WO2009106246A1 - Polycarbonate mit cyclischen oligomeren und verbessertem fliessverhalten - Google Patents
Polycarbonate mit cyclischen oligomeren und verbessertem fliessverhalten Download PDFInfo
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- WO2009106246A1 WO2009106246A1 PCT/EP2009/001086 EP2009001086W WO2009106246A1 WO 2009106246 A1 WO2009106246 A1 WO 2009106246A1 EP 2009001086 W EP2009001086 W EP 2009001086W WO 2009106246 A1 WO2009106246 A1 WO 2009106246A1
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- acid
- polycarbonate
- polycarbonates
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- DSFRVAOCXVEPRA-UHFFFAOYSA-N O=S(c1ccccc1)(OCC(COS(c1ccccc1)(=O)=O)OS(c1ccccc1)(=O)=O)=O Chemical compound O=S(c1ccccc1)(OCC(COS(c1ccccc1)(=O)=O)OS(c1ccccc1)(=O)=O)=O DSFRVAOCXVEPRA-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/307—General preparatory processes using carbonates and phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Definitions
- This invention relates to compositions having improved theological and electrical properties based on polycarbonate with rearrangement structures and reduced content of cyan oligomers, as well as molded articles and extrudates of these polycarbonate compositions.
- EP-A 0 517 044, WO 2006/072344 and EP-A 1 609 818 and documents cited therein describe, for example, the phase boundary surfaces and the melt process for the production of polycarbonate.
- EP-A 0953605 describes a flow improvement of polycarbonate compositions with the teaching to act to increase the Cyclenanteil.
- polycarbonate compositions do not have these disadvantages to the same extent and at the same time show lower melt viscosities, ie better flow behavior and thus improved processing behavior in injection molding, and improved electrical properties, preferably better insulation, if the content of cyan oligomers is reduced is and also Umlagerungsstrukruren, which arise from carbonate structures, are present.
- This is all the more surprising because higher and not reduced Ohgomerengehalte known to improve flow (see EP-A 0953605).
- mathfunctionallocation structures drove to branches that normally lead to an increase in the melt viscosity and thus to poorer flow. The effect according to the invention was therefore not to be expected for the person skilled in the art.
- phenyl groups can be monosubstituted or disubstituted independently of one another by C 1 -C -alkyl, halogen, such as chlorine or bromine, preferably C 1 -C 4 -alkyl, especially methyl, and X has the meaning given for formula (Ia),
- n is an integer from 2 to 6 and
- Z is a radical of the formula (Ia)
- R 1 and R 2 are each independently H, Ci-C 8 alkyl, preferably H or Ci - are alkyl, particularly preferably represents hydrogen or methyl, and - C 4
- X is a single bond, C 1 - to C 6 -alkylene, C 2 - to C 5 -alkylidene or C 5 - to C 6 -
- Cycloalkylidene which may be substituted by C 1 - to C 6 -alkyl, preferably methyl or ethyl, is.
- the structural units of the formulas (II) to (V) are also referred to simply as rearrangement structures.
- the structural units are derived and result from the diphenol or diphenol mixture used for the preparation of the polycarbonate.
- the phenyl rings of the rearrangement structures unsubstituted.
- the cyclic oligomers of the general formula (I) present in the polycarbonate compositions according to the invention are preferably present in amounts of 0.2 to 1.2, more preferably 0.2 to 1.1 and most preferably 0.3 to 1 wt .-% ,
- the rearrangement structures defined above occur in different amounts and proportions to one another. Their amount can be determined by total saponification of the polycarbonate composition.
- the amount of compound of formula (II) or (Ha) released thereby is 50 to 800 ppm, preferably 70 to 750 ppm, more preferably 100 to 700 ppm and most preferably 100 to 600 ppm,
- the amount of compound of formula (IQ) or (IHa) released thereby (below the detection limit of ⁇ 5 ppm) is up to 100 ppm, preferably from 0 to 80 ppm, more preferably from 0 to 70 ppm and most preferably from 0 to 60 ppm.
- the amount of compound of formula (IV) or (IVa) released thereby is 0 (below the detection limit of ⁇ 5 ppm) up to 60 ppm, preferably from 0 to 50 ppm, more preferably from 0 to 40 ppm and most preferably from 15 to 30 ppm.
- the amount of compound of formula (V) or (Va) released thereby (below the detection limit of ⁇ 5 ppm) is up to 250 ppm, preferably from 5 to 200 ppm, more preferably from 5 to 180 ppm and most preferably from 10 to 150 ppm.
- compositions according to the invention which contain the rearrangement structures essential to the invention and reduced content of cyclic carbonates, aromatic dihydroxy compounds are transesterified in the melt with carbonic acid diesters with the aid of certain catalysts and optionally further additives.
- polycarbonate compositions according to the invention having reduced cyclic carbonate contents and rearrangement structures are prepared by the melt transesterification process from aromatic dihydroxy compounds with carbonic acid diesters in the presence of ammonium or phosphonium salts as catalysts.
- suitable diphenols are those of the formula (1)
- R 1 and R 2 independently of one another are H, C 1 -C 6 -alkyl or, preferably, H or C 1 -C 4 -alkyl, particularly preferably hydrogen or methyl, and
- X represents a single bond, Q to C 6 alkylene, C 2 - to C 5 alkylidene or C 5 to C 6 - cycloalkylidene, which may be substituted with C r to C 6 alkyl, preferably methyl or ethyl.
- X is preferably a single bond, methylene, isopropylidene, cyclohexylidene or 3,3,5-trimethylcyclohexylidene, particularly preferably isopropylidene or 3,3,5-trimethylcyclohexylidene.
- dihydroxyaryl compounds examples include dihydroxybenzenes, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) -cycloalkanes, and their nuclear alkylated compounds.
- Dihydroxyaryl compounds are well known or can be prepared by well-known methods (e.g., WO 2006/072344, EP-A 1609818 and references cited therein).
- Preferred diphenols of the formula (1) are: 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 4,4'-dihydroxydiphenyl.
- Both a dihydroxyaryl compound to form homopolycarbonates and various dihydroxyaryl compounds to form copolycarbonates can be used. The latter is particularly important when products are to be produced with special property combinations.
- predominantly OH-end relaxationgestoppte oligocarbonates can be used as the starting compound.
- the dihydroxyaryl compounds can also be used with residual contents of the monohydroxyaryl compounds from which they have been prepared or the low molecular weight oligocarbonates containing residual monohydroxyaryl compounds which have been eliminated in the preparation of the oligomers.
- the residual contents of the monomer hydroxyaryl compounds may be up to 20%, preferably 10%, more preferably up to 5% and most preferably up to 2% (see for example EP-A 1 240 232).
- the dihydroxyaryl compounds used, as well as all other raw materials, chemicals and auxiliaries added to the synthesis, may be contaminated with the impurities derived from their own synthesis, handling and storage, although it is desirable and desirable to work with as clean as possible raw materials, chemicals and adjuvants.
- Suitable diaryl carbonates for the reaction with the dihydroxyaryl compounds are those of the formula (2)
- R, R 'and R may be the same or different independently of one another and are hydrogen, optionally branched C 1 -C 34 alkyl, C 7 -C 34 -alkyl or C 6 -C 34 -aryl, R furthermore also -COO R '"is hydrogen, optionally branched Ci-C 34 alkyl, C 7 -C 34 alkylaryl or C 6 -C 34 aryl.
- diaryl carbonates are described, for example, in EP-A 1 609 818.
- Preferred diaryl compounds are diphenyl carbonate, 4-tert-butylphenyl phenyl carbonate, di- (4-tert-butylphenyl) carbonate, biphenyl -4-yl phenyl carbonate, di (biphenyl-4-yl) carbonate, 4 - (1-methyl-1-phenylethyl) -phenyl-phenyl-carbonate and di- [4- (1-methyl-1-phenylethyl) -phenyl] -carbonate.
- diphenyl carbonate is particularly preferred.
- the diaryl carbonates can also be used with residual contents of the monohydroxyaryl compounds from which they were prepared.
- the residual contents of the monohydroxyaryl compounds may be up to 20%, preferably 10%, more preferably up to 5% and most preferably up to 2%.
- the diaryl carbonates are generally from 1.02 to 1.30 mol, preferably from 1.04 to 1.25 mol, particularly preferably from 1.06 to 1.22 mol, very particularly preferably from 1.06 to 1.20 moles per mole of dihydroxyaryl used. It is also possible to use mixtures of the abovementioned diaryl carbonates.
- R, R 'and R have the meaning given in formula (2) with the proviso that in this case R can not be H, but R' and R" can be H.
- a monohydroxyaryl compound is to be selected whose boiling point is higher than that of the monohydroxyaryl compound which was used to prepare the diaryl carbonate used.
- the monohydroxyaryl compound can be added at any time in the course of the reaction. It is preferably added at the beginning of the reaction or else at any point in the course of the process.
- the proportion of free monohydroxyaryl compound may be 0.2-20 mol%, preferably 0.4-10 mol%, based on the dihydroxyaryl compound.
- the end groups can also be altered by concomitant use of a diaryl carbonate whose base mono-hydroxyaryl compound has a higher boiling point than the base monohydroxyaryl compound of the main diaryl carbonate.
- the diaryl carbonate can be added at any time in the course of the reaction. It is preferably added at the beginning of the reaction or else at any point in the course of the process.
- Diarylcarbonates with the higher-boiling base MonohydroxyarylENS to the total Diarylcarbonatmenge used can 1-40 mol%, preferably 1-20 mol% and particularly preferably 1-10 mol% amount.
- Phosphonium salts in the context of the invention are those of the general formula (4)
- R 7 10 are the same or different C r Ci 0 alkyls, C 6 -C 4 aryls, C 7 -C 15 arylalkyl or C 5 -C 6 cycloalkyls, preferably methyl or C 6 -C 14 aryls, especially may preferably be methyl or phenyl
- X may be an anion such as hydroxide, sulfate, hydrogen sulfate, bicarbonate, carbonate or a halide, preferably chloride or an alkylate or arylate of the formula -OR, where R is a C 6 -Ci 4 -aryl, C 7 -C 5 -arylalkyl or C 5 -C 6 -cycloalkyl, preferably phenyl.
- catalysts are tetraphenylphosphonium chloride, tetraphenylphosphonium hydroxide and tetraphenylphosphonium phenolate, particularly preferred is tetraphenylphosphonium phenolate.
- catalysts may be used as cocatalyst in addition to the onium salt of the above type to increase the rate of polycondensation.
- alkaline salts of alkali metals and alkaline earth metals such as hydroxides, alkoxides and aryloxides of lithium, sodium and potassium, preferably hydroxides, alkoxides or aryloxides of sodium.
- alkaline salts of alkali metals and alkaline earth metals such as hydroxides, alkoxides and aryloxides of lithium, sodium and potassium, preferably hydroxides, alkoxides or aryloxides of sodium.
- sodium hydroxide and sodium phenolate as well as the disodium salt of 2,2-bis (4-hydroxyphenyl) -propane.
- the amounts of the alkaline salts of alkali metals and alkaline earth metals as cocatalyst may range from 1 to 500 ppb, preferably from 5 to 300 ppb, and most preferably from 5 to 200 ppb, each calculated as sodium and based on polycarbonate to be formed.
- alkaline salts of alkali metals and alkaline earth metals can already be used in the preparation of the oligocarbonates, that is to say at the beginning of the synthesis, or they can also be mixed in before the polycondensation in order to suppress unwanted side reactions. Furthermore, it is also possible to add additional amounts of onium catalysts of the same type or another before the polycondensation.
- the addition of the catalysts is carried out in solution in order to avoid harmful excess concentrations during the metering.
- the solvents are system- and process-inherent compounds such as, for example, dihydroxyaryl compounds, diaryl carbonates or monohydroxyaryl compounds. Particular preference is given to monohydroxyaryl compounds because it is familiar to the person skilled in the art that the dihydroxyaryl compounds and diaryl carbonates readily change and decompose at already slightly elevated temperatures, in particular under the action of a catalyst.
- These include polycarbonate grades.
- the preferred compound is phenol. Phenol is also an obvious choice because the catalyst tetraphenylphosphonium phenolate, which is preferably used, is isolated in the production as a mixed crystal with phenol.
- the weight average molecular weights of the polycarbonates are generally from 15,000 to 40,000, preferably from 17,000 to 36,000, more preferably from 17,000 to 34,000 g / mol, and are determined by GPC against a polycarbonate calibration.
- the polycarbonates generally have an extremely low content of cations and anions of less than 60 ppb each, preferably ⁇ 40 ppb and particularly preferably ⁇ 20 ppb (calculated as Na cation), where as cations are those of alkali metals and alkaline earth metals which for example, as an impurity derived from the raw materials used and the phosphonium and ammonium salts.
- cations are those of alkali metals and alkaline earth metals which for example, as an impurity derived from the raw materials used and the phosphonium and ammonium salts.
- Other ions such as Fe, Ni, Cr, Zn, Sn, Mo, Al ions and their homologues can be contained in the raw materials or originate from the materials of the plant used by removal or corrosion.
- the content of these ions is less than 2 ppm in total, preferably less than 1 ppm and more preferably less than 0.5 ppm.
- Anions are those of inorganic acids and of organic acids in equivalent amounts (eg, chloride, sulfate, carbonate, phosphate, phosphite, oxalate, etc.).
- the aim is thus the smallest amounts that can be achieved only by using pure raw materials.
- pure raw materials are e.g. only after cleaning procedures such as recrystallization, distillation, topping with washes u. ⁇ . Available.
- the process according to the invention for the production of polycarbonate by the transesterification process can be designed batchwise or else continuously. After the dihydroxyaryl compounds and diaryl carbonates, if appropriate with further compounds, are in the form of a melt, the reaction is started in the presence of the catalyst essential to the invention. The conversion or the molecular weight is at increasing temperatures and falling Press in suitable apparatus and devices by removing the cleaved Monohydroxyarylharm increased until the desired final state is reached.
- the end groups are characterized in type and concentration by the method or plant used to produce the polycarbonate.
- the temperatures over the entire process are generally 180 to 330 0 C at pressures of 15 bar, absolute to 0.01 mbar, absolute.
- the continuous process for the preparation of polycarbonates is characterized in that one or more dihydroxyaryl compounds with the diaryl carbonate, optionally also other added reactants using the catalysts, after a precondensation without separating the Monohydroxyarylharm formed in then then several reaction evaporator With gradually increasing temperatures and gradually decreasing pressures, the molecular weight is built up to the desired level.
- the apparatus, apparatus and reactors suitable for the individual reaction-evaporator stages are, according to the process course, heat exchangers, expansion apparatuses, separators, columns, evaporators, stirred vessels and reactors or other commercially available apparatus which provide the necessary residence time at selected temperatures and pressures.
- the chosen devices must allow the necessary heat input and be designed to meet the continuous vacuum and aqueous acid viscosities. All devices are connected by pumps, piping and valves. Of course, the pipelines between all devices should be as short as possible and the bends of the lines should be kept as low as possible to avoid unnecessarily prolonged dwell times.
- the external that is to say technical framework conditions and concerns for installations of chemical plants have to be considered.
- the reactants may either be melted together or else the solid dihydroxyaryl compound in the diaryl carbonate melt or the solid diaryl carbonate in the melt of the dihydroxyaryl compound or both raw materials are melted together, preferably directly from the preparation.
- the residence times of the separate melts of the raw materials, in particular those of the melt of the dihydroxyaryl compound, are adjusted as short as possible.
- the melt mixture can linger longer due to the reduced melting point of the raw material mixture compared to the individual raw materials at correspondingly lower temperatures without sacrificing quality.
- the catalyst preferably dissolved in phenol, admixed and the melt is heated to the reaction temperature.
- This is at the beginning of the technically significant process for the production of polycarbonate from 2,2-bis (4-hydroxyphenyl) propane and diphenyl 180 to 220 0 C, preferably 190 to 210 0 C, most preferably 190 0 C.
- the reaction equilibrium is adjusted without removing the hydroxyaryl compound formed.
- the reaction can be run at atmospheric pressure, but for technical reasons even at overpressure.
- the preferred pressure in technical systems is 2 to 15 bar absolute.
- the melt mixture is in a first vacuum chamber, the pressure of 100 to 400 mbar, preferably adjusted to 150 to 300 mbar, relaxed and then directly heated in a suitable device at the same pressure back to the inlet temperature. In the relaxation process, the resulting hydroxyaryl compound is evaporated with remaining monomers.
- the reaction mixture is in a second vacuum chamber, the pressure of 50 to 200 mbar, preferably 80 to 150 mbar, relaxed and immediately afterwards in a suitable device at the same pressure to a temperature of 190 to 250 0 C, preferably 210 to 240 0 C, particularly preferably 210 to 230 0 C, heated.
- the resulting Hydroxyarylharm is evaporated with remaining monomers
- the reaction mixture is in a third vacuum chamber, the pressure of 30 to 150 mbar, preferably 50 to 120 mbar, relaxed and directly then in a suitable Vor ⁇ chtung at the same pressure to a temperature of 220 to 280 0 C, preferably 240 to 27O 0 C, more preferably 240 to 260 0 C, heated.
- the resulting HydroxyarylENS is evaporated with remaining monomers.
- the reaction mixture is in a further vacuum chamber whose pressure at 5 to 100 mbar, preferably 15 to 100 mbar, particularly preferably 20 to 80 mbar , Relaxed and directly thereafter in a suitable Vor ⁇ chtung at the same pressure to a temperature of 250 to 300 0 C, preferably 260 to 290 0 C, particularly preferably 260 to 280 0 C, heated.
- a suitable Vor ⁇ chtung at the same pressure to a temperature of 250 to 300 0 C, preferably 260 to 290 0 C, particularly preferably 260 to 280 0 C, heated.
- Viscosity of the oligomeric carbonate is between 1.04 and 1.20, preferably between 1.05 and 1.15, particularly preferably between 1.06 and 1.10.
- the oligocarbonate thus produced is after a residence time of 5 to 20 min in a sump template possibly pumped with the same pressure and same temperature as in the last flash / evaporator stage in a disc or basket reactor and at 250 to 310 0 C, preferred 250 to 29O 0 C, more preferably 250 to 280 0 C, at pressures of 1 to 15 mbar, preferably 2 to 10 mbar, at residence times of 30 to 90 minutes, preferably 30 to 60 minutes, further condensed.
- the product reaches a rel. Viscosity of 1.12 to 1.28, preferably 1.13 to 1.26, more preferably 1.13 to 1.24.
- the melt leaving this reactor is brought to the desired final viscosity or the final molecular weight in a further disk or basket reactor.
- the temperatures are 270 to 330 ° C., preferably 280 to 320 ° C., particularly preferably 280 to 310 ° C., the pressure 0.01 to 3 mbar, preferably 0.2 to 2 mbar, with residence times of 60 to 180 mm, preferably 75 to 150 mm.
- the rel. Viscosities are adjusted to the level required for the intended application and are 1.18 to 1.40, preferably 1.18 to 1.36, more preferably 1.18 to 1.34.
- the function of the two basket reactors can also be summarized in a basket reactor.
- the vapors from all process stages are immediately derived, collected and processed. This work-up is usually des ⁇ iia ⁇ v to achieve h ⁇ hc purities Je * recovered substances. This can be done, for example, according to German patent application no. 10 100 404. Recovery and isolation of the cleaved monohydroxy aryl compound in its purest form is a matter of course from an economic and ecological point of view.
- the monohydroxyaryl compound can be used directly for producing a dihydroxyaryl compound or a diaryl carbonate.
- the disk or basket reactors are characterized by the fact that they provide a very large, constantly renewing surface on a vacuum at high residence times.
- the disk or basket reactors are geometrically formed according to the melt viscosities of the products. Suitable examples are reactors, as described in DE 4447 422 C2 and EP A 1 253 163, or two-shaft reactors, as described in WO A 99/28 370.
- oligocarbonates even very low molecular weight, and the finished polycarbonates are usually promoted by gear pumps, screws of various designs or positive displacement pumps special design.
- Particularly suitable materials for the production of apparatus, reactors, pipelines, pumps and valves are stainless steels of the type Cr Ni (Mo) 18/10 such. B. 1.4571 or 1.4541 (Stahlschreibl 2001, Verlag: Stahl Whyl Wegst GmbH, Th-Heuss-Strasse 36, D-71672 Marbach) and Ni-base alloys of the type C, such. B. 2.4605 or 2.4610 (Stahlêtl 2001, Publisher: Stahl Whyl Wegst GmbH, Th-Heuss-Strckee 36, D-71672 Marbach).
- the stainless steels are used up to process temperatures of about 29O 0 C and the Ni-base alloys at process temperatures above about 290 0 C used.
- the polycarbonate obtained can be provided with other customary additives and additives (for example auxiliaries and reinforcing substances) after the addition of the inventive inhibitors to modify properties.
- additives and additives serves the extension of the useful life (eg hydrolysis or degradation stabilizers), the improvement of color stability (eg thermal and UV stabilizers), the simplification of processing (eg demulsifier, flow aids), the improvement of performance characteristics (eg Antistatic agents), improving the flame retardancy, influencing the visual impression (eg organic colorants, pigments) or adapting the polymer properties to specific loads (impact modifiers, finely divided minerals, fibrous materials, quartz powder, glass and carbon fibers). Everything can be combined as desired to set and achieve the desired properties.
- Such additives and additives are e.g. in "Plastics Additives", R. Gumbleter and H. Müller, Hanser Publishers 1983.
- additives and additives can be added individually in any mixtures or several different mixtures of the polymer melt, directly at the Isolation of the polymer or after melting of granules in a so-called compounding step.
- the additives and additives or mixtures thereof may be added as a solid, ie as a powder, or as a melt of the polymer melt.
- Another type of dosing is the use of masterbatches or mixtures of masterbatches of the additives or additive mixtures.
- Suitable additives are described, for example, in Additives for Plastics Handbook, John Murphy, Elsevier, Oxford 1999 or Plastics Additives Handbook Hans Zweifel, Hanser, Kunststoff 2001.
- Tris (2,4-di-tert-butylphenyl) phosphite (Irgafos 168), tetrakis (2,4-di-tert-butylphenyl) [1,1'-biphenyl] -4,4'-diylbisphosphonite are preferably suitable thermostabilizers.
- Trisoctyl phosphate, octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox 1076), bis (2,4-dicumylphenyl) pentaerythritol diphosphite (Doverphos S-9228), bis (2,6-di-tert-butyl) tert -butyl-4-methylphenyl) pentaerythritol diphosphite (ADK STAB PEP-36) or triphenylphosphine. They are used alone or in a mixture (eg Irganox B900 or Doverphos S-92228 with Irganox B900 or Irganox 1076).
- Pentaerythritol tetrastearate, glycerol monostearate, stearyl stearate or propanediol stearate are preferably suitable as mold release agents. They are used alone or in a mixture.
- Suitable light stabilizers are preferably benzotriazoles, triazines, benzophenones, cyanoacrylates, cinnamic acid esters or oxalanilides. They are used alone or in a mixture.
- inhibitors (quenchers) for deactivating catalyst residues of the polymer melt can be dissolved in pure form, in an inert solvent or added as a masterbatch.
- Suitable inhibitors are acid components such as Lewis or Brönsted acids or esters of strong acids.
- the pKa of the inhibitor should not be greater than 5, preferably less than 3.
- the acid component or its esters are added in order to deactivate the reaction mixture, that is to bring the reaction to a complete standstill in the ideal case.
- Suitable acid components are: ortho-phosphoric acid, phosphorous acid, pyrophosphoric acid, hypophosphoric acid, polyphosphoric acids, benzenephosphonic acid, sodium dihydrogenphosphate, boric acid, arylboronic acids, hydrochloric acid (hydrochloric acid), sulfuric acid, ascorbic acid, oxalic acid, benzoic acid, salicylic acid, formic acid, acetic acid, Adipic acid, citric acid, benzenesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid and all other phenyl-substituted benzenesulfonic, nitric, terephthalic, isophthalic, stearic and other fatty acids, acid chlorides such as phenyl chloroformate, stearic acid chloride, acetoxy-BP-A, benzoyl chloride and esters, half esters and bridged esters the above-mentioned
- Preferred suitable inhibitors are bridged esters of organic sulfur-containing acids selected from at least one compound
- R 1 is independently hydrogen or Ci-C 2 o alkyl, preferably C 1 -C 8 - alkyl, particularly preferably represents unsubstituted C 6 -alkyl, very particularly preferably Ci-C4-alkyl, wherein alkyl by Halogen may be substituted, in particular represents hydrogen or methyl,
- R 2 and R 3 independently of one another are hydrogen, or C 1 -C 6 -alkyl, C 4 -C 30 -alkylcarboxyl, preferably C 1 -C 4 -alkyl, C 6 -C 2 -5-alkylcarboxyl, particularly preferably C 8 - C 2 o-Alkylcarboxyl, in particular for hydrogen, C ⁇ -alkylcarboxyl or Ci 5 alkylcarboxyl or
- R 1 has the meaning given above
- n is an integer from 0 to 8, preferably 0 to 6, in particular 0, 1 or 2 stands.
- ortho-phosphoric acid pyrophosphoric acid, polyphosphoric acids, benzenephosphonic acid, benzoic acid, benzenesulphonic acid, toluenesulphonic acid, dodecylbenzenesulphonic acid and all other phenyl-substituted benzenesulphonic acids and esters, monoesters and bridged esters of the abovementioned acids, for example toluenesulphonic acid ester, phosphoric acid ester, phosphorous acid ester, phosphonic acid ester and other water-acidifying components such as tri-iso-octyl phosphate, Ultranox® 640 and BDP in question.
- the metered addition of the acidic components can take place in solid, liquid or gaseous form.
- the acidic component is continuously mixed homogeneously in the product stream to be liberated from the monomers in the production process directly after reaching the desired final molecular weight, to begin immediately thereafter with the evaporation of the residual monomers.
- the additive is carried out to improve individual product properties behind the acid dosage and the residual monomer reduction and not combined with the step of residual monomer reduction, because often additives are used, which in the vacuum, which is essential for the reduction of the residual monomers, volatile are and then poorly adjust in the required concentrations in the polymer.
- the acidic components are added in liquid form. Since the amounts to be dosed are very small, solutions of the acidic components are preferably used.
- Suitable solvents are those which do not interfere with the process, are chemically inert and evaporate rapidly.
- Solvents are all organic solvents having a boiling point at normal pressure of 30 to 300 0 C, preferably from 30 to 250 0 C and more preferably from 30 to 200 0 C and water - this includes water of crystallization - m question. Preferably, those compounds are selected which occur in the respective processes. Depending on the requirement profile of the product to be produced, any remaining residues do not reduce the quality.
- solvents include alkanes, cycloalkanes and aromatics, which may also be substituted.
- the substituents may be aliphatic, cyclohephatic or aromatic radicals in various combinations as well as halogens or a hydroxyl group.
- Heteroatoms, such as, for example, oxygen, can also be bridgehead between aliphatic, cycloaliphatic or aromatic radicals, it being possible for the radicals to be identical or different.
- Other solvents are kuiuicu ⁇ u ⁇ li Ketöiic u ⁇ u Esici ⁇ igdiiibilici sheuic ⁇ MJWIC cyulisuhe be Carb ⁇ naie.
- Examples are, in addition to water, n-pentane, n-hexane, n-heptane and their isomers, cyclohexane, toluene and xylene, methylene chloride, ethyl chloride, ethylene chloride, chlorobenzene, methanol, ethanol, propanol, butanol and their isomers, phenol, o-, m and p-cresol, diethyl ether, dimethyl ketone, polyethylene glycols, polypropylene glycols, ethyl acetate, ethylene carbonate and propylene carbonate.
- suitable for the polycarbonate process are water, phenol, propylene carbonate, ethylene carbonate and toluene.
- Particularly suitable are water, phenol and propylene carbonate.
- static mixers or other mixers leading to homogeneous mixing are suitable.
- the present application also relates to extrudates and shaped articles, in particular those for use in the transparent region, which are obtainable from the compositions according to the invention.
- Areas of application may be: safety windows, shields of helmets, foils, blown bodies such as water bottles, translucent panels, such as solid panels or in particular hollow panels, for example for covering buildings such as stations, greenhouses and lighting systems, traffic light housing or traffic signs, foams with open or closed optionally printable Surface, threads and wires (sa DE-A 11 37 167), lighting applications, optionally using glass fibers for applications in the translucent field, translucent settings containing barium sulfate and or titanium dioxide and or zirconium oxide or organic polymeric acrylate (EP) A 0 634 445, EP-A 0 269 324) for the production of light-permeable and light-scattering molded parts, precision injection-molded parts, such as holders, eg lens holders; here are optionally polycarbonates with glass fibers and an optionally additional content of 1-10 wt.% Molybdenum disulfide (based on the entire molding composition) used, optical device parts, in particular lenses for photo and film cameras (DE-A 27 01 173)
- the relative solution viscosity ⁇ ⁇ ] was determined in dichloromethane at a concentration of 5 g / l at 25 ° C with a Ubelohdeviskosimeter.
- the content of phenolic OH was obtained by IR measurement.
- a difference measurement of a solution of 2 g of polymer in 50 ml of dichloromethane was measured against pure dichloromethane and the difference in extinction at 3582 cm ' l determined.
- the flow behavior of the polymer melts is determined at different temperatures in a capillary rheometer according to ISO 11443.
- the polycarbonate samples are previously dried for this purpose at 130 0 C overnight.
- the specific surface resistance is determined on standard test specimens according to DIN IEC 60093.
- the sample is dissolved with methylene chloride. By adding acetone, the majority of the polymer is precipitated. The undissolved portions are filtered off, the filtrate is concentrated to dryness. The dry residue is dissolved with THF and the oligomers are determined by HPLC with UV detection.
- the sample is saponified with sodium methylate under reflux.
- the saponification solution is acidified and concentrated to dryness.
- the dry residue is dissolved with acetonitrile and the phenolic compounds (Ha to Va) are determined by HPLC with UV detection.
- the polycarbonate PCl was prepared in a melt process as follows.
- the melt is then via an expansion valve in a below 200 mbar standing
- Case fume evaporator heated again to 190 0 C and collected in a template. After a residence time of 20 minutes, the melt is poured into the next three similarly constructed stages pumped. The conditions in the 2. 1 1. 14th stage are 100/74/40 mbar; 220 ° / 225 ° / 273 ° C and 20/10/10 minutes. The resulting oligomer has a rel. Viscosity of 1.08. All vapors are passed through pressure controls in a column under vacuum and discharged as condensates.
- the oligomer is condensed in a subsequent disc reactor at 280 0 C and 3.0 mbar at a residence time of 45 minutes to a higher molecular weight product.
- the rel. Viscosity is 1.195.
- the vapors are condensed.
- a partial flow of 150 kg melt / h is branched off by means of a gear pump, mixed with 150 g of a 5% solution of the quencher of formula 6 in phenol / h, via a static mixer with a Length-to-diameter ratio of 20 passed and returned to the main melt stream.
- the added quencher is homogeneously distributed throughout the melt stream by means of another static mixer.
- the melt thus treated is further exposed in a further disc reactor at 290 0 C, 0.7 mbar and at a mean residence time of 120 minutes, the process conditions, discharged and granulated.
- the vapors are condensed in the vacuum system and behind it.
- the polycarbonates PC2 and PC3 are prepared analogously to PCl.
- PC4 and PC5 are comparative examples in which the polycarbonates (bisphenol A as diphenol) were prepared by the interfacial process
- Table 1 gives the data of the polycarbonate compositions prepared according to the above experiments, including the determined defect structure and cyclic proportions: Table 1:
- polycarbonate compositions according to the invention PC6, PC8, PC10 and PC12 have significantly higher surface resistances and thus have a better insulating behavior.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
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RU2010139787/04A RU2491305C9 (ru) | 2008-02-29 | 2009-02-17 | Поликарбонаты с улучшенной характеристикой текучести, содержащие циклические олигомеры |
ES09714130T ES2395802T3 (es) | 2008-02-29 | 2009-02-17 | Policarbonatos con oligómeros cíclicos y comportamiento de fluencia mejorado |
US12/919,924 US8110649B2 (en) | 2008-02-29 | 2009-02-17 | Polycarbonates comprising cyclic oligomers and having an improved flow behavior |
EP09714130A EP2250210B1 (de) | 2008-02-29 | 2009-02-17 | Polycarbonate mit cyclischen oligomeren und verbessertem fliessverhalten |
CN2009801068013A CN101959930B (zh) | 2008-02-29 | 2009-02-17 | 具有环状低聚物和改进的流动行为的聚碳酸酯 |
JP2010547992A JP5508290B2 (ja) | 2008-02-29 | 2009-02-17 | 環状オリゴマーを有し、流動性が改良されたポリカーボネート |
PL09714130T PL2250210T3 (pl) | 2008-02-29 | 2009-02-17 | Poliwęglany z cyklicznymi oligomerami i polepszonymi właściwościami przepływu |
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DE102008011903A DE102008011903A1 (de) | 2008-02-29 | 2008-02-29 | Polycarbonate mit cyclischen Oligomeren und verbessertem Fließverhalten |
DE102008011903.2 | 2008-02-29 |
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PCT/EP2009/001086 WO2009106246A1 (de) | 2008-02-29 | 2009-02-17 | Polycarbonate mit cyclischen oligomeren und verbessertem fliessverhalten |
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US (1) | US8110649B2 (de) |
EP (1) | EP2250210B1 (de) |
JP (1) | JP5508290B2 (de) |
KR (1) | KR101591117B1 (de) |
CN (1) | CN101959930B (de) |
DE (1) | DE102008011903A1 (de) |
ES (1) | ES2395802T3 (de) |
PL (1) | PL2250210T3 (de) |
RU (1) | RU2491305C9 (de) |
WO (1) | WO2009106246A1 (de) |
Cited By (2)
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WO2011038843A1 (de) * | 2009-09-30 | 2011-04-07 | Bayer Materialscience Ag | Uv-stabile polycarbonat-zusammensetzung mit verbesserten eigenschaften |
EP2308920A3 (de) * | 2009-09-30 | 2011-11-30 | Bayer MaterialScience AG | Polycarbonatzusammensetzung mit verbesserter Thermostabilität |
Families Citing this family (2)
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WO2016016418A1 (de) * | 2014-08-01 | 2016-02-04 | Covestro Deutschland Ag | Copolycarbonat-zusammensetzungen mit verzweigungsstrukturen und cyclischen oligomeren und verbesserten rheologischen eigenschaften |
KR102404309B1 (ko) | 2016-03-30 | 2022-05-31 | 미츠비시 가스 가가쿠 가부시키가이샤 | 방향족 폴리카보네이트 수지 조성물 및 방향족 폴리카보네이트 수지의 제조 방법 |
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WO2011038843A1 (de) * | 2009-09-30 | 2011-04-07 | Bayer Materialscience Ag | Uv-stabile polycarbonat-zusammensetzung mit verbesserten eigenschaften |
EP2308920A3 (de) * | 2009-09-30 | 2011-11-30 | Bayer MaterialScience AG | Polycarbonatzusammensetzung mit verbesserter Thermostabilität |
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Also Published As
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US8110649B2 (en) | 2012-02-07 |
PL2250210T3 (pl) | 2013-03-29 |
ES2395802T3 (es) | 2013-02-15 |
US20110003945A1 (en) | 2011-01-06 |
KR20100117628A (ko) | 2010-11-03 |
JP5508290B2 (ja) | 2014-05-28 |
RU2010139787A (ru) | 2012-04-10 |
DE102008011903A1 (de) | 2009-09-03 |
EP2250210B1 (de) | 2012-10-24 |
RU2491305C9 (ru) | 2014-04-10 |
RU2491305C2 (ru) | 2013-08-27 |
EP2250210A1 (de) | 2010-11-17 |
CN101959930A (zh) | 2011-01-26 |
JP2011513522A (ja) | 2011-04-28 |
CN101959930B (zh) | 2012-11-21 |
KR101591117B1 (ko) | 2016-02-03 |
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