CA2306157A1 - Preparation of dihydroxydiphenyl-copolycarbonates by melt re-esterification - Google Patents
Preparation of dihydroxydiphenyl-copolycarbonates by melt re-esterification Download PDFInfo
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- CA2306157A1 CA2306157A1 CA002306157A CA2306157A CA2306157A1 CA 2306157 A1 CA2306157 A1 CA 2306157A1 CA 002306157 A CA002306157 A CA 002306157A CA 2306157 A CA2306157 A CA 2306157A CA 2306157 A1 CA2306157 A1 CA 2306157A1
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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
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
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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
-
- 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
-
- 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
Abstract
The invention relates to a method for preparing special copolycarbonates from dihydroxydiphenylene in accordance with the polycarbonate preparation method in the melt, using N-alkyl-substituted piperidines and morpholines as catalysts.
Description
WO 99/19380 CA o 2 3 0 615 7 2 0 0 0 - 0 4 - o ~ pCT/EP98/06212 Process for the preparation of special copolvcarbonates by melt transesterification The subject of the present invention is a process for the preparation of thermoplastic copolycarbonates from 0.1 mol-% to 35 mol-%, preferably from 10 mol-% to 30 mol-% and in particular from 20 mol-% to 30 mol-%, of 4,4-dihydroxydiphenylene corresponding to Formula (~
R, Rz Rs Rs HO ~ ~ I ~ off (I) Ra Ra R~ Ra wherein Rl - R$ independently of one another are H or C,-C3 alkyl, and from complementary quantities, that is to say from 99.9 mol-% to 65-%, preferably from 90 mol-% to 70 mol-%
and in particular from 80 mol-% to 70 mol-%, of other diphenols corresponding to Formula (II) R3 R"
Ho ~ ~ x ~ ~ off (II) Rig R,z wherein R9 - R,, independently of one another are H, CH3, Cl or Br and X is C,-CS
alkylene, CZ-CS alkylidene, CS-C6 cycloalkylene, Cj C,°
cycloalkylidene, -S- or -O-, in accordance with the known polycarbonate preparation W099/19380 CA 02306157 2000-04-0~
R, Rz Rs Rs HO ~ ~ I ~ off (I) Ra Ra R~ Ra wherein Rl - R$ independently of one another are H or C,-C3 alkyl, and from complementary quantities, that is to say from 99.9 mol-% to 65-%, preferably from 90 mol-% to 70 mol-%
and in particular from 80 mol-% to 70 mol-%, of other diphenols corresponding to Formula (II) R3 R"
Ho ~ ~ x ~ ~ off (II) Rig R,z wherein R9 - R,, independently of one another are H, CH3, Cl or Br and X is C,-CS
alkylene, CZ-CS alkylidene, CS-C6 cycloalkylene, Cj C,°
cycloalkylidene, -S- or -O-, in accordance with the known polycarbonate preparation W099/19380 CA 02306157 2000-04-0~
process in a melt, said process being characterised in that use is made of N-alkyl-substituted piperidines and/or N-alkyl-substituted morpholines by way of catalysts in quantities from 10'Z to 10-a mol, preferably from 10'z to 10-S mol, per mol diphenol, the allcyl substituents being Ca C~Z alkyl groups, preferably CZ C$ alkyl groups and in particular CZ Cs alkyl groups.
Preferred N-alkyl piperidines are N-ethyl piperidine, N-propyl piperidine, N-isopropyl piperidine. Preferred N-alkyl morpholines are N-ethyl morpholine, N-propyl morpholine and N-isopropyl morpholine. N-ethyl piperidine is particularly preferred.
They may be employed on their own or in combination, together or in succession.
Preferred dihydroxydiphenyl is 4,4-dihydroxydiphenyl. Preferred diphenols (II) are 2,2-bis-(4-hydroxyphenyl)propane, 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexene and 1,1-bis-(4-hydroxyphenyl)-1-phenylethane.
According to EP-A-544 407 or US-PS-5,401,826 corresponding copolycarbonates are prepared in accordance with the melt-transesterification process. By way of catalysts use may be made of nitrogen bases, ammonium salts, alkali hydroxides, alkali salts, alkaline-earth hydroxides and alkaline-earth salts.
A disadvantageous aspect is that, with the use of alkali catalysts, secondary reactions occur in the form of undesirable branchings which have an influence on the colour and also on the mechanical properties.
Dihydroxydiphenyls are also named as comonomers in DE-OS 3 832 396. They may be employed in quantities from 0 to 98 mol-%, preferably from 0 to 95 mol-%, in particular from 0 to 90 mol-% and in quite particularly preferred manner in quantities between 0 and 80 mol-%.
Preparation may be effected in accordance with the known polycarbonate preparation processes, preferably in accordance with the interphase process.
W0 99/ 193 80 CA 0 2 3 0 615 7 2 0 0 0 - 0 4 - o ~ pCT/EP98/06212 According to DE-OS 2 119 779 the preparation of poiycarbonates with diphenyl structures is preferably effected in solution, to be specific in accordance with the interphase process and the process in homogeneous phase.
Now it was the object of the present invention to improve the process according to EP-A-544 407 and to prepare solvent-free, sparsely branched, chemical-resistant copolycarbonates with good yields that exhibit good transparency, little intrinsic colour (YI) and high resistance to ageing.
The polycarbonates that can be obtained by the process according to the invention are distinguished by a bright intrinsic colour and high transmission of light even after relatively long temperature loading. In addition they are largely free from undesirable imperfections in the polycarbonate itself and naturally solvent-free.
Largely free from undesirable imperfections in the polycarbonate in the sense of the process according to the invention means that the content of branching units corresponding to Formula (I1T) COOH
HO I ~ X ~ ~ O I ~ X I ~ OH (II1) (R)~ (R)~ (R)~ (R)~
with X C,-Cg alkylidene or cycloalkylidene, S or single bond, R CH,, Cl, Br and n 0, 1 or 2, - WO 99/19380 CA 02306157 2000-04-0~ PCT/EP98/06212 in the polycarbonate after total saponification and HPLC determination has a value of no more than 300 ppm, preferably no more than 100 ppm.
Suitable by way of carbonic acid derivatives in the process according to the invention are carbonic C6 C,4 diaryl esters, preferably the diesters of phenol or alkyl-substituted phenols, that is to say, for example, diphenyl carbonate or dicresyl carbonate. Relative to 1 mol bisphenol the carbonic diesters are employed in quantities from 1.01 to 1.30 mol, preferably 1.02 mol to 1.15 mol.
The reaction according to the invention may be carried out in one stage without isolation of an oligocarbonate stage, or in two stages or more than two stages with isolation of at least one oligocarbonate intermediate product.
It should be noted that the initial materials for the reaction according to the invention, 1 S that is to say the diphenols and the carbonic diaryl esters and catalysts, are free of alkali ions and alkaline earth ions, it being possible for quantities of less than 0.1 ppm of alkali and alkaline earth ions to be tolerated. Diphenols or carbonic diaryl esters that are pure in this sense can be obtained by the carbonic diaryl esters or diphenols being recrystallised, washed or distilled. With the process according to the invention the content of alkali and alkaline-earth metal ions both in the diphenol and in the carbonic diester and in the catalyst should amount to less than 0.1 ppm.
In detail, the process according to the invention is preferably carried out as follows:
dihydroxy compounds and carbonic diesters are melted down in a molar ratio of 1 mol to between 1.01 and 1.30 mol, preferably 1 mol to between 1.02 and 1.15 mol, and heated to temperatures from 80°C to 250°C, preferably 100°C to 230°C and in particular 120°C to 190°C, under atmospheric pressure in 0.1 hours to 5 hours, preferably 0.25 hours to 3 hours. After addition of the catalyst the monophenol is distilled off and an oligocarbonate is produced by lowering the pressure to 3 mbar and raising the temperature to 260°C.
WO 99/ 193 80 CA 0 2 3 0 615 7 2 0 0 0 - 0 4 - o ~ PCT/EP98/06212 In the second stage the polycarbonate is produced by polycondensation of the oligocarbonate by further increasing the temperature to between 270°C
and 320°C, preferably between 270°C and 295°C, at a pressure between 3 and 0.1 mbar.
The oligocarbonates of the first stage have average molecular weights M W of 3,000-24,000, preferably 5,000-20,000, ascertained by measuring the relative solution viscosity in dichloromethane or in mixtures of equal quantities by weight of phenol and o-dichlorobenzene, calibrated by light scattering. The molecular weights of the oligocarbonates of the 1 st stage depend on the desired final viscosity of the polycarbonates; accordingly, copolycarbonates of low molecular weight are obtained in the 2nd stage by the condensation of oligocarbonates of low molecular weight and copolycarbonates of higher molecular weight are obtained by the condensation of oligocarbonates of higher molecular weight.
The reaction according to the invention of the aromatic dihydroxy compounds and of the carbonic diester may be carried out continuously or discontinuously, for example in stirrer vessels, film-type evaporators, cascades of stirrer vessels, extruders, kneaders, simple disc-type reactors and high-viscosity disc-type reactors.
The copolycarbonates obtained are isolated by, for example, the melt being conducted through an extnzder, cooled and granulated.
The copolycarbonates that can be obtained by the process according to the invention have average molar masses M W from 18,000 to 60,000, preferably 19,000 to 40,000, ascertained by measuring the rel. solution viscosity in dichloromethane or in mixtures of equal quantities by weight of phenol and o-dichlorobenzene, calibrated by light scattering.
With a view to limiting the average molar masses M W of the polymers, phenols that are not readily volatile, such as cumylphenol, 4-phenylphenol, may be employed in quantities from 0.01 to 10 mol-% per mol diphenol.
W099/19380 CA 02306157 2000-04-0~ PCT/EP98/06212 The copolycarbonates that can be obtained in accordance with the invention may be processed in known manner to form various moulded articles and articles of daily use, for example by extrusion or by injection moulding.
The polycarbonates that can be obtained in accordance with the invention may by reason of their pattern of properties, in particular on account of their resistance to chemicals, be employed in particular in the automotive field as sheeting, plates, dashboard fittings or housing parts, but also in the optical field as lenses and data storage devices and also as articles of daily use, for example as tableware.
Consequently, also a subject of the present invention is the use of the polycarbonates that can be obtained in accordance with the invention for the production of chemical-resistant moulded articles.
With a view to modifying the properties of the copolycarbonates that can be obtained in accordance with the invention, auxiliary materials and reinforcing materials may also be admixed to said copolycarbonates. Materials to be taken into consideration as such are, inter alias stabilisers, flow aids, mould-release agents, fire-protection agents, pigments, finely divided minerals, fibrous materials, for example alkyl phosphites and aryl phosphites, alkyl phosphates and aryl phosphates, alkyl phosphanes and aryl phosphanes, low-molecular carbonic esters, halogen compounds, salts, chalk, quartz powder, glass fibres and carbon fibres.
Moreover, other polymers, for example polyolefins, polyurethanes or polystyrene, may also be admixed to the polycarbonates that can be obtained in accordance with the invention.
The addition of these substances is preferably carried out with the aid of conventional units to produce the finished polycarbonate but, depending on requirements, may also be carried out at another stage of the process according to the invention.
WO 99/19380 CA 02306157 2000-04-0~ PCT/EP98/06212 -7_ Example Preparation of the polycarbonates via the melt-transesterification process 114.15 g (0.500 mol) bisphenol A and 113.54 g (0.530 mol) diphenyl carbonate are weighed into a 500 ml three-necked flask with stirrer, internal thermometer and Vigreux column (30 cm, metallised) with bridge. The apparatus is freed of atmospheric oxygen by application of vacuum and flushing with nitrogen (3 times) and the mixture is heated up to 150°C. Now 6.87 pl N-ethyl piperidine (0.01 mol-%, relative to bisphenol A) are added and the phenol that arises is distilled off at 100 mbar. At the same time the temperature is raised to 250°C. The vacuum is now enhanced in stages to 1 mbar and the temperature is increased to 260°C.
Subsequently the temperature is increased to 280°C and the reaction mixture is stirred at 0.1 mbar for 1.5 hours. The relative solution viscosity amounts to 1.296 (dichloromethane, 25°C, 5 g/1). The phenolic OH value of the polycarbonate amounts to 70 ppm.
The copolycarbonates in Table 1 were produced correspondingly (BPA = 2,2-bis-(4-hydroxyphenyl)propane, TMC - 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, DOD = 4,4'-dihydroxydiphenyl).
WO 99/19380 CA 02306157 2000-04-0~ PCT/EP98/06212 _g_ Table 1 Composition of the copolycarbonates No. BPA TMC DOD r~re,_ Tg Branching units [mol-%] [mol-%] [mol-%] test [C] Formula III [ppm]
piece 1 100 - - 1.296 153 20 2 90 - 10 1.333 156 6 3 80 - 20 1.356 161 10 4 70 - 30 1.388 163 13 65 35 - 1.259 188 5 6 58.5 31.5 10 1.286 186 10 7 52 28 20 1.328 188 14 8 45.5 24.5 30 1.334 188 8 In order to investigate the mechanical properties of the material by means of a tensile test in accordance with DIN 53 455 {ISO 527), in each case 20 dumb-bell strips No. 3 (4 mm thiclrness) were produced by injection moulding. The results of the tensile tests are compiled in Table 2.
W099/19380 CA 02306157 2000-04-0~ PCT/EP98/06212 Table 2 Mechanical properties of the copolycarbonates No. Modulus Tear Yield Yield Elongation of resistance stress elongation at elasticity/mmz /mm2 tear /mm2 In order to investigate the stress cracking (ESC), 80 x 10 x 4 mm flat bars in a mixture of isooctane/toluene were supported on a template with 0 %, 0.6 % and 1.0 %
outer fibre strain for 30 sec at 23°C. After 1 h load-free exposure to air and also 1 h storage at 110°C the specimen is assessed visually and the Charily impact strength (DIN 53 453, ISO 179) in respect of the unnotched specimen is measured. The results are compiled in Table 3.
Preferred N-alkyl piperidines are N-ethyl piperidine, N-propyl piperidine, N-isopropyl piperidine. Preferred N-alkyl morpholines are N-ethyl morpholine, N-propyl morpholine and N-isopropyl morpholine. N-ethyl piperidine is particularly preferred.
They may be employed on their own or in combination, together or in succession.
Preferred dihydroxydiphenyl is 4,4-dihydroxydiphenyl. Preferred diphenols (II) are 2,2-bis-(4-hydroxyphenyl)propane, 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexene and 1,1-bis-(4-hydroxyphenyl)-1-phenylethane.
According to EP-A-544 407 or US-PS-5,401,826 corresponding copolycarbonates are prepared in accordance with the melt-transesterification process. By way of catalysts use may be made of nitrogen bases, ammonium salts, alkali hydroxides, alkali salts, alkaline-earth hydroxides and alkaline-earth salts.
A disadvantageous aspect is that, with the use of alkali catalysts, secondary reactions occur in the form of undesirable branchings which have an influence on the colour and also on the mechanical properties.
Dihydroxydiphenyls are also named as comonomers in DE-OS 3 832 396. They may be employed in quantities from 0 to 98 mol-%, preferably from 0 to 95 mol-%, in particular from 0 to 90 mol-% and in quite particularly preferred manner in quantities between 0 and 80 mol-%.
Preparation may be effected in accordance with the known polycarbonate preparation processes, preferably in accordance with the interphase process.
W0 99/ 193 80 CA 0 2 3 0 615 7 2 0 0 0 - 0 4 - o ~ pCT/EP98/06212 According to DE-OS 2 119 779 the preparation of poiycarbonates with diphenyl structures is preferably effected in solution, to be specific in accordance with the interphase process and the process in homogeneous phase.
Now it was the object of the present invention to improve the process according to EP-A-544 407 and to prepare solvent-free, sparsely branched, chemical-resistant copolycarbonates with good yields that exhibit good transparency, little intrinsic colour (YI) and high resistance to ageing.
The polycarbonates that can be obtained by the process according to the invention are distinguished by a bright intrinsic colour and high transmission of light even after relatively long temperature loading. In addition they are largely free from undesirable imperfections in the polycarbonate itself and naturally solvent-free.
Largely free from undesirable imperfections in the polycarbonate in the sense of the process according to the invention means that the content of branching units corresponding to Formula (I1T) COOH
HO I ~ X ~ ~ O I ~ X I ~ OH (II1) (R)~ (R)~ (R)~ (R)~
with X C,-Cg alkylidene or cycloalkylidene, S or single bond, R CH,, Cl, Br and n 0, 1 or 2, - WO 99/19380 CA 02306157 2000-04-0~ PCT/EP98/06212 in the polycarbonate after total saponification and HPLC determination has a value of no more than 300 ppm, preferably no more than 100 ppm.
Suitable by way of carbonic acid derivatives in the process according to the invention are carbonic C6 C,4 diaryl esters, preferably the diesters of phenol or alkyl-substituted phenols, that is to say, for example, diphenyl carbonate or dicresyl carbonate. Relative to 1 mol bisphenol the carbonic diesters are employed in quantities from 1.01 to 1.30 mol, preferably 1.02 mol to 1.15 mol.
The reaction according to the invention may be carried out in one stage without isolation of an oligocarbonate stage, or in two stages or more than two stages with isolation of at least one oligocarbonate intermediate product.
It should be noted that the initial materials for the reaction according to the invention, 1 S that is to say the diphenols and the carbonic diaryl esters and catalysts, are free of alkali ions and alkaline earth ions, it being possible for quantities of less than 0.1 ppm of alkali and alkaline earth ions to be tolerated. Diphenols or carbonic diaryl esters that are pure in this sense can be obtained by the carbonic diaryl esters or diphenols being recrystallised, washed or distilled. With the process according to the invention the content of alkali and alkaline-earth metal ions both in the diphenol and in the carbonic diester and in the catalyst should amount to less than 0.1 ppm.
In detail, the process according to the invention is preferably carried out as follows:
dihydroxy compounds and carbonic diesters are melted down in a molar ratio of 1 mol to between 1.01 and 1.30 mol, preferably 1 mol to between 1.02 and 1.15 mol, and heated to temperatures from 80°C to 250°C, preferably 100°C to 230°C and in particular 120°C to 190°C, under atmospheric pressure in 0.1 hours to 5 hours, preferably 0.25 hours to 3 hours. After addition of the catalyst the monophenol is distilled off and an oligocarbonate is produced by lowering the pressure to 3 mbar and raising the temperature to 260°C.
WO 99/ 193 80 CA 0 2 3 0 615 7 2 0 0 0 - 0 4 - o ~ PCT/EP98/06212 In the second stage the polycarbonate is produced by polycondensation of the oligocarbonate by further increasing the temperature to between 270°C
and 320°C, preferably between 270°C and 295°C, at a pressure between 3 and 0.1 mbar.
The oligocarbonates of the first stage have average molecular weights M W of 3,000-24,000, preferably 5,000-20,000, ascertained by measuring the relative solution viscosity in dichloromethane or in mixtures of equal quantities by weight of phenol and o-dichlorobenzene, calibrated by light scattering. The molecular weights of the oligocarbonates of the 1 st stage depend on the desired final viscosity of the polycarbonates; accordingly, copolycarbonates of low molecular weight are obtained in the 2nd stage by the condensation of oligocarbonates of low molecular weight and copolycarbonates of higher molecular weight are obtained by the condensation of oligocarbonates of higher molecular weight.
The reaction according to the invention of the aromatic dihydroxy compounds and of the carbonic diester may be carried out continuously or discontinuously, for example in stirrer vessels, film-type evaporators, cascades of stirrer vessels, extruders, kneaders, simple disc-type reactors and high-viscosity disc-type reactors.
The copolycarbonates obtained are isolated by, for example, the melt being conducted through an extnzder, cooled and granulated.
The copolycarbonates that can be obtained by the process according to the invention have average molar masses M W from 18,000 to 60,000, preferably 19,000 to 40,000, ascertained by measuring the rel. solution viscosity in dichloromethane or in mixtures of equal quantities by weight of phenol and o-dichlorobenzene, calibrated by light scattering.
With a view to limiting the average molar masses M W of the polymers, phenols that are not readily volatile, such as cumylphenol, 4-phenylphenol, may be employed in quantities from 0.01 to 10 mol-% per mol diphenol.
W099/19380 CA 02306157 2000-04-0~ PCT/EP98/06212 The copolycarbonates that can be obtained in accordance with the invention may be processed in known manner to form various moulded articles and articles of daily use, for example by extrusion or by injection moulding.
The polycarbonates that can be obtained in accordance with the invention may by reason of their pattern of properties, in particular on account of their resistance to chemicals, be employed in particular in the automotive field as sheeting, plates, dashboard fittings or housing parts, but also in the optical field as lenses and data storage devices and also as articles of daily use, for example as tableware.
Consequently, also a subject of the present invention is the use of the polycarbonates that can be obtained in accordance with the invention for the production of chemical-resistant moulded articles.
With a view to modifying the properties of the copolycarbonates that can be obtained in accordance with the invention, auxiliary materials and reinforcing materials may also be admixed to said copolycarbonates. Materials to be taken into consideration as such are, inter alias stabilisers, flow aids, mould-release agents, fire-protection agents, pigments, finely divided minerals, fibrous materials, for example alkyl phosphites and aryl phosphites, alkyl phosphates and aryl phosphates, alkyl phosphanes and aryl phosphanes, low-molecular carbonic esters, halogen compounds, salts, chalk, quartz powder, glass fibres and carbon fibres.
Moreover, other polymers, for example polyolefins, polyurethanes or polystyrene, may also be admixed to the polycarbonates that can be obtained in accordance with the invention.
The addition of these substances is preferably carried out with the aid of conventional units to produce the finished polycarbonate but, depending on requirements, may also be carried out at another stage of the process according to the invention.
WO 99/19380 CA 02306157 2000-04-0~ PCT/EP98/06212 -7_ Example Preparation of the polycarbonates via the melt-transesterification process 114.15 g (0.500 mol) bisphenol A and 113.54 g (0.530 mol) diphenyl carbonate are weighed into a 500 ml three-necked flask with stirrer, internal thermometer and Vigreux column (30 cm, metallised) with bridge. The apparatus is freed of atmospheric oxygen by application of vacuum and flushing with nitrogen (3 times) and the mixture is heated up to 150°C. Now 6.87 pl N-ethyl piperidine (0.01 mol-%, relative to bisphenol A) are added and the phenol that arises is distilled off at 100 mbar. At the same time the temperature is raised to 250°C. The vacuum is now enhanced in stages to 1 mbar and the temperature is increased to 260°C.
Subsequently the temperature is increased to 280°C and the reaction mixture is stirred at 0.1 mbar for 1.5 hours. The relative solution viscosity amounts to 1.296 (dichloromethane, 25°C, 5 g/1). The phenolic OH value of the polycarbonate amounts to 70 ppm.
The copolycarbonates in Table 1 were produced correspondingly (BPA = 2,2-bis-(4-hydroxyphenyl)propane, TMC - 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, DOD = 4,4'-dihydroxydiphenyl).
WO 99/19380 CA 02306157 2000-04-0~ PCT/EP98/06212 _g_ Table 1 Composition of the copolycarbonates No. BPA TMC DOD r~re,_ Tg Branching units [mol-%] [mol-%] [mol-%] test [C] Formula III [ppm]
piece 1 100 - - 1.296 153 20 2 90 - 10 1.333 156 6 3 80 - 20 1.356 161 10 4 70 - 30 1.388 163 13 65 35 - 1.259 188 5 6 58.5 31.5 10 1.286 186 10 7 52 28 20 1.328 188 14 8 45.5 24.5 30 1.334 188 8 In order to investigate the mechanical properties of the material by means of a tensile test in accordance with DIN 53 455 {ISO 527), in each case 20 dumb-bell strips No. 3 (4 mm thiclrness) were produced by injection moulding. The results of the tensile tests are compiled in Table 2.
W099/19380 CA 02306157 2000-04-0~ PCT/EP98/06212 Table 2 Mechanical properties of the copolycarbonates No. Modulus Tear Yield Yield Elongation of resistance stress elongation at elasticity/mmz /mm2 tear /mm2 In order to investigate the stress cracking (ESC), 80 x 10 x 4 mm flat bars in a mixture of isooctane/toluene were supported on a template with 0 %, 0.6 % and 1.0 %
outer fibre strain for 30 sec at 23°C. After 1 h load-free exposure to air and also 1 h storage at 110°C the specimen is assessed visually and the Charily impact strength (DIN 53 453, ISO 179) in respect of the unnotched specimen is measured. The results are compiled in Table 3.
Table 3 Charily impact strength in respect of the unnotched specimen of specimens stored in isooctane/toluene.
Isooctane/toluene Isooctane/toluene 70:30 50:50 [kJ/m2] with 0 [kJ/m2J [kJ/m2]
% outer with with fibre strain 0.6 10 %
% outer outer fibre fibre strain strain 1 n.b. n.b.* 3 n.b./22* 7*/** 4*/**
2 n.b. n.b. n.b. n.b. 29*
3 n.b. n.b. n.b. n.b. 58*
4 n.b. n.b. n.b. n.b. n.b.
5 n.b. 4*/** 4*** **** ****
6 n.b. 33* S* **** ****
7 n.b. n.b. 27* 7* 5*/**
8 n.b. n.b. n.b. n.b. 10*/**
n. b. not broken * edge crack ** surface crack * * * transverse cracks * * * * broken on template
Isooctane/toluene Isooctane/toluene 70:30 50:50 [kJ/m2] with 0 [kJ/m2J [kJ/m2]
% outer with with fibre strain 0.6 10 %
% outer outer fibre fibre strain strain 1 n.b. n.b.* 3 n.b./22* 7*/** 4*/**
2 n.b. n.b. n.b. n.b. 29*
3 n.b. n.b. n.b. n.b. 58*
4 n.b. n.b. n.b. n.b. n.b.
5 n.b. 4*/** 4*** **** ****
6 n.b. 33* S* **** ****
7 n.b. n.b. 27* 7* 5*/**
8 n.b. n.b. n.b. n.b. 10*/**
n. b. not broken * edge crack ** surface crack * * * transverse cracks * * * * broken on template
Claims (4)
1. Process for the preparation of thermoplastic copolycarbonates from 0.1 mol-% to 35 mol-% of 4,4-dihydroxydiphenylene corresponding to Formula (I) wherein R1 - R8 independently of one another are H or C1-C3 alkyl, and from complementary quantities, that is to say from 99.9 mol-% to 65%, of other diphenols corresponding to Formula (III) wherein R9 - R12 independently of one another are H, CH3, Cl or Br and X is C1-C5 alkylene, C2-C5 alkylidene, C5-C6 cycloalkylene, C5-C10 cycloalkylidene, , -S- or -O-, in accordance with the known polycarbonate preparation process in a melt, wherein use is made of N-alkyl-substituted piperidines or morpholines by way of catalysts in quantities from 10-2 to 10-8 mol per mol diphenol, the alkyl substituents being C2-C12 alkyl groups.
2. Process according to Claim 1, characterised in that use is made of N-ethyl piperidine by way of catalyst.
3. Process according to Claim 1, characterised in that the content of branching units corresponding to Formula (III) with X C1-C8 alkylidene or cycloalkylidene, S or single bond, R CH3, Cl, Br and n 0, 1 or 2, in the polycarbonate after total saponification and HPLC determination has a value of no more than 300 ppm.
4. Use of the polycarbonates that can be obtained in accordance with Claim 1 for the production of chemical-resistant moulded articles.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19744693A DE19744693A1 (en) | 1997-10-10 | 1997-10-10 | Production of thermoplastic copolycarbonates useful for moldings resistant to chemicals |
| DE19744693.0 | 1997-10-10 | ||
| PCT/EP1998/006212 WO1999019380A1 (en) | 1997-10-10 | 1998-09-30 | Preparation of dihydroxydiphenyl-copolycarbonates by melt re-esterification |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2306157A1 true CA2306157A1 (en) | 1999-04-22 |
Family
ID=7845093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002306157A Abandoned CA2306157A1 (en) | 1997-10-10 | 1998-09-30 | Preparation of dihydroxydiphenyl-copolycarbonates by melt re-esterification |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP1023357A1 (en) |
| JP (1) | JP2001520242A (en) |
| KR (1) | KR20010031016A (en) |
| CN (1) | CN1266442A (en) |
| AU (1) | AU9541798A (en) |
| BR (1) | BR9812888A (en) |
| CA (1) | CA2306157A1 (en) |
| DE (1) | DE19744693A1 (en) |
| ID (1) | ID24573A (en) |
| IL (1) | IL135003A0 (en) |
| NO (1) | NO20001167D0 (en) |
| TW (1) | TW426704B (en) |
| WO (1) | WO1999019380A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6740714B2 (en) * | 2001-07-20 | 2004-05-25 | Bayer Aktiengesellschaft | Polycarbonate blends |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1325080A1 (en) * | 2000-09-26 | 2003-07-09 | Bayer Aktiengesellschaft | Copolycarbonate-based composition |
| JP2002114841A (en) * | 2000-10-06 | 2002-04-16 | Mitsui Chemicals Inc | Optical part |
| JP2002114842A (en) * | 2000-10-06 | 2002-04-16 | Mitsui Chemicals Inc | Polycarbonate resin and optical part composed by including the same |
| JP4514080B2 (en) * | 2000-12-28 | 2010-07-28 | 三井化学株式会社 | Polycarbonate resin composition and optical component comprising the same |
| US6608163B2 (en) | 2001-01-17 | 2003-08-19 | General Electric Company | Polycarbonate copolymers having improved hydrolytic stability |
| US7183371B2 (en) * | 2004-11-01 | 2007-02-27 | General Electric Company | Method for making polycarbonate |
| CN102464545A (en) | 2010-11-11 | 2012-05-23 | 中国石油天然气股份有限公司 | Method for preparing 1-octylene by performing ethylene oligomerization |
| TWI693244B (en) * | 2015-01-20 | 2020-05-11 | 德商科思創德意志股份有限公司 | Preparation of highly heat-resistant (co) polycarbonates by the transesterification method |
| WO2023149329A1 (en) * | 2022-02-07 | 2023-08-10 | 三菱ケミカル株式会社 | Polycarbonate resin composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2735775A1 (en) * | 1977-08-09 | 1979-02-22 | Bayer Ag | PROCESS FOR THE PRODUCTION OF POLYCARBONATE |
| JPS61264020A (en) * | 1985-05-17 | 1986-11-21 | Idemitsu Kosan Co Ltd | Aromatic polycarbonate and production thereof |
| DE3919046A1 (en) * | 1989-06-10 | 1990-12-20 | Bayer Ag | NEW THERMOTROPE POLYCARBONATES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR THE PRODUCTION OF MOLDED BODIES, FILAMENTS, FIBERS AND FILMS |
| JPH05117382A (en) * | 1991-10-29 | 1993-05-14 | Nippon G Ii Plast Kk | Copolymerized polycarbonate, its production and composition composed thereof |
| US5475079A (en) * | 1993-04-28 | 1995-12-12 | Daicel Chemical Industries, Ltd. | (CO) polycarbonate composition and process for preparing the same |
| JPH08165341A (en) * | 1994-12-15 | 1996-06-25 | Idemitsu Kosan Co Ltd | Production of polycarbonate |
-
1997
- 1997-10-10 DE DE19744693A patent/DE19744693A1/en not_active Withdrawn
-
1998
- 1998-09-21 TW TW087115670A patent/TW426704B/en not_active IP Right Cessation
- 1998-09-30 EP EP98948996A patent/EP1023357A1/en not_active Withdrawn
- 1998-09-30 BR BR9812888-4A patent/BR9812888A/en not_active IP Right Cessation
- 1998-09-30 KR KR1020007003823A patent/KR20010031016A/en not_active Application Discontinuation
- 1998-09-30 IL IL13500398A patent/IL135003A0/en unknown
- 1998-09-30 WO PCT/EP1998/006212 patent/WO1999019380A1/en not_active Application Discontinuation
- 1998-09-30 JP JP2000515948A patent/JP2001520242A/en active Pending
- 1998-09-30 CN CN98808044A patent/CN1266442A/en active Pending
- 1998-09-30 CA CA002306157A patent/CA2306157A1/en not_active Abandoned
- 1998-09-30 AU AU95417/98A patent/AU9541798A/en not_active Abandoned
- 1998-09-30 ID IDW20000622D patent/ID24573A/en unknown
-
2000
- 2000-03-07 NO NO20001167A patent/NO20001167D0/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6740714B2 (en) * | 2001-07-20 | 2004-05-25 | Bayer Aktiengesellschaft | Polycarbonate blends |
Also Published As
| Publication number | Publication date |
|---|---|
| BR9812888A (en) | 2000-08-08 |
| NO20001167L (en) | 2000-03-07 |
| TW426704B (en) | 2001-03-21 |
| EP1023357A1 (en) | 2000-08-02 |
| WO1999019380A1 (en) | 1999-04-22 |
| AU9541798A (en) | 1999-05-03 |
| NO20001167D0 (en) | 2000-03-07 |
| KR20010031016A (en) | 2001-04-16 |
| CN1266442A (en) | 2000-09-13 |
| DE19744693A1 (en) | 1999-04-15 |
| JP2001520242A (en) | 2001-10-30 |
| IL135003A0 (en) | 2001-05-20 |
| ID24573A (en) | 2000-07-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |