of components A to C) is added.
• the addition can take place at any point in the process at any point in time.
• Component C) is preferably added to the reaction mixture at an early point in time.
• Component C is preferably dissolved in component B, preferably using agitators and heat, and added as a mixture to the polycarbonate melt.
• Component C) can also be added before component B) and / or component A) are added.
• component C) can also be melted together with the polycarbonate at the beginning of the reaction or plasticized together with polycarbonate in the case of reactive extrusion.
• Component C) can be introduced directly or in the form of a masterbatch.
• Component C) can be combined with other components, e.g. a catalyst - e.g. according to the structure (K) - are mixed.
• the substrate material for the masterbatch is e.g. Polycarbonate in question, in particular polycarbonate according to component A) mentioned.
• component C) is preferably containing 0.5 to 99.9 parts by weight component C)
• a polycarbonate composition is provided containing
• Zi, Z2 and Z3 each independently represent methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, propenyl, butenyl, C5 to Cl 8 alkyl, methacryloxypropyl; Monodicarbinol, methoxy, ethoxy, propoxy, butoxy, epoxypropoxypropyl, phenyl, hydroxy, hydrogen, chlorine, fluorine or CN, Rs and R each independently represent an aliphatic or an aromatic group, with the proviso that in formula (I) or (Ia) at least one Rs represents an aliphatic and at least one R represents an aromatic group and
• s, si, S , S and S each independently represent a natural number between 1 and 250, (iii) optionally at least one further polymer which is different from component (i), and
• the polysiloxane-polycarbonate block co-condensate is preferably composed of the following structural units (XI) and (X2):
• Rx is a divalent substituted or unsubstituted aromatic radical, a divalent linear or cyclic aliphatic radical
• Rx is a divalent substituted or unsubstituted aromatic radical or Rx is a divalent linear or cyclic aliphatic radical.
• Ry independently of one another, is a linear or branched aliphatic radical, preferably C1-Cl 2 alkyl, particularly preferably C1 to C4 alkyl, in particular methyl, or a substituted or unsubstituted aromatic radical, preferably phenyl.
• the proportion of aromatic Rx radicals in the formula (XI) is 60-100% by weight and the proportion of aliphatic radicals 0-40% by weight, based on the sum of the diphenols used in% by weight.
• the SiCoPc can preferably be built up from siloxane blocks, which can be derived from the formula (1) given above. According to the invention, the term “allow to derive” preferably means that the corresponding building block is esterified into the resulting polymer via the hydroxyl groups.
• R 5 is hydrogen or C1 to C4 alkyl, preferably hydrogen or methyl, particularly preferably hydrogen.
• R 6 and R 7 independently represent C1 to C4 alkyl, preferably methyl.
• Ci to C t -alkyl can, preferably for a single bond, -O-, isopropylidene or for a C5 to C 6 -cycloalkylidene radical which can be substituted one or more times by Ci to C t -alkyl, and in particular for isopropylidene.
• V stands for oxygen, C2-C6 alkylene or C3 to C6 alkylidene, preferably for oxygen or C3 alkylene.
• W is oxygen, C2 to C6-alkylene or C3- to C6-alkylidene, preferably oxygen or C3-alkylene,
• P and q each independently represent 0 or 1.
• o stands for an average number of repeating units of 10 to 400, preferably 10 to 100, particularly preferably 15 to 50.
• m stands for an average number of repeating units of 1 to 10, preferably 1 to 6, particularly preferably 1.5 to 5.
• siloxane block of the SiCoPC of component (i) particularly preferably results from siloxanes of the formulas (2) and (3) given above,
• RI stands for hydrogen, C1-C4-alkyl, preferably for hydrogen or methyl and particularly preferably for hydrogen,
• R2 independently of one another for aryl or alkyl, preferably for methyl,
• X for a single bond, -S02-, -CO-, -O-, -S-, CI- to C6-alkylene, C2- to C5-alkylidene or for C6- to C12-arylene, which optionally contains aromatic with further heteroatoms Wrestling can be condensed, stands,
• X preferably represents a single bond, C1 to C5-alkylene, C2 to C5-alkylidene, C5 to C12-cycloalkylidene, -O-, -SO- -CO-, -S-, -SO2-, particularly preferably X represents a single bond , Isopropylidene, C5 to C12 cycloalkylidene or oxygen, and very particularly preferably isopropylidene,
• n is an average number from 10 to 400, preferably 10 and 100, particularly preferably 10 to 50 and
• m represents an average number from 1 to 10, preferably from 1 to 6 and particularly preferably from 1.5 to 5.
• component (i) is preferably the polysiloxane-polycarbonate block co-condensate produced by the process according to the invention.
• the polysiloxane-polycarbonate block cocondensate has a D90 value of the siloxane domain size of less than 120 nm, preferably less than 110 nm, and particularly preferably less than 100 nm. It is also preferred that the proportion of particles with a diameter of less than 100 nm is greater than 70%, particularly preferably greater than 80% and very particularly preferably greater than 90%, based on the total number of siloxane domains. The D90 value and / or the proportion of particles with a diameter of less than 100 nm is determined using AFM. The parameters described in the example section and the method described there are preferably used for this purpose.
• the siloxane block of the polysiloxane-polycarbonate block cocondensate can have the following structure (IV a)
• n is an average number from 10 to 400, preferably 10 to 100, particularly preferably 15 to 50, k is 0 or 1.
• R3 independently comprises the following structural elements (V) or (VI):
• R4 is independently hydrogen, halogen and / or a C1 to CIO, preferably C1 to C4, linear or branched, unsubstituted or mono- to fourfold substituted alkyl radical or alkoxy radical, preferably the alkyl and alkoxy radicals are unsubstituted, and R4 is particularly preferred Hydrogen,
• e is 0 or a natural number from 2 to 12, preferably 2 to 6, where in the event that e is 0, k is 1,
• R6 and R7 independently of one another, represent H, Cl-Cl 8 -alkyl, Cl-C18-alkoxy, halogen such as Cl or Br or for each optionally substituted aryl- or aralkyl, preferably independently of one another for H or Cl-C12-alkyl, particularly preferred are H or Cl-C8-alkyl and very particularly preferably, independently of one another, H or methyl, and
• XI is preferably CI to C5-alkylene, C2 to C5-alkylidene, C6 to C9-cyclohexylidene -O-, -SO-, -CO-, -S-, -S02-, particularly preferably isopropylidene, 3,3, 5-trimethylcyclohexylidene or oxygen, especially for isopropylidene.
• the siloxane block can be derived from the following structure where a in formula (VII), (VIII) or (IX) stands for an average number from 10 to 400, preferably 10 to 100 and particularly preferably 15 to 50.
• siloxane blocks can be linked once or several times via terephthalic acid or isophthalic acid to the following structural elements shown by way of example
• R2, R3, n and k have the meaning given above for structural element (IV a).
• Corresponding siloxane blocks for reaction with polycarbonate or for reaction with diphenols derived from the formula (III) or (purple) with phosgene or diaryl carbonates each have terminal phenolic OH groups.
• Ie where R2, R3, n, k and p have the meanings given for the structural element (IXb).
• Component (ii) according to the invention has already been defined in more detail above under component C).
• Component (iii) is at least one further polymer which is different from component (i). It is preferably a polycarbonate, polyester carbonate, polystyrene, styrene copolymers, aromatic polyesters such as polyethylene terephthalate (PET), PET-cyclohexanedimethanol copolymer (PETG), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), cyclic polyolefin, poly or Poly or copolyacrylates and poly or copolymethacrylate such as Poly- or copolymethyl methacrylates (such as PMMA) and copolymers with styrene such as e.g.
• PET polyethylene terephthalate
• PEN polyethylene naphthalate
• PBT polybutylene terephthalate
• cyclic polyolefin poly or Poly or copolyacrylates and poly or copolyme
• polystyrene acrylonitrile PS AN
• thermoplastic polyurethanes polymers based on cyclic olefins (e.g. TOPAS®, a commercial product from Ticona).
• Component (iii) is particularly preferably a polycarbonate.
• Polycarbonates in the context of the present invention are both homopolycarbonates and copolycarbonates and / or polyester carbonates; the polycarbonates can be linear or branched in a known manner. Mixtures of polycarbonates can also be used according to the invention.
• the polycarbonates including the thermoplastic, aromatic polyester carbonates preferably have average molecular weights M n (determined by measuring the relative viscosity at 25 ° C. in CH 2 Cl 2 and a concentration of 0.5 g per 100 ml CH 2 Cl 2) of 20,000 g / mol to 32,000 g / mol , preferably from 23,000 g / mol to 31,000 g / mol, in particular from 24,000 g / mol to 31,000 g / mol.
• Some, up to 80 mol%, preferably from 20 mol% to 50 mol%, of the carbonate groups in the polycarbonates used according to the invention can be replaced by aromatic dicarboxylic acid ester groups.
• aromatic polyester carbonates Such polycarbonates, which contain both acid residues of carbonic acid and acid residues of aromatic dicarboxylic acids built into the molecular chain, are referred to as aromatic polyester carbonates. In the context of the present invention, they are subsumed under the generic term thermoplastic, aromatic polycarbonates.
• the polycarbonates are produced in a known manner from diphenols, carbonic acid derivatives, optionally chain terminators and optionally branching agents, with some of the carbonic acid derivatives being replaced by aromatic dicarboxylic acids or derivatives of dicarboxylic acids, depending on the amount in the aromatic polycarbonates to produce the polyester carbonates Replacing carbonate structural units by aromatic dicarboxylic acid ester structural units.
• dihydroxyaryl compounds examples include dihydroxybenzenes, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) aryls, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) ) ketones, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, l, r-bis (hydroxyphenyl) diisopropylbenzenes and their ring alkylated and ring halogenated compounds.
• Diphenols suitable for the production of the polycarbonates to be used according to the invention are, for example, hydroquinone, resorcinol, dihydroxydiphenyl, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ethers, bis - (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, a, a'-bis (hydroxyphenyl) diisopropylbenzenes and their alkylated, ring alkylated and ring halogenated compounds.
• Preferred diphenols are 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -l-phenylpropane, 1,1-bis- (4-hydroxyphenyl) -phenylethane, 2,2-bis- (4-hydroxyphenyl ) propane, 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 1,3-bis- [2- (4-hydroxyphenyl) -2-propyl] benzene (bisphenol M), 2,2-bis- (3-methyl-4-hydroxyphenylj-propane, bis- (3,5-dimethyl-4-hydroxyphenyl) -methane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenylj-propane, bis- (3 , 5-dimethyl-4-hydroxyphenyl) sulfone, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2 -methylbutane, 1,3-bis- [2- (3,5 -dimethyl- 4-
• diphenols are 4,4'-dihydroxydiphenyl, 1,1-bis- (4-hydroxyphenyl) -phenyl-ethane, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis (3,5 -dimethyl-4-hydroxyphenyl) -propane, l, l-bis (4- hydroxyphenyl) cyclohexane and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (Bisphenol TMC).
• the monofunctional chain terminators required to regulate the molecular weight such as phenols or alkylphenols, especially phenol, p-tert. Butylphenol, iso-octylphenol, cumylphenol, their chlorocarbonic acid esters or acid chlorides of monocarboxylic acids or mixtures of these chain terminators are either added to the reaction with the bisphenolate or bisphenolates or added at any point in the synthesis as long as phosgene or chlorocarbonic acid end groups are still in the reaction mixture are present, or in the case of the acid chlorides and chlorocarbonic acid esters as chain terminators, as long as sufficient phenolic end groups of the polymer being formed are available.
• the chain terminator (s) are preferably added after the phosgenation at one point or at a time when no more phosgene is present but the catalyst has not yet been metered in, or they are metered in before the catalyst, together with the catalyst or in parallel.
• branching agents or branching mixtures to be used are added to the synthesis in the same way, but usually before the chain terminators.
• trisphenols, quarter phenols or acid chlorides of tricarboxylic or tetracarboxylic acids or mixtures of the polyphenols or the acid chlorides are used.
• Some of the compounds with three or more than three phenolic hydroxyl groups which can be used as branching agents are, for example, phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2, 4,6-dimethyl-2, 4,6-tri- (4-hydroxyphenyl) -heptane, l, 3,5-tris- (4-hydroxyphenyl) -benzene, l, l, l-tri- (4- hydroxyphenyl) ethane, tris (4-hydroxyphenyl) phenylmethane, 2,2-bis- [4,4-bis- (4-hydroxyphenyl) -cyclohexyl] -propane, 2,4-bis- (4-hydroxyphenyl- isopropyl) phenol, tetra (4-hydroxyphenyl) methane.
• trifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.
• Preferred branching agents are 3,3-bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole and 1,1,1-tri- (4-hydroxyphenyl) ethane.
• the amount of branching agents to be optionally used is 0.05 mol% to 2 mol%, again based on the moles of the diphenols used in each case.
• the branching agents can either be initially introduced with the diphenols and the chain terminators in the aqueous alkaline phase or dissolved in an organic solvent and added before the phosgenation.
• Aromatic dicarboxylic acids suitable for preparing the polyester carbonates are, for example, orthophthalic acid, terephthalic acid, isophthalic acid, tert-butyl isophthalic acid, 3,3'-diphenyldicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, 3,4'-benzophenonedicarboxylic acid, 4,4 '- Diphenylether dicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 2,2-bis (4-carboxyphenyl) propane, trimethyl-3-phenylindane-4,5'-dicarboxylic acid.
• aromatic dicarboxylic acids terephthalic acid and / or isophthalic acid are particularly preferred.
• dicarboxylic acids are the dicarboxylic acid dihalides and the dicarboxylic acid dialkyl esters, in particular the dicarboxylic acid dichlorides and the dicarboxylic acid dimethyl esters.
• the replacement of the carbonate groups by the aromatic dicarboxylic acid ester groups takes place essentially stoichiometrically and also quantitatively, so that the molar ratio of the reactants is also found in the finished polyester carbonate.
• the incorporation of the aromatic dicarboxylic acid ester groups can take place either randomly or in blocks.
• Preferred methods of production of the polycarbonates to be used according to the invention, including the polyester carbonates, are the known interfacial process and the known Melt transesterification processes (cf., for example, WO 2004/063249 A1, WO 2001/05866 A1, WO 2000/105867, US Pat. No. 5,340,905 A, US Pat. No. 5,097,002 A, US Pat. No. 5,717,057 A).
• phosgene and optionally dicarboxylic acid dichlorides are used as acid derivatives, in the latter case preferably diphenyl carbonate and optionally dicarboxylic acid diester.
• Catalysts, solvents, work-up, reaction conditions, etc. for the production of poly carbonate or polyester carbonate are adequately described and known in both cases.
• At least one further additive can be present as component (iv) in the polymer composition according to the invention.
• This at least one additive can be additives and / or fillers and reinforcing materials. These additives and / or fillers and reinforcing materials can be used in amounts of 0.0% by weight to 5.0% by weight, preferably 0.01% by weight to 1.00% by weight, based on the sum of the Components (i) to (iv) are mixed in.
• Possible additives are selected from at least one from the group of flame retardants, UV protection agents, gamma stabilizers, antistatic agents, optical brighteners, flow improvers, thermal stabilizers, inorganic pigments, mold release agents and processing aids.
• the additives are conventional polymer additives, such as e.g. those described in EP-A 0 839 623, WO-A 96/15102, EP-A 0 500 496 or “Plastics Additives Flandbook”, Plans Zweifel, 5th Edition 2000, Planser Verlag, Kunststoff.
• additives can be added to the polymer melt individually or in any desired mixtures or several different mixtures. This can be done directly during the isolation of the polymer (e.g. via a side unit such as a side extruder) as a pure substance or in the form of a masterbatch
• Polycarbonate are fed or after melting the polycarbonate granulate in a so-called compounding step.
• the additives or mixtures thereof can be added to the polymer melt as a solid, that is to say as a powder, or as a melt.
• Another type of dosing is the use of masterbatches or mixtures of masterbatches of the additives or additive mixtures.
• the polymer composition contains thermal stabilizers or processing stabilizers.
• Phosphites and phosphonites and phosphines are particularly suitable. Examples are triphenyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol-tert-phosphite, diisodecylpentaerythritol, bis (2,4-butylphenyl) -tertyp
• Triphenylphosphine TPP
• Irgafos® 168 tris (2,4-di-tert-butylphenyl) phosphite
• tris nonylphenyl phosphite or mixtures thereof
• phenolic antioxidants such as alkylated monophenols, alkylated thioalkylphenols, hydroquinones and alkylated hydroquinones can be used.
• Irganox® 1010 penentaerythritol 3- (4-hydroxy-3,5-di-tert-butylphenyl) propionate; CAS: 6683-19-8) and Irganox 1076® (2,6-di-tert-butyl -4- (octadecanoxycarbonylethyl) phenol
• Irganox® 1010 penentaerythritol 3- (4-hydroxy-3,5-di-tert-butylphenyl) propionate
• Irganox 1076® 2,6-di-tert-butyl -4- (octadecanoxycarbonylethyl) phenol
• Suitable UV absorbers are described, for example, in EP 1 308 084 A1, in DE 102007011069 A1 and in DE 10311063 A1.
• Particularly suitable ultraviolet absorbers are hydroxy-benzotriazoles, such as 2- (3 ', 5'-bis- (l, l-dimethylbenzyl) -2'-hydroxyphenyl) -benzotriazole (Tinuvin® 234, Ciba Specialty Chemicals, Basel), 2- (2'-Hydroxy-5 '- (tert-octyl) -phenyl) -benzotriazole (Tinuvin® 329, Ciba Specialty Chemicals, Basel), 2- (2'-Hydroxy-3' - (2-butyl) - 5 '- (tert-butyl) -phenyl) -benzotriazole (Tinuvin® 350, Ciba Specialty Chemicals, Basel), bis- (3- (2H-benztriazolyl) -2-hydroxy-5-tert-octyl) methane, (Tinuvin ® 360, Ciba Specialty Chemicals, Basel), (2
• the polymer compositions according to the invention can optionally contain mold release agents.
• Particularly suitable mold release agents for the composition according to the invention are pentaerythritol tetrastearate (PETS) or glycerol monostearate (GMS).
• the polycarbonate composition according to the invention preferably comprises
• component (i) 10-99.95, preferably 50-99.5, particularly preferably 80-99.5% by weight of component (i), in a particular embodiment 98.0-99.5% by weight of component (i)
• component (iii) 0 to 90% by weight, preferably 0 to 50% by weight, particularly preferably 0 to 20% by weight of component (iii) and
• component (iv) 0 to 15% by weight of component (iv).
• The% by weight are based on the sum of components (i) to (iv).
• the polycarbonate composition particularly preferably consists of components (i) to (iv).
• The% by weight result in 100% by weight.
• the term “polycarbonate composition” preferably means that the composition comprises at least 85% by weight of polycarbonate, including the polycarbonate contained in component (i). Additional polycarbonate, which is optionally different from component (i), can be contained in the composition due to component (iii).
• block cocondensates obtainable by the process according to the invention and the polycarbonate compositions according to the invention can be processed into any desired shaped bodies in a manner known for thermoplastic polycarbonates.
• compositions according to the invention can in this context, for example, by hot pressing, spinning, blow molding, deep drawing, extrusion or injection molding into products,
• Shaped bodies or molded objects are transferred. Use in multilayer systems is also of interest.
• the application of the composition obtainable according to the invention can, for example, in a multi-component injection molding or as a substrate for a coextrusion Layer can be used. However, it can also be applied to the fully formed base body, for example by lamination with a film or by coating with a solution.
• Sheets or moldings made of base and optional cover layers / optional cover layers can be produced by (co) extrusion, direct skinning, direct coating, insert molding, film back injection molding, or other suitable processes known to the person skilled in the art.
• polysiloxane-polycarbonate block cocondensates obtainable by the process according to the invention and the polycarbonate compositions according to the invention can be used wherever the known aromatic polycarbonates have hitherto been used and where, in addition, good flowability coupled with improved demolding behavior and high toughness at low temperatures and improved chemical resistance are required, such as z. B. for the production of large motor vehicle exterior parts and switch boxes for outdoor use, of sheets, twin wall sheets, parts for electrics and electronics as well as optical memories.
• the block cocondensates can be used in the IT area for computer cases and multimedia cases, mobile phone shells as well as in the household area such as in washing machines or dishwashers, in the sports area e.g. be used as material for helmets.
• Zi, Z2 and Z3 each independently represent methyl, ethyl, propyl, butyl, isopropyl, isobutyl, vinyl, propenyl, butenyl, C5 to Cl 8 alkyl, methacryloxypropyl; Monodicarbinol, methoxy, ethoxy, propoxy, butoxy, epoxypropoxypropyl, phenyl, hydroxy, hydrogen, chlorine, fluorine or CN, Rs and R each independently represent an aliphatic or an aromatic group, with the proviso that in formula (I) or (Ia) at least one Rs represents an aliphatic and at least one R represents an aromatic group and
• s, si, S , S and S each independently stand for a natural number between 1 and 250, provided for reducing the particle size distribution of the siloxane domains in a polysiloxane-polycarbonate block cocondensate in a process for producing this polysiloxane-polycarbonate block cocondensate.
• a compound of the general formula (I) or (Ia) is particularly well suited to mediate between the different phases in the preparation of a polysiloxane-polycarbonate block cocondensate and thereby a smaller particle size distribution of the siloxane domains to cause.
• the method for producing the polysiloxane-polycarbonate block cocondensate preferably comprises at least one reactive extrusion or at least one melt transesterification.
• the process very particularly preferably comprises reactive extrusion.
• siloxane of the general chemical formula (I) or (Ia) is described in more detail above under component C) (and also component (ii)). These preferences also apply to the use according to the invention.
• melt volume rate is determined according to ISO 1133 (year 2011) (at 300 ° C; 1.2 kg) unless other conditions have been described.
• the relative solution viscosity (
• siloxane domain size by means of atomic force microscopy (AFM)
• the siloxane domain size and distribution were determined by means of atomic force microscopy.
• the corresponding sample in the form of a melt cake for laboratory batches or granules for extrusion batches
• a Bruker D3100 AFM microscope was used.
• the AFM image was recorded at room temperature (25 ° C., 30% relative humidity).
• the "Soft Intermittent Contact Mode” or the "Tapping Mode” were used for the measurement.
• a tapping mode cantilver (Nanoworld pointprobe) with a spring constant of approx. 2.8 Nm-1 and a resonance frequency of approx.
• phase contrast recordings (number of particles greater than 200) are evaluated as described above.
• the individual diameters are classified using the image evaluation software and a distribution of the diameters is created. This means that the assignment to the individual D values takes place.
• the D value indicates the proportion of particles that is smaller than the specified value. With a D90 value of x, 90% of the particles are smaller than x. Furthermore, the proportion of particles which are smaller than 100 nm is determined from the distribution.
• Component A Pol carbonate
• PC 1 The starting material used for reactive extrusion is linear bisphenol A polycarbonate with end groups based on phenol with a solution viscosity of 1.17 (see description above). This polycarbonate does not contain any additives such as UV stabilizers, mold release agents or thermal stabilizers. The polycarbonate was produced using a melt transesterification process as described in DE 102008019503. The polycarbonate has a phenolic end group content of 0.16%.
• Component B siloxane
• FIG. 1 shows a scheme for the production of the siloxane-containing block cocondensates.
• Polycarbonate (component A)) is metered into the twin-screw extruder (1) via the gravimetric feed (2).
• the extruder (type ZSE 27 MAXX from Leistritz Extrusionstechnik GmbH, Nuremberg) is a co-rotating twin-screw extruder with vacuum zones for separating the vapors.
• the extruder consists of 11 housing parts (a to k) - see FIG. 1. In housing part a, polycarbonate is added via the differential metering scale (2) and in housing b and c the polycarbonate is melted.
• the liquid siloxane component (component B) is added in the housing part d.
• the housing parts d and e also serve to mix in the liquid siloxane component (component B).
• the housing parts e, g, i and j are provided with vent openings to remove the condensation products.
• the housing part e is assigned to the first vacuum stage and the housing parts g i and j to the second vacuum stage.
• the vacuum in the first vacuum stage was between 45 and 65 mbar absolute pressure.
• the vacuum in the second vacuum stage is less than 1 mbar.
• the siloxane (component B) is placed in a tank (3) and fed to the extruder via a metering pump (4).
• the vacuum is generated by the vacuum pumps (5) and (6).
• the vapors are carried away from the extruder and collected in 2 condensers (9).
• the melt strand is led into a water bath (10) and comminuted by the granulator (11).
• polycarbonate component A
• component C component C
• the resulting polycondensate was light in color and had an MVR of 4.4.
• 624 objects were identified that could be assigned to a soft phase and thus to the siloxane phase.
• the size distribution of the objects had a D90 diameter of 185 nm.
• the largest object identified corresponded to an equivalent circle diameter of 516 nm.
• Comparative Example 3 and Example 4 are essentially comparable with one another. Although a slightly different extruder speed and barrel temperature were used, polymers with comparable MVR result. The examples thus differ in the addition of component C) in Example 4 and its absence in Comparative Example 3.
• Comparative Example 5 and Example 6 Similar conclusions can be drawn for the comparability of Comparative Example 5 and Example 6, as well as Comparative Example 7 and Examples 8 and 9.
• the comparisons are suitable for assessing the effect of adding component C) (or also its amount).
• example 4 according to the invention shows the positive influence of the low molecular weight siloxane according to the invention.
• Example 4 according to the invention has a significantly lower D90 value compared to Comparative Example 3 and thus provides a polymer morphology with a smaller siloxane domain size. Lower viscosities can be achieved by increasing the reaction temperature (Comparative Example 5 and Example 6).
• Example 6 according to the invention which contains the low molecular weight siloxane additive according to the invention of component C), shows a significantly lower D90 value than comparative example 5.
• Example 9 according to the invention has a similar D90 value to comparative example 7 - but the proportion of particles with a volume ⁇ 200 nm is significantly greater than in example 9 according to the invention. Particles with a large volume are particularly critical with regard to processing problems , for example in injection molding. If the proportion of the siloxane component according to the invention (Example 8) is increased, further advantages are achieved, which can be seen from the lower D90 value and from a better volume distribution (no more particles with a volume> 200 nm) of the particles.
• Component A polycarbonate
• PC A The starting material for reactive extrusion is linear bisphenol A polycarbonate with end groups based on phenol from Covestro GmbH AG with a melt volume index of 59 - 62 cm 3 / 10min measured at 300 ° C and 1.2 kg load (according to ISO 1033) used.
• This polycarbonate does not contain any additives such as UV stabilizers, mold release agents or thermal stabilizers.
• the polycarbonate was produced using a melt transesterification process as described in DE 102008019503. The polycarbonate has a phenolic end group content of approx. 600 ppm.
• PC B The starting material for reactive extrusion is linear bisphenol A polycarbonate with end groups based on phenol with a solution viscosity of approx. 1.17. This polycarbonate does not contain any additives such as UV stabilizers, mold release agents or Thermal stabilizers.
• the polycarbonate was produced using a melt transesterification process as described in DE 102008019503. The polycarbonate has a phenolic end group content of approx. 1600 ppm.
• Component B is a compound having Component B:
• Octaphenylcyclotetrasiloxane (CAS: 546-56-5)., 95% from ABCR GmbH & Co.KG (Karlsruhe Germany). Catalyst masterbatch (without siloxane-based additional components):
• the catalyst used is tetraphenylphosphonium phenolate from Rhein Chemie Rheinau GmbH (Mannheim Germany) in the form of a masterbatch. Tetraphenylphosphonium phenolate was used as a mixed crystal with phenol and contains approx. 70% tetraphenylphosphonium phenolate. The following amounts relate to the substance obtained from Rhein Chemie (as mixed crystal with phenol).
• the masterbatch was produced as a 0.25% mixture.
• 4982 g of PC A polycarbonate were tumbled with 18 g of tetraphenylphosphonium phenolate in a gymnastics wheel mixer for 30 minutes.
• the masterbatch was metered in at a ratio of 1:10 so that the catalyst was present in a proportion of 0.025% by weight in the total amount of polycarbonate.
• Example 12 shows that the addition of a compound having both aliphatic and aromatic groups compared to a compound having only aromatic groups in the preparation of a polysiloxane-polycarbonate block cocondensate increases leads to a reduced siloxane domain distribution.

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