CA2664397A1 - Polycarbonates and copolycarbonates having improved adhesion to metals - Google Patents
Polycarbonates and copolycarbonates having improved adhesion to metals Download PDFInfo
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- CA2664397A1 CA2664397A1 CA002664397A CA2664397A CA2664397A1 CA 2664397 A1 CA2664397 A1 CA 2664397A1 CA 002664397 A CA002664397 A CA 002664397A CA 2664397 A CA2664397 A CA 2664397A CA 2664397 A1 CA2664397 A1 CA 2664397A1
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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
- C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
- C08G64/12—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen containing nitrogen
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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
- C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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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
Abstract
The present invention provides polycarbonates and copolycarbonates with a higher glass transition temperature and hence also use temperature and improved metal adhesion, processes for their production and their use for producing blends, moldings and extrudates obtainable therefrom. The invention further provides novel bisphenols and their use for preparing (co)polycarbonates.
Description
BMS 06 1 120 - WO-nat Polycarbonates and copolycarbonates havin2 improved adhesion to metals The present invention provides polycarbonates and copolycarbonates having a relatively high glass transition temperature and therefore also use temperature and improved adhesion to metals, processes for the preparation thereof and the use thereof for the preparation of blends, and mouldings and extrudates obtainable therefrom. The invention furthermore provides two novel bisphenols and the use thereof for the preparation of (co)polycarbonates.
Aromatic polycarbonates belong to the group of industrial thermoplastics. They are distinguished by combination of the technologically important properties of transparency, heat distortion resistance and toughness.
To obtain high molecular weight polycarbonates by the phase interface process, the alkali metal salts of bisphenols are reacted with phosgene in the two-phase mixture.
The molecular weight can be controlled by the amount of monophenols, such as e.g.
phenol or tert-butylphenol. Practically exclusively linear polymers are formed in these reactions. This can be demonstrated by end group analysis. By targeted use of so-called branching agents, as a rule polyhydroxylated compounds, branched polycarbonates are also obtained in this context.
For the preparation of polycarbonates by the phase interface process, reference may be made by way of example to H. Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, vol. 9, lnterscience Publishers, New York p. 33 et seq. and to Polymer Reviews, vol. 10, "Condensation Polymers by Interfacial and Solution Methods", Paul W. Morgan, Interscience Publishers, New York 1965, chap. VIII, p. 325.
For the preparation of polycarbonates by the melt transesterification process, the bisphenols are reacted in the melt with diaryl carbonates, usually diphenyl BMS 06 1 120- WO-nat carbonate, in the presence of catalysts, such as alkali metal salts or ammonium or phosphonium compounds.
The melt transesterification process is described, for example, in the Encyclopedia of Polymer Science, vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, vol. 9, John Wiley and Sons, Inc. (1964) and DE-C
31 512.
Polycarbonates based on 2-hydrocarbyl-3,3-bis(4-hydroxyaryl)phthalimidines as 10 monomers, which can be prepared by synthesis from phenolphthalein and an aniline hydrochloride derivative in aniline, are known from EP-A 1 582 549. This preparation is very involved and does not proceed satisfactorily. This bisphenol class thus has the industrial disadvantage of being accessible in only a very cumbersome manner.
However, due to their lack of adhesion to metals, the polycarbonates and copolycarbonates already described in the prior art have the disadvantage that they may have only a limited suitability or a suitability which is not optimum for use as a metallized component in e.g. high temperature uses.
There was therefore the object of providing polycarbonates or copolycarbonates and processes for the preparation thereof which avoid these disadvantages. This object is achieved, surprisingly, by the use of the class according to the invention of bisphenols of the general formulae (1 a) and (1 b) (isomer mixture) (also called bisphenols of the formula (1) in the following) BMS 06 1 120- WO-nat O
R? 0 N
R \ I \ R' ` I \
OH OH
HO HO
(1 a) (1 b) in which R' independently of one another represents hydrogen or CI -C1o alkyl, preferably hydrogen or CI-C6 alkyl, particularly preferably hydrogen or CI-C4 alkyl, very particularly preferably hydrogen or methyl, R 2 represents Cl-Clo alkyl, preferably CI-C6 alkyl, particularly preferably alkyl, or in each case optionally substituted phenyl or benzyl, in particular methyl, phenyl or benzyl, wherein the radicals mentioned for R' are preferred as substituents for phenyl and benzyl.
Alkyl in the context of the present invention is in each case linear or branched.
Particularly preferably, R2 represents phenyl which is optionally substituted by the radicals mentioned in R~, represented by the formula (lc) and (]d) (isomer mixture) BMS 06 1 120- WO-nat ~
?&~
R - ~ ~ N O
RROH R OH
HO HO
(1c) (1d) wherein R' has the abovementioned meaning.
The bisphenol of the formula (le) and (lf) (isomer mixture) ~ N O b%N
OH OH
HO HO
(1e) (1f) is very particularly preferred.
These bisphenols of the formula (I) according to the invention can be prepared from phenol derivatives and N-substituted isatin derivatives in an acid-catalyzed reaction.
This can be carried out by means of reactions analogous to that which is described for the preparation of unsubstituted isatin-bisphenols (H. N. Song et al., Synthetic BMS 06 l 120- WO-nat Communications 1999, 29 (19), 3303 and R. Berendes, H. Klos, Patent Specification No. 488760, Patent Office of the German Reich 1930).
The synthesis of the bisphenols according to the invention is preferably carried out as a condensation reaction of corresponding phenols and isatin derivatives, as the following example shows:
HO
HCI
N
~ a 1(e) 3,3-bis(4-hydroxyphenyl)-] -phenyl-] H-indol-2-one OH
0y , / N I \
/ \\ OH
- 1(f) 2,2-bis(4-hydroxyphenyl)-l -phenyl-] H-indol-3-one, an isomer mixture being obtained.
Very particularly preferably, the condensation is carried out with hydrochloric acid as the acid catalyst at temperatures of between 0 and 60 C with a stoichiometric ratio of phenol derivative to ketone derivative of 10 to 1, a mercaptan or thiocarboxylic acid compound (e.g. dodecylmercaptan, mercaptopropionic acid or thioacetic acid) preferably being present as a sulfur-containing compound, preferably only in an amount of about 0.01 to 25 %, based on the ketone compound.
The hydrochloric acid is very particularly preferably passed in as HCI gas.
BMS 06 1 120- WO-nat The condensation can be carried out in substance or in solution. In this context, inert solvents, such as, for example, chlorinated hydrocarbons, such as methylene chloride or dichloroethane, or toluene, xylenes or chlorobenzenes, are employed.
The reaction is particularly preferably carried out in substance with an excess of phenol.
A further synthesis possibility for the preparation of N-phenylisatin is the use of commercially obtainable isatin (e.g. BASF AG) in the form of an N-arylation reaction. The following organometallic syntheses known from the literature are available in this context.
a O
N
H
isatin Cul or Pd cat or Cu0 Hal Ullmann reaction NHMe DMF
ligand c I Hal = CI, Br, I
reflux NHMe Lit.: 55 % yield llo C Lit.: > 90 % yield 0 HO,B-OH N \ I \ ~
c'o I / ~~ I \
0 N-phenylisatin Cu(oAc)2 O
Suzuki coupling CH2CI2 o Cu(OAc)2 or Cu(OAc)2 systems Et3N or pyridine ~
v N
H Et3N or pyridine RT
RT Lit.: 70 - 87 % yield H
Lit.: 53 - 72 % yield BMS 06 1 120- WO-nat A further synthesis possibility for the preparation of N-phenylisatin is the use of the isonitrosoacetanilide isatin process (formerly for the preparation of indigo, Traugott Sandmeyer, Geigy Basel 1919). The following reaction steps are carried out in this:
OH
~ I
i ~
OH N
/ NH + CI OH - --Y I / ~
c N 0 cl (chloral hydrate) /
(H2NOH)2 HZSO, \ I
diphenylamine oximidoacetanilide (isonitrosoacetanilide) Hz0 0 HzSO, conc.
I\ O H20 0 / N (NH4)ZSO4 ~
a N-phenylisatin N-phenylisatin-R-imide A further synthesis possibility for the preparation of N-phenylisatin is via the reaction stage of a nitrone. The following reaction steps are carried out in this:
BMS 06 1 120- WO-nat o II
~NH + ~Cl NjilCI
CI
~ ~, ~ ~
N
O O
\N N
N N II N\ I
CI
DMF 0:11 HCI
CHO O
N HCI ~ O
O HO
+ N N C~% N
H \ RT
- H2N &N' b The phenols employed are known or can be prepared by processes known from the literature, for example by Friedel Crafts alkylation (Organikum, Organish-chemisches Grundpraktikum, corrected reprint of the 20th edition, Wiley-VCH, Weinheim, p. 355, 1999). Very many phenols are also commercially obtainable (suppliers e.g. Aldrich, Fluka, Acros etc.).
The isatin derivatives used are likewise known or can be prepared by processes known from the literature, for example by alkylation of the corresponding isatin parent substance. For example, they are accessible from the corresponding sodium or potassium salts of the isatin parent substance by reaction with alkyl halides in absolute alcohol (G. Heller, O. Notzel, Ber. Dtsch. Chem. Ges. 1907, 40, 1294). An alternative synthesis possibility is offered by alkylation via 0-alkylated isourea derivatives (E. Vowinkel, Chem. Ber. 1966, 99, 1479, or L. J. Mathia, Synthesis 1979, 561). These can be obtained by reaction of N,N'-dicyclohexylcarbodiimide with an alcohol in the presence of copper(l) chloride (E. Schmidt, F.
Moosmuller, BMS 06 1 120- WO-nat Liebigs Ann. Chem. 1955, 597, 235). Some N-substituted isatins are also commercially obtainable (suppliers e.g. ChemPur GmbH, Karlsruhe, Germany or Alfa Aesar, Karlsruhe, German or Sigma-Aldrich or Lancaster Synthesis Ltd.
Newgate, United Kingdom).
The present invention likewise provides polycarbonates or copolycarbonates which are prepared using the bisphenols according to the invention, and the corresponding preparation processes.
The (co)polycarbonates according to the invention are based on bisphenols of the general formulae (la,) and (lbi) (isomer mixture) as a recurring monomer unit N
O
R
` I \
R' O--O (la,) O
R? N
R
R' O-O (1bi) wherein R' and R2 have the abovementioned meaning.
Preferred bisphenols are likewise those mentioned above.
BMS 06 1 120- WO-nat In the case of (co)polycarbonates, in addition to one or more bisphenols of the formula (1), these can contain as a further monomer unit bisphenols of the formula (2) O X O -R4 R4 (2) in which R3 and R4 independently of one another represent H, CI-C18-alkyl, Cl-Clg-alkoxy, halogen, such as Cl or Br, or in each case optionally substituted aryl or aralkyl, preferably H or CI-C12-alkyl, particularly preferably H or Ci-C8-alkyl and very particularly preferably H or methyl, and X represents a single bond, -SO2-. -CO-, -0-, -S-, C1- to C6-alkylene, C2- to alkylidene or C5- to C6-cycloalkylidene, which can be substituted by Cl- to C6-alkyl, preferably methyl or ethyl, or furthermore C6- to C12-arylene, which can optionally be fused with further aromatic rings containing hetero atoms.
Preferably, X represents a single bond, C, to CS-alkylene, C2 to C5-alkylidene, C5 to C6-cycloalkylidene, -0-, -SO-, -CO-, -S-, -SO2- or a radical of the formula (1 b) (X )m (]b) wherein Rs and R6 can be chosen individually for each Xl and independently of one another denote hydrogen or C, to C6-alkyl, preferably hydrogen, methyl or ethyl, and BMS 06 1 120- WO-nat Xi denotes carbon and m denotes an integer from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom X1, R5 and R6 are simultaneously alkyl.
Examples which are mentioned of the diphenols of the formula (2) which can be employed in addition to the bisphenois of the formula (1) according to the invention are hydroquinone, resorcinol, dihydroxybiphenyls, 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 compounds thereof alkylated on the nucleus and halogenated on the nucleus, and also a,co-bis-(hydroxyphenyl)-polysiloxanes.
Preferred diphenols of the formula (2) are, for example, 4,4'-dihydroxybiphenyl (DOD), 4,4'-dihydroxybiphenyl ether (DOD ether), 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A), 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC), 1, 1 -bis-(4-hydroxyphenyl)-cyclohexane, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-I -phenylethane, 1,1-bis[2-(4-hydroxyphenyl)-2-propyI]-benzene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]-benzene (bisphenol M), 2,2-bis-(3-methyl-4-hydroxyphenyl)-propane, 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-methane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxy-phenyl) sulfone, 2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane and 2,2-bis-(3,5-dibromo-4-hydroxy-phenyl)-propane.
Particularly preferred bisphenols are, for example, 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A), 4,4'-dihydroxybiphenyl (DOD), 4,4'-dihydroxybiphenyl ether (DOD ether), 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]-benzene (bisphenol M), BMS 06 1 120- WO-nat 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, 1,1-bis-(4-hydroxyphenyl)-1-phenylethane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC).
2,2-Bis-(4-hydroxyphenyl)-propane (bisphenol A), 4,4'-dihydroxybiphenyl (DOD), 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]-benzene (bisphenol M) and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC) are very particularly preferred.
The bisphenols of the formula (1) can be used either alone or in a mixture with one another or in a mixture with one or more bisphenols of the formula (2);
polycarbonates in the context of the present invention are to be understood as meaning both homopolycarbonates and copolycarbonates.
Copolycarbonates in general contain, in addition to a diphenol chosen from compounds of the formula (1), up to 95 mol%, preferably up to 80 mol%, particularly preferably up to 70 mol% of at least one further diphenol chosen from compounds of the formula (2) (based on the sum of the moles of diphenols employed). The copolycarbonates preferably contain as the lower limit at least 5 mol%, in particular 10 mol% (based on the sum of the moles of diphenols employed) chosen from compounds of the formula (2). Particularly preferred copolycarbonates contain 40-60, in particular 45-55 mol% of diphenol of the formula (1) and 60-40, in particular 45-55 mol% of diphenol of the formula (2) (based on the sum of the moles of diphenols employed).
The copolycarbonate can also be prepared, in particular, from a mixture of three bisphenols, one originating from the class of N-substituted isatin-bisphenols and the other two originating from the bisphenols described above. This is very particularly preferably the combination of the bisphenol structure (lb) with bisphenol A
and bisphenol TMC. In this context, compositions of 50 mol% of bisphenol A, 25 mol%
BMS 06 1 120- WO-nat of the bisphenol from the class of N-substituted isatin-bisphenols and 25 mol%
of TMC are very particularly preferred.
The polycarbonates and copolycarbonates according to the invention in general have average molecular weights (weight-average) of from 2,000 to 200,000, preferably 3,000 to 150,000, in particular 5,000 to 100,000, very particularly preferably 8,000 to 80,000, in particular 12,000 to 70,000 (determined by GPC with polycarbonate calibration).
The diphenols are known from the literature or can be prepared by processes known from the literature (see e.g. H. J. Buysch et al., Ullmann's Encyclopedia of Industrial Chemistry, VCH, New York 1991, 5th ed., vol. 19, p. 348).
The polycarbonates and copolycarbonates can also be branched. Certain small amounts, preferably amounts of between 0.05 and 5 mol%, particularly preferably 0.1 to 3 mol%, very particularly preferably 0.1 to 2 mol%, based on the moles of diphenois employed, of trifunctional compounds, such as e.g. isatin-biscresol (IBC) or phloroglucinol, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)-hep-2-ene; 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane; 1,3,5-tri-(4-hydroxyphenyl)-benzene;
1,1,1-tri-(4-hydroxyphenyl)-ethane (THPE); tri-(4-hydroxyphenyl)-phenylmethane;
2,2-bis-[4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propane; 2,4-bis-(4-hydroxyphenyl-isopropyl)-phenol; 2,6-bis-(2-hydroxy-5'-methyl-benzyl)-4-methylphenol; 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane; hexa-(4-(4-hydroxyphenyl-isopropyl)-phenyl)-orthoterephthalic acid ester; tetra-(4-hydroxyphenyl)-methane, tetra-(4-(4-hydroxyphenyl-isopropyl)-phenoxy)-methane; a.,a',a"-tris-(4-hydroxy-phenyl)-1,3,5-triisopropylbenzene; 2,4-dihydroxybenzoic acid; trimesic acid;
cyanuric chloride; 3,3-bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole;
1,4-bis-(4',4"-dihydroxytriphenyl)-methyl)-benzene and, in particular: 1,1,1-tri-(4-hydroxyphenyl) -ethane and bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydro-indole are employed as so-called branching agents for this purpose. Isatin-biscresol BMS 06 1 120- WO-nat and 1,1,1-tri-(4-hydroxyphenyl)-ethane and bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole are preferably employed as branched agents.
The use of these branching agents results in branched structures. The resulting long-chain branching leads to rheological properties of the polycarbonates obtained which manifest themselves in a structural viscosity compared with linear types.
The present invention furthermore relates to a process for the preparation of the polycarbonates and copolycarbonates according to the invention, characterized in that bisphenols and, where appropriate, branching agents are dissolved in aqueous alkaline solution and are reacted with a source of carbonate, such as phosgene, optionally dissolved in a solvent, in a two-phase mixture of an aqueous alkaline solution, an organic solvent and a catalyst, preferably an amine compound. The reaction procedure can also be in several stages. Such processes for the preparation of polycarbonate are known in principle as the two-phase interface process e.g. from H. Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, vol. 9, Interscience Publishers, New York 1964 p. 33 et seq. and from Polymer Reviews, vol. 10, "Condensation Polymers by Interfacial and Solution Methods", Paul W.
Morgan, Interscience Publishers, New York 1965, chap. VIII, p. 325, and the person skilled in the art is therefore familiar with the basic conditions.
In this context, the concentration of the bisphenols in the aqueous alkaline solution is 2 to 25 wt.%, preferably 2 to 20 wt.%, particularly preferably 2 to 18 wt.%
and very particularly preferably 3 to 15 wt.%. The aqueous alkaline solution comprises water, in which hydroxides of alkali or alkaline earth metals are dissolved.
Sodium hydroxide and potassium hydroxide are preferred.
If phosgene is used as the source of carbonate, the volume ratio of aqueous alkaline solution to organic solvent is 5:95 to 95:5, preferably 20:80 to 80:20, particularly preferably 30:70 to 70:30 and very particularly preferably 40:60 to 60:40. The molar ratio of bisphenol to phosgene is less than 1:10, preferably less than 1:6, BMS 06 1 120- WO-nat particularly preferably less than 1:4 and very particularly preferably less than 1:3.
The concentration of the branched polycarbonates and copolycarbonates according to the invention in the organic phase is 1.0 to 25 wt.%, preferably 2 to 20 wt.%, particularly preferably 2 to 18 wt.% and very particularly preferably 3 to 15 wt.%.
The concentration of the amine compound, based on the amount of bisphenol employed, is 0.1 to 10 mol%, preferably 0.2 to 8 mol%, particularly preferably 0.3 to 6 mol% and very particularly preferably 0.4 to 5 mol%.
Bisphenols are to be understood as meaning the abovementioned diphenols, with contents of the abovementioned branching agents. The source of carbonate is phosgene, diphosgene or triphosgene, preferably phosgene. In the case where phosgene is employed, a solvent can optionally be dispensed with and the phosgene can be passed directly into the reaction mixture.
Tertiary amines, such as triethylamine or N-alkylpiperidines, can be employed as the catalyst. Trialkylamines and 4-(dimethylamino)pyridine are suitable as catalysts.
Triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutylamine, N-methylpiperidine, N-ethylpiperidine and N-propylpiperidine are particularly suitable.
Halogenated hydrocarbons, such as methylene chloride and/or chlorobenzene, dichlorobenzene, trichlorobenzene or mixtures thereof, or aromatic hydrocarbons, such as e.g. toluene or xylenes, are possible as the organic solvent.
The reaction temperature can be -5 C to 100 C, preferably 0 C to 80 C, particularly preferably 10 C to 70 C and very particularly preferably 10 C
to 60 C.
Alternatively, the polycarbonates according to the invention can also be prepared by the melt transesterification process. The melt transesterification process is BMS 06 1 120- WO-nat described, for example, in the Encyclopedia of Polymer Science, vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, vol. 9, John Wiley and Sons, Inc. (1964) and DE-C 10 31 512.
In the melt transesterification process, the aromatic dihydroxy compounds already described for the phase interface process are transesterified in the melt with carbonic acid diesters with the aid of suitable catalysts and optionally further additives.
Carbonic acid diesters in the context of the invention are those of the formula (6) and (7) R' O
\^/ 0 0 ~ ~ (6) R - R"
R' R R (7) O-~-O b R R"
R' wherein R, R' and R" independently of one another can represent H, optionally branched Cl-C34-alkyl/cycloalkyl, C7-C34-alkaryl or C6-C34-aryl, for example diphenyl carbonate, butylphenyl phenyl carbonate, di-butylphenyl carbonate, isobutylphenyl phenyl carbonate, di-isobutylphenyl carbonate, tert-butylphenyl phenyl carbonate, di-tert-butylphenyl carbonate, n-pentylphenyl phenyl carbonate, di-(n-pentylphenyl) carbonate, BMS 06 1 120- WO-nat n-hexylphenyl phenyl carbonate, di-(n-hexylphenyl) carbonate, cyclohexylphenyl phenyl carbonate, dicyclohexylphenyl carbonate, phenylphenol phenyl carbonate, di-phenylphenol carbonate, isooctylphenyl phenyl carbonate, di-isooctylphenyl carbonate, n-nonylphenyl phenyl carbonate, di-(n-nonylphenyl) carbonate, cumylphenyl phenyl carbonate, di-cumylphenyl carbonate, naphthylphenyl phenyl carbonate, di-naphthylphenyl carbonate, di-tert-butylphenyl phenyl carbonate, di-(di-tert-butylphenyl) carbonate, dicumylphenyl phenyl carbonate, di-(dicumylphenyl) carbonate, 4-phenoxyphenyl phenyl carbonate, di-(4-phenoxyphenyl) carbonate, 3-pentadecylphenyl phenyl carbonate, di-(3-pentadecylphenyl) carbonate, tritylphenyl phenyl carbonate, di-tritylphenyl carbonate, preferably diphenyl carbonate, tert-butylphenyl phenyl carbonate, di-tert-butylphenyl carbonate, phenylphenol phenyl carbonate, di-phenylphenol carbonate, cumylphenyl phenyl carbonate, di-cumylphenyl carbonate, particularly preferably diphenyl carbonate.
Mixtures of the carbonic acid diesters mentioned can also be employed.
The content of carbonic acid ester is 100 to 130 mol%, preferably 103 to 120 mol%, particularly preferably 103 to 109 mol%, based on the dihydroxy compound.
Catalysts in the context of the invention which are employed in the melt transesterification process are basic catalysts as described in the literature mentioned, such as, for example, alkali and alkaline earth metal hydroxides and oxides, and also ammonium or phosphonium salts, called onium salts in the BMS 06 1 120- WO-nat following. In this context, onium salts, particularly preferably phosphonium salts, are preferably employed. Phosphonium salts in the context of the invention are those of the formula (8) 1+
[R1R3J 8 wherein R1-4 can be the same or different Cl-Clo-alkyls, C6-Clo-aryls, C7-Clo-aralkyls or C5-C6-cycloalkyls, preferably methyl or C6-C]4-aryls, particularly preferably methyl or phenyl, and X- can be an anion, such as hydroxide, sulfate, hydrogen sulfate, bicarbonate, carbonate, a halide, preferably chloride, or an alcoholate of the formula OR, wherein R can be C6-C14-aryl or C7-C12-aralkyl, preferably phenyl.
Preferred catalysts are tetraphenylphosphonium chloride, tetraphenylphosphonium hydroxide, tetraphenylphosphonium phenolate, particularly preferably tetraphenylphosphonium phenolate.
The catalysts are preferably employed in amounts of from 10-8 to 10-3 mol, based on one mol of bisphenol, particularly preferably in amounts of from 10-' to 10-4 mol.
Further catalysts can be used, alone or optionally in addition to the onium salt, in order to increase the speed of the polymerization. These include salts of alkali metals and alkaline earth metals, such as hydroxides, alkoxides and aryloxides of BMS 06 1 120- WO-nat lithium, sodium and potassium, preferably hydroxide, alkoxide or aryloxide salts of sodium. Sodium hydroxide and sodium phenolate are most preferred. The amounts of the cocatalyst can be in the range of from I to 200 ppb, preferably 5 to 150 ppb and most preferably 10 to 125 ppb, in each case calculated as sodium.
The transesterification reaction of the aromatic dihydroxy compound and the carbonic acid diester in the melt is preferably carried out in two stages. In the first stage, melting of the aromatic dihydroxy compound and the carbonic acid diester takes place at temperatures of from 80 to 250 C, preferably 100 to 230 C, particularly preferably 120 to 190 C, under normal pressure in the course of 0 to 5 hours, preferably 0.25 to 3 hours. After addition of the catalyst, the oligocarbonate is prepared from the aromatic dihydroxy compound and the carbonic acid diester by distilling off the monophenol by applying a vacuum (down to 2 mm Hg) and increasing the temperature (up to 260 C). The main amount of vapours from the process are obtained here. The oligocarbonate prepared in this way has a weight-average molar mass MW (determined by measurement of the rel. solution viscosity in methylene chloride or in mixtures of equal amounts by weight of phenol/o-dichlorobenzene calibrated by light scattering) in the range of from 2,000 g/mol to 18,000 g/mol, preferably from 4,000 g/mol to 15,000 g/mol.
In the second stage, the polycarbonate is prepared in the polycondensation by further increasing the temperature to 250 to 320 C, preferably 270 to 295 C, under a pressure of <2 mm Hg. The remainder of vapours are removed from the process here.
The catalysts can also be employed in combination (two or more) with one another.
If alkali/alkaline earth metal catalysts are employed, it may be advantageous to add the alkali/alkaline earth metal catalysts at a later point in time (e.g. after the oligocarbonate synthesis, during the polycondensation in the second stage).
BMS 06 1 120- WO-nat In the context of the process according to the invention, the reaction of the aromatic dihydroxy compound and the carbonic acid diester to give the polycarbonate can be carried out discontinuously or preferably continuously, for example in stirred tanks, thin film evaporators, falling film evaporators, stirred tank cascades, extruders, kneaders, simple disc reactors and high-viscosity disc reactors.
Analogously to the phase interface process, branched poly- or copolycarbonates can be prepared by using polyfunctional compounds.
Embodiments which utilize the parameters, compounds, definitions and explanations mentioned under preferred, particularly preferred or very particularly preferred or preferably etc. are preferred, particularly preferred or very particularly preferred.
However, the definitions, parameters, compounds and explanations mentioned generally or mentioned in preferred ranges in the description can also be combined with one another as desired, that is to say between the particular ranges and preferred ranges.
The polycarbonates and copolycarbonates according to the invention can be worked up and processed to any desired shaped articles in a known manner, for example by extrusion, injection moulding or extrusion blow moulding.
Other aromatic polycarbonates and/or other aromatic polyester carbonates and/or other aromatic polyesters can also be admixed to the polycarbonates and copolycarbonates according to the invention in a known manner, for example by compounding.
The conventional additives for these thermoplastics, such as fillers, UV
stabilizers, heat stabilizers, antistatics and pigments, can also be added in the conventional amounts to the polycarbonates and copolycarbonates according to the invention;
the mould release properties, the flow properties and/or the flame resistance can BMS 06 1 120- WO-nat optionally also be improved by addition of external mould release agents, flow agents and/or flameproofing agents (e.g. alkyl and aryl phosphites and phosphates, alkyl- and arylphosphanes and low molecular weight carboxylic acid alkyl and aryl esters, halogen compounds, salts, chalk, quartz flour, glass fibres and carbon fibres, pigments and a combination thereof. Such compounds are described e.g. in WO
99/55772, p. 15 - 25, and in the corresponding chapters of the "Plastics Additives Handbook", ed. Hans Zweifel, 5th edition 2000, Hanser Publishers, Munich).
The polycarbonates and copolycarbonates according to the invention, optionally in a mixture with other thermoplastics, such as, for example, graft polymers based on acrylonitrile/butadiene/styrene or graft copolymers based on acrylate rubber (see, for example, the graft polymers described in EP-A 640 655) and/or conventional additives, when processed to any desired shaped articles/extrudates, can be employed in all instances where polycarbonates, polyester carbonates and polyesters which are already known are employed. Further possible uses of the polycarbonates according to the invention are:
1. Safety panes, which as is known are required in many areas of buildings, vehicles and aircraft, and also as visors of helmets.
2. Production of films, in particular films for skis.
3. Production of blow-moulded articles (see also US Patent 2 964 794), for example I to 5 gallon water bottles.
4. Production of transparent sheets, in particular hollow chamber sheets, for example for covering buildings such as railway stations, greenhouses and lighting installations.
5. Production of optical data storage media.
BMS 06 1 120- WO-nat 6. For production of traffic light housings or traffic signs.
7. For production of foams (see, for example, DE-B 1 031 507).
8. For production of threads and wires (see, for example, DE-B 1 137 167 and DE-A 1 785 137).
9. As translucent plastics with a content of glass fibres for lighting purposes (see, for example, DE-A 1 554 020).
10. As translucent plastics with a content of barium sulfate, titanium dioxide and/or zirconium oxide or organic polymeric acrylate rubbers (EP-A 0 634 445, EP-A 269324) for the production of transparent and light-scattering mouldings.
11. For the production of precision injection mouldings, such as, for example, lens holders. Polycarbonates with a content of glass fibres which optionally additionally contain about 1 to 10 wt.% of MoSZ, based on the total weight, are used for this purpose.
12. For the production of optical equipment components, in particular lenses for photographic and film cameras (see, for example, DE-A 2 701 173).
13. As light transmission carriers, in particular as light conductor cables (EP-A 0 089 801).
14. As electrical insulating materials for electrical conductors and for plug housings and plug connectors.
15. Production of mobile telephone housings with improved resistance to perfume, shaving lotion and skin perspiration.
BMS 06 1 120- WO-nat 16. Network interface devices.
17. As a carrier material for organic photoconductors.
18. For the production of lamps, e.g. searchlights, as so-called headlamps, light-diffusing panes or internal lenses, as well as long-distance lamps.
19. For medical uses, such as e.g. oxygenators, dialyzers.
20. For foodstuffs uses, such as e.g. bottles, utensils and chocolate moulds.
21. For uses in the automobile field where contact with fuels and lubricants may occur, such as, for example, bumpers, optionally in the form of suitable blends with ABS or suitable rubbers.
22. For sports articles, such as e.g. slalom poles or ski boot buckles.
23. For household articles, such as e.g. kitchen sinks and letterbox housings.
Aromatic polycarbonates belong to the group of industrial thermoplastics. They are distinguished by combination of the technologically important properties of transparency, heat distortion resistance and toughness.
To obtain high molecular weight polycarbonates by the phase interface process, the alkali metal salts of bisphenols are reacted with phosgene in the two-phase mixture.
The molecular weight can be controlled by the amount of monophenols, such as e.g.
phenol or tert-butylphenol. Practically exclusively linear polymers are formed in these reactions. This can be demonstrated by end group analysis. By targeted use of so-called branching agents, as a rule polyhydroxylated compounds, branched polycarbonates are also obtained in this context.
For the preparation of polycarbonates by the phase interface process, reference may be made by way of example to H. Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, vol. 9, lnterscience Publishers, New York p. 33 et seq. and to Polymer Reviews, vol. 10, "Condensation Polymers by Interfacial and Solution Methods", Paul W. Morgan, Interscience Publishers, New York 1965, chap. VIII, p. 325.
For the preparation of polycarbonates by the melt transesterification process, the bisphenols are reacted in the melt with diaryl carbonates, usually diphenyl BMS 06 1 120- WO-nat carbonate, in the presence of catalysts, such as alkali metal salts or ammonium or phosphonium compounds.
The melt transesterification process is described, for example, in the Encyclopedia of Polymer Science, vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, vol. 9, John Wiley and Sons, Inc. (1964) and DE-C
31 512.
Polycarbonates based on 2-hydrocarbyl-3,3-bis(4-hydroxyaryl)phthalimidines as 10 monomers, which can be prepared by synthesis from phenolphthalein and an aniline hydrochloride derivative in aniline, are known from EP-A 1 582 549. This preparation is very involved and does not proceed satisfactorily. This bisphenol class thus has the industrial disadvantage of being accessible in only a very cumbersome manner.
However, due to their lack of adhesion to metals, the polycarbonates and copolycarbonates already described in the prior art have the disadvantage that they may have only a limited suitability or a suitability which is not optimum for use as a metallized component in e.g. high temperature uses.
There was therefore the object of providing polycarbonates or copolycarbonates and processes for the preparation thereof which avoid these disadvantages. This object is achieved, surprisingly, by the use of the class according to the invention of bisphenols of the general formulae (1 a) and (1 b) (isomer mixture) (also called bisphenols of the formula (1) in the following) BMS 06 1 120- WO-nat O
R? 0 N
R \ I \ R' ` I \
OH OH
HO HO
(1 a) (1 b) in which R' independently of one another represents hydrogen or CI -C1o alkyl, preferably hydrogen or CI-C6 alkyl, particularly preferably hydrogen or CI-C4 alkyl, very particularly preferably hydrogen or methyl, R 2 represents Cl-Clo alkyl, preferably CI-C6 alkyl, particularly preferably alkyl, or in each case optionally substituted phenyl or benzyl, in particular methyl, phenyl or benzyl, wherein the radicals mentioned for R' are preferred as substituents for phenyl and benzyl.
Alkyl in the context of the present invention is in each case linear or branched.
Particularly preferably, R2 represents phenyl which is optionally substituted by the radicals mentioned in R~, represented by the formula (lc) and (]d) (isomer mixture) BMS 06 1 120- WO-nat ~
?&~
R - ~ ~ N O
RROH R OH
HO HO
(1c) (1d) wherein R' has the abovementioned meaning.
The bisphenol of the formula (le) and (lf) (isomer mixture) ~ N O b%N
OH OH
HO HO
(1e) (1f) is very particularly preferred.
These bisphenols of the formula (I) according to the invention can be prepared from phenol derivatives and N-substituted isatin derivatives in an acid-catalyzed reaction.
This can be carried out by means of reactions analogous to that which is described for the preparation of unsubstituted isatin-bisphenols (H. N. Song et al., Synthetic BMS 06 l 120- WO-nat Communications 1999, 29 (19), 3303 and R. Berendes, H. Klos, Patent Specification No. 488760, Patent Office of the German Reich 1930).
The synthesis of the bisphenols according to the invention is preferably carried out as a condensation reaction of corresponding phenols and isatin derivatives, as the following example shows:
HO
HCI
N
~ a 1(e) 3,3-bis(4-hydroxyphenyl)-] -phenyl-] H-indol-2-one OH
0y , / N I \
/ \\ OH
- 1(f) 2,2-bis(4-hydroxyphenyl)-l -phenyl-] H-indol-3-one, an isomer mixture being obtained.
Very particularly preferably, the condensation is carried out with hydrochloric acid as the acid catalyst at temperatures of between 0 and 60 C with a stoichiometric ratio of phenol derivative to ketone derivative of 10 to 1, a mercaptan or thiocarboxylic acid compound (e.g. dodecylmercaptan, mercaptopropionic acid or thioacetic acid) preferably being present as a sulfur-containing compound, preferably only in an amount of about 0.01 to 25 %, based on the ketone compound.
The hydrochloric acid is very particularly preferably passed in as HCI gas.
BMS 06 1 120- WO-nat The condensation can be carried out in substance or in solution. In this context, inert solvents, such as, for example, chlorinated hydrocarbons, such as methylene chloride or dichloroethane, or toluene, xylenes or chlorobenzenes, are employed.
The reaction is particularly preferably carried out in substance with an excess of phenol.
A further synthesis possibility for the preparation of N-phenylisatin is the use of commercially obtainable isatin (e.g. BASF AG) in the form of an N-arylation reaction. The following organometallic syntheses known from the literature are available in this context.
a O
N
H
isatin Cul or Pd cat or Cu0 Hal Ullmann reaction NHMe DMF
ligand c I Hal = CI, Br, I
reflux NHMe Lit.: 55 % yield llo C Lit.: > 90 % yield 0 HO,B-OH N \ I \ ~
c'o I / ~~ I \
0 N-phenylisatin Cu(oAc)2 O
Suzuki coupling CH2CI2 o Cu(OAc)2 or Cu(OAc)2 systems Et3N or pyridine ~
v N
H Et3N or pyridine RT
RT Lit.: 70 - 87 % yield H
Lit.: 53 - 72 % yield BMS 06 1 120- WO-nat A further synthesis possibility for the preparation of N-phenylisatin is the use of the isonitrosoacetanilide isatin process (formerly for the preparation of indigo, Traugott Sandmeyer, Geigy Basel 1919). The following reaction steps are carried out in this:
OH
~ I
i ~
OH N
/ NH + CI OH - --Y I / ~
c N 0 cl (chloral hydrate) /
(H2NOH)2 HZSO, \ I
diphenylamine oximidoacetanilide (isonitrosoacetanilide) Hz0 0 HzSO, conc.
I\ O H20 0 / N (NH4)ZSO4 ~
a N-phenylisatin N-phenylisatin-R-imide A further synthesis possibility for the preparation of N-phenylisatin is via the reaction stage of a nitrone. The following reaction steps are carried out in this:
BMS 06 1 120- WO-nat o II
~NH + ~Cl NjilCI
CI
~ ~, ~ ~
N
O O
\N N
N N II N\ I
CI
DMF 0:11 HCI
CHO O
N HCI ~ O
O HO
+ N N C~% N
H \ RT
- H2N &N' b The phenols employed are known or can be prepared by processes known from the literature, for example by Friedel Crafts alkylation (Organikum, Organish-chemisches Grundpraktikum, corrected reprint of the 20th edition, Wiley-VCH, Weinheim, p. 355, 1999). Very many phenols are also commercially obtainable (suppliers e.g. Aldrich, Fluka, Acros etc.).
The isatin derivatives used are likewise known or can be prepared by processes known from the literature, for example by alkylation of the corresponding isatin parent substance. For example, they are accessible from the corresponding sodium or potassium salts of the isatin parent substance by reaction with alkyl halides in absolute alcohol (G. Heller, O. Notzel, Ber. Dtsch. Chem. Ges. 1907, 40, 1294). An alternative synthesis possibility is offered by alkylation via 0-alkylated isourea derivatives (E. Vowinkel, Chem. Ber. 1966, 99, 1479, or L. J. Mathia, Synthesis 1979, 561). These can be obtained by reaction of N,N'-dicyclohexylcarbodiimide with an alcohol in the presence of copper(l) chloride (E. Schmidt, F.
Moosmuller, BMS 06 1 120- WO-nat Liebigs Ann. Chem. 1955, 597, 235). Some N-substituted isatins are also commercially obtainable (suppliers e.g. ChemPur GmbH, Karlsruhe, Germany or Alfa Aesar, Karlsruhe, German or Sigma-Aldrich or Lancaster Synthesis Ltd.
Newgate, United Kingdom).
The present invention likewise provides polycarbonates or copolycarbonates which are prepared using the bisphenols according to the invention, and the corresponding preparation processes.
The (co)polycarbonates according to the invention are based on bisphenols of the general formulae (la,) and (lbi) (isomer mixture) as a recurring monomer unit N
O
R
` I \
R' O--O (la,) O
R? N
R
R' O-O (1bi) wherein R' and R2 have the abovementioned meaning.
Preferred bisphenols are likewise those mentioned above.
BMS 06 1 120- WO-nat In the case of (co)polycarbonates, in addition to one or more bisphenols of the formula (1), these can contain as a further monomer unit bisphenols of the formula (2) O X O -R4 R4 (2) in which R3 and R4 independently of one another represent H, CI-C18-alkyl, Cl-Clg-alkoxy, halogen, such as Cl or Br, or in each case optionally substituted aryl or aralkyl, preferably H or CI-C12-alkyl, particularly preferably H or Ci-C8-alkyl and very particularly preferably H or methyl, and X represents a single bond, -SO2-. -CO-, -0-, -S-, C1- to C6-alkylene, C2- to alkylidene or C5- to C6-cycloalkylidene, which can be substituted by Cl- to C6-alkyl, preferably methyl or ethyl, or furthermore C6- to C12-arylene, which can optionally be fused with further aromatic rings containing hetero atoms.
Preferably, X represents a single bond, C, to CS-alkylene, C2 to C5-alkylidene, C5 to C6-cycloalkylidene, -0-, -SO-, -CO-, -S-, -SO2- or a radical of the formula (1 b) (X )m (]b) wherein Rs and R6 can be chosen individually for each Xl and independently of one another denote hydrogen or C, to C6-alkyl, preferably hydrogen, methyl or ethyl, and BMS 06 1 120- WO-nat Xi denotes carbon and m denotes an integer from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom X1, R5 and R6 are simultaneously alkyl.
Examples which are mentioned of the diphenols of the formula (2) which can be employed in addition to the bisphenois of the formula (1) according to the invention are hydroquinone, resorcinol, dihydroxybiphenyls, 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 compounds thereof alkylated on the nucleus and halogenated on the nucleus, and also a,co-bis-(hydroxyphenyl)-polysiloxanes.
Preferred diphenols of the formula (2) are, for example, 4,4'-dihydroxybiphenyl (DOD), 4,4'-dihydroxybiphenyl ether (DOD ether), 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A), 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC), 1, 1 -bis-(4-hydroxyphenyl)-cyclohexane, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-I -phenylethane, 1,1-bis[2-(4-hydroxyphenyl)-2-propyI]-benzene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]-benzene (bisphenol M), 2,2-bis-(3-methyl-4-hydroxyphenyl)-propane, 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-methane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxy-phenyl) sulfone, 2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane and 2,2-bis-(3,5-dibromo-4-hydroxy-phenyl)-propane.
Particularly preferred bisphenols are, for example, 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A), 4,4'-dihydroxybiphenyl (DOD), 4,4'-dihydroxybiphenyl ether (DOD ether), 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]-benzene (bisphenol M), BMS 06 1 120- WO-nat 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, 1,1-bis-(4-hydroxyphenyl)-1-phenylethane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC).
2,2-Bis-(4-hydroxyphenyl)-propane (bisphenol A), 4,4'-dihydroxybiphenyl (DOD), 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]-benzene (bisphenol M) and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC) are very particularly preferred.
The bisphenols of the formula (1) can be used either alone or in a mixture with one another or in a mixture with one or more bisphenols of the formula (2);
polycarbonates in the context of the present invention are to be understood as meaning both homopolycarbonates and copolycarbonates.
Copolycarbonates in general contain, in addition to a diphenol chosen from compounds of the formula (1), up to 95 mol%, preferably up to 80 mol%, particularly preferably up to 70 mol% of at least one further diphenol chosen from compounds of the formula (2) (based on the sum of the moles of diphenols employed). The copolycarbonates preferably contain as the lower limit at least 5 mol%, in particular 10 mol% (based on the sum of the moles of diphenols employed) chosen from compounds of the formula (2). Particularly preferred copolycarbonates contain 40-60, in particular 45-55 mol% of diphenol of the formula (1) and 60-40, in particular 45-55 mol% of diphenol of the formula (2) (based on the sum of the moles of diphenols employed).
The copolycarbonate can also be prepared, in particular, from a mixture of three bisphenols, one originating from the class of N-substituted isatin-bisphenols and the other two originating from the bisphenols described above. This is very particularly preferably the combination of the bisphenol structure (lb) with bisphenol A
and bisphenol TMC. In this context, compositions of 50 mol% of bisphenol A, 25 mol%
BMS 06 1 120- WO-nat of the bisphenol from the class of N-substituted isatin-bisphenols and 25 mol%
of TMC are very particularly preferred.
The polycarbonates and copolycarbonates according to the invention in general have average molecular weights (weight-average) of from 2,000 to 200,000, preferably 3,000 to 150,000, in particular 5,000 to 100,000, very particularly preferably 8,000 to 80,000, in particular 12,000 to 70,000 (determined by GPC with polycarbonate calibration).
The diphenols are known from the literature or can be prepared by processes known from the literature (see e.g. H. J. Buysch et al., Ullmann's Encyclopedia of Industrial Chemistry, VCH, New York 1991, 5th ed., vol. 19, p. 348).
The polycarbonates and copolycarbonates can also be branched. Certain small amounts, preferably amounts of between 0.05 and 5 mol%, particularly preferably 0.1 to 3 mol%, very particularly preferably 0.1 to 2 mol%, based on the moles of diphenois employed, of trifunctional compounds, such as e.g. isatin-biscresol (IBC) or phloroglucinol, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)-hep-2-ene; 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane; 1,3,5-tri-(4-hydroxyphenyl)-benzene;
1,1,1-tri-(4-hydroxyphenyl)-ethane (THPE); tri-(4-hydroxyphenyl)-phenylmethane;
2,2-bis-[4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propane; 2,4-bis-(4-hydroxyphenyl-isopropyl)-phenol; 2,6-bis-(2-hydroxy-5'-methyl-benzyl)-4-methylphenol; 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane; hexa-(4-(4-hydroxyphenyl-isopropyl)-phenyl)-orthoterephthalic acid ester; tetra-(4-hydroxyphenyl)-methane, tetra-(4-(4-hydroxyphenyl-isopropyl)-phenoxy)-methane; a.,a',a"-tris-(4-hydroxy-phenyl)-1,3,5-triisopropylbenzene; 2,4-dihydroxybenzoic acid; trimesic acid;
cyanuric chloride; 3,3-bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole;
1,4-bis-(4',4"-dihydroxytriphenyl)-methyl)-benzene and, in particular: 1,1,1-tri-(4-hydroxyphenyl) -ethane and bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydro-indole are employed as so-called branching agents for this purpose. Isatin-biscresol BMS 06 1 120- WO-nat and 1,1,1-tri-(4-hydroxyphenyl)-ethane and bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole are preferably employed as branched agents.
The use of these branching agents results in branched structures. The resulting long-chain branching leads to rheological properties of the polycarbonates obtained which manifest themselves in a structural viscosity compared with linear types.
The present invention furthermore relates to a process for the preparation of the polycarbonates and copolycarbonates according to the invention, characterized in that bisphenols and, where appropriate, branching agents are dissolved in aqueous alkaline solution and are reacted with a source of carbonate, such as phosgene, optionally dissolved in a solvent, in a two-phase mixture of an aqueous alkaline solution, an organic solvent and a catalyst, preferably an amine compound. The reaction procedure can also be in several stages. Such processes for the preparation of polycarbonate are known in principle as the two-phase interface process e.g. from H. Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, vol. 9, Interscience Publishers, New York 1964 p. 33 et seq. and from Polymer Reviews, vol. 10, "Condensation Polymers by Interfacial and Solution Methods", Paul W.
Morgan, Interscience Publishers, New York 1965, chap. VIII, p. 325, and the person skilled in the art is therefore familiar with the basic conditions.
In this context, the concentration of the bisphenols in the aqueous alkaline solution is 2 to 25 wt.%, preferably 2 to 20 wt.%, particularly preferably 2 to 18 wt.%
and very particularly preferably 3 to 15 wt.%. The aqueous alkaline solution comprises water, in which hydroxides of alkali or alkaline earth metals are dissolved.
Sodium hydroxide and potassium hydroxide are preferred.
If phosgene is used as the source of carbonate, the volume ratio of aqueous alkaline solution to organic solvent is 5:95 to 95:5, preferably 20:80 to 80:20, particularly preferably 30:70 to 70:30 and very particularly preferably 40:60 to 60:40. The molar ratio of bisphenol to phosgene is less than 1:10, preferably less than 1:6, BMS 06 1 120- WO-nat particularly preferably less than 1:4 and very particularly preferably less than 1:3.
The concentration of the branched polycarbonates and copolycarbonates according to the invention in the organic phase is 1.0 to 25 wt.%, preferably 2 to 20 wt.%, particularly preferably 2 to 18 wt.% and very particularly preferably 3 to 15 wt.%.
The concentration of the amine compound, based on the amount of bisphenol employed, is 0.1 to 10 mol%, preferably 0.2 to 8 mol%, particularly preferably 0.3 to 6 mol% and very particularly preferably 0.4 to 5 mol%.
Bisphenols are to be understood as meaning the abovementioned diphenols, with contents of the abovementioned branching agents. The source of carbonate is phosgene, diphosgene or triphosgene, preferably phosgene. In the case where phosgene is employed, a solvent can optionally be dispensed with and the phosgene can be passed directly into the reaction mixture.
Tertiary amines, such as triethylamine or N-alkylpiperidines, can be employed as the catalyst. Trialkylamines and 4-(dimethylamino)pyridine are suitable as catalysts.
Triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutylamine, N-methylpiperidine, N-ethylpiperidine and N-propylpiperidine are particularly suitable.
Halogenated hydrocarbons, such as methylene chloride and/or chlorobenzene, dichlorobenzene, trichlorobenzene or mixtures thereof, or aromatic hydrocarbons, such as e.g. toluene or xylenes, are possible as the organic solvent.
The reaction temperature can be -5 C to 100 C, preferably 0 C to 80 C, particularly preferably 10 C to 70 C and very particularly preferably 10 C
to 60 C.
Alternatively, the polycarbonates according to the invention can also be prepared by the melt transesterification process. The melt transesterification process is BMS 06 1 120- WO-nat described, for example, in the Encyclopedia of Polymer Science, vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, vol. 9, John Wiley and Sons, Inc. (1964) and DE-C 10 31 512.
In the melt transesterification process, the aromatic dihydroxy compounds already described for the phase interface process are transesterified in the melt with carbonic acid diesters with the aid of suitable catalysts and optionally further additives.
Carbonic acid diesters in the context of the invention are those of the formula (6) and (7) R' O
\^/ 0 0 ~ ~ (6) R - R"
R' R R (7) O-~-O b R R"
R' wherein R, R' and R" independently of one another can represent H, optionally branched Cl-C34-alkyl/cycloalkyl, C7-C34-alkaryl or C6-C34-aryl, for example diphenyl carbonate, butylphenyl phenyl carbonate, di-butylphenyl carbonate, isobutylphenyl phenyl carbonate, di-isobutylphenyl carbonate, tert-butylphenyl phenyl carbonate, di-tert-butylphenyl carbonate, n-pentylphenyl phenyl carbonate, di-(n-pentylphenyl) carbonate, BMS 06 1 120- WO-nat n-hexylphenyl phenyl carbonate, di-(n-hexylphenyl) carbonate, cyclohexylphenyl phenyl carbonate, dicyclohexylphenyl carbonate, phenylphenol phenyl carbonate, di-phenylphenol carbonate, isooctylphenyl phenyl carbonate, di-isooctylphenyl carbonate, n-nonylphenyl phenyl carbonate, di-(n-nonylphenyl) carbonate, cumylphenyl phenyl carbonate, di-cumylphenyl carbonate, naphthylphenyl phenyl carbonate, di-naphthylphenyl carbonate, di-tert-butylphenyl phenyl carbonate, di-(di-tert-butylphenyl) carbonate, dicumylphenyl phenyl carbonate, di-(dicumylphenyl) carbonate, 4-phenoxyphenyl phenyl carbonate, di-(4-phenoxyphenyl) carbonate, 3-pentadecylphenyl phenyl carbonate, di-(3-pentadecylphenyl) carbonate, tritylphenyl phenyl carbonate, di-tritylphenyl carbonate, preferably diphenyl carbonate, tert-butylphenyl phenyl carbonate, di-tert-butylphenyl carbonate, phenylphenol phenyl carbonate, di-phenylphenol carbonate, cumylphenyl phenyl carbonate, di-cumylphenyl carbonate, particularly preferably diphenyl carbonate.
Mixtures of the carbonic acid diesters mentioned can also be employed.
The content of carbonic acid ester is 100 to 130 mol%, preferably 103 to 120 mol%, particularly preferably 103 to 109 mol%, based on the dihydroxy compound.
Catalysts in the context of the invention which are employed in the melt transesterification process are basic catalysts as described in the literature mentioned, such as, for example, alkali and alkaline earth metal hydroxides and oxides, and also ammonium or phosphonium salts, called onium salts in the BMS 06 1 120- WO-nat following. In this context, onium salts, particularly preferably phosphonium salts, are preferably employed. Phosphonium salts in the context of the invention are those of the formula (8) 1+
[R1R3J 8 wherein R1-4 can be the same or different Cl-Clo-alkyls, C6-Clo-aryls, C7-Clo-aralkyls or C5-C6-cycloalkyls, preferably methyl or C6-C]4-aryls, particularly preferably methyl or phenyl, and X- can be an anion, such as hydroxide, sulfate, hydrogen sulfate, bicarbonate, carbonate, a halide, preferably chloride, or an alcoholate of the formula OR, wherein R can be C6-C14-aryl or C7-C12-aralkyl, preferably phenyl.
Preferred catalysts are tetraphenylphosphonium chloride, tetraphenylphosphonium hydroxide, tetraphenylphosphonium phenolate, particularly preferably tetraphenylphosphonium phenolate.
The catalysts are preferably employed in amounts of from 10-8 to 10-3 mol, based on one mol of bisphenol, particularly preferably in amounts of from 10-' to 10-4 mol.
Further catalysts can be used, alone or optionally in addition to the onium salt, in order to increase the speed of the polymerization. These include salts of alkali metals and alkaline earth metals, such as hydroxides, alkoxides and aryloxides of BMS 06 1 120- WO-nat lithium, sodium and potassium, preferably hydroxide, alkoxide or aryloxide salts of sodium. Sodium hydroxide and sodium phenolate are most preferred. The amounts of the cocatalyst can be in the range of from I to 200 ppb, preferably 5 to 150 ppb and most preferably 10 to 125 ppb, in each case calculated as sodium.
The transesterification reaction of the aromatic dihydroxy compound and the carbonic acid diester in the melt is preferably carried out in two stages. In the first stage, melting of the aromatic dihydroxy compound and the carbonic acid diester takes place at temperatures of from 80 to 250 C, preferably 100 to 230 C, particularly preferably 120 to 190 C, under normal pressure in the course of 0 to 5 hours, preferably 0.25 to 3 hours. After addition of the catalyst, the oligocarbonate is prepared from the aromatic dihydroxy compound and the carbonic acid diester by distilling off the monophenol by applying a vacuum (down to 2 mm Hg) and increasing the temperature (up to 260 C). The main amount of vapours from the process are obtained here. The oligocarbonate prepared in this way has a weight-average molar mass MW (determined by measurement of the rel. solution viscosity in methylene chloride or in mixtures of equal amounts by weight of phenol/o-dichlorobenzene calibrated by light scattering) in the range of from 2,000 g/mol to 18,000 g/mol, preferably from 4,000 g/mol to 15,000 g/mol.
In the second stage, the polycarbonate is prepared in the polycondensation by further increasing the temperature to 250 to 320 C, preferably 270 to 295 C, under a pressure of <2 mm Hg. The remainder of vapours are removed from the process here.
The catalysts can also be employed in combination (two or more) with one another.
If alkali/alkaline earth metal catalysts are employed, it may be advantageous to add the alkali/alkaline earth metal catalysts at a later point in time (e.g. after the oligocarbonate synthesis, during the polycondensation in the second stage).
BMS 06 1 120- WO-nat In the context of the process according to the invention, the reaction of the aromatic dihydroxy compound and the carbonic acid diester to give the polycarbonate can be carried out discontinuously or preferably continuously, for example in stirred tanks, thin film evaporators, falling film evaporators, stirred tank cascades, extruders, kneaders, simple disc reactors and high-viscosity disc reactors.
Analogously to the phase interface process, branched poly- or copolycarbonates can be prepared by using polyfunctional compounds.
Embodiments which utilize the parameters, compounds, definitions and explanations mentioned under preferred, particularly preferred or very particularly preferred or preferably etc. are preferred, particularly preferred or very particularly preferred.
However, the definitions, parameters, compounds and explanations mentioned generally or mentioned in preferred ranges in the description can also be combined with one another as desired, that is to say between the particular ranges and preferred ranges.
The polycarbonates and copolycarbonates according to the invention can be worked up and processed to any desired shaped articles in a known manner, for example by extrusion, injection moulding or extrusion blow moulding.
Other aromatic polycarbonates and/or other aromatic polyester carbonates and/or other aromatic polyesters can also be admixed to the polycarbonates and copolycarbonates according to the invention in a known manner, for example by compounding.
The conventional additives for these thermoplastics, such as fillers, UV
stabilizers, heat stabilizers, antistatics and pigments, can also be added in the conventional amounts to the polycarbonates and copolycarbonates according to the invention;
the mould release properties, the flow properties and/or the flame resistance can BMS 06 1 120- WO-nat optionally also be improved by addition of external mould release agents, flow agents and/or flameproofing agents (e.g. alkyl and aryl phosphites and phosphates, alkyl- and arylphosphanes and low molecular weight carboxylic acid alkyl and aryl esters, halogen compounds, salts, chalk, quartz flour, glass fibres and carbon fibres, pigments and a combination thereof. Such compounds are described e.g. in WO
99/55772, p. 15 - 25, and in the corresponding chapters of the "Plastics Additives Handbook", ed. Hans Zweifel, 5th edition 2000, Hanser Publishers, Munich).
The polycarbonates and copolycarbonates according to the invention, optionally in a mixture with other thermoplastics, such as, for example, graft polymers based on acrylonitrile/butadiene/styrene or graft copolymers based on acrylate rubber (see, for example, the graft polymers described in EP-A 640 655) and/or conventional additives, when processed to any desired shaped articles/extrudates, can be employed in all instances where polycarbonates, polyester carbonates and polyesters which are already known are employed. Further possible uses of the polycarbonates according to the invention are:
1. Safety panes, which as is known are required in many areas of buildings, vehicles and aircraft, and also as visors of helmets.
2. Production of films, in particular films for skis.
3. Production of blow-moulded articles (see also US Patent 2 964 794), for example I to 5 gallon water bottles.
4. Production of transparent sheets, in particular hollow chamber sheets, for example for covering buildings such as railway stations, greenhouses and lighting installations.
5. Production of optical data storage media.
BMS 06 1 120- WO-nat 6. For production of traffic light housings or traffic signs.
7. For production of foams (see, for example, DE-B 1 031 507).
8. For production of threads and wires (see, for example, DE-B 1 137 167 and DE-A 1 785 137).
9. As translucent plastics with a content of glass fibres for lighting purposes (see, for example, DE-A 1 554 020).
10. As translucent plastics with a content of barium sulfate, titanium dioxide and/or zirconium oxide or organic polymeric acrylate rubbers (EP-A 0 634 445, EP-A 269324) for the production of transparent and light-scattering mouldings.
11. For the production of precision injection mouldings, such as, for example, lens holders. Polycarbonates with a content of glass fibres which optionally additionally contain about 1 to 10 wt.% of MoSZ, based on the total weight, are used for this purpose.
12. For the production of optical equipment components, in particular lenses for photographic and film cameras (see, for example, DE-A 2 701 173).
13. As light transmission carriers, in particular as light conductor cables (EP-A 0 089 801).
14. As electrical insulating materials for electrical conductors and for plug housings and plug connectors.
15. Production of mobile telephone housings with improved resistance to perfume, shaving lotion and skin perspiration.
BMS 06 1 120- WO-nat 16. Network interface devices.
17. As a carrier material for organic photoconductors.
18. For the production of lamps, e.g. searchlights, as so-called headlamps, light-diffusing panes or internal lenses, as well as long-distance lamps.
19. For medical uses, such as e.g. oxygenators, dialyzers.
20. For foodstuffs uses, such as e.g. bottles, utensils and chocolate moulds.
21. For uses in the automobile field where contact with fuels and lubricants may occur, such as, for example, bumpers, optionally in the form of suitable blends with ABS or suitable rubbers.
22. For sports articles, such as e.g. slalom poles or ski boot buckles.
23. For household articles, such as e.g. kitchen sinks and letterbox housings.
24. For housings, such as e.g. electrical distribution boxes 25. Housings for electric toothbrushes and hairdryer housings.
26. Transparent washing machine portholes with improved resistance to the wash solution.
27. Safety glasses, visors or optical corrective glasses.
28. Lamp covers for kitchen equipment with improved resistance to kitchen fumes, in particular oil vapours.
BMS 06 1 120- WO-nat 29. Packaging films for medicaments.
BMS 06 1 120- WO-nat 29. Packaging films for medicaments.
30. Chip boxes and chip supports.
31. For other uses, such as e.g. fattening stable doors or animal cages.
32. Safety helmets This Application likewise provides the shaped articles and mouldings and extrudates from the polymers according to the invention.
BMS 06 1 120- WO-nat Examples A) Preparation of bisphenol of the formula (1) Example 1:
Preparation of N-phenylisatin ONH + CI O A
x toluene N O
\
diphenylamine oxalyl chloride toluene AIC13 T = 114 C
- HCI
O
N
o N-phenyfisatin 660 g (5.20 mol) oxalic acid dichloride, dissolved in 1,600 ml anhydrous toluene, are initially introduced into a previously heated apparatus at room temperature.
798 g (4.72 mol) diphenylamine, likewise dissolved in 1,200 mi anhydrous toluene, are pumped in by means of a Telab pump (setting: 10 strokes/minute at 30 %) in the course of 1.5 hours under intensive stirring. During this procedure, the reaction BMS 06 1 120- WO-nat batch is thermostatically controlled at 45 C. The maximum temperature reached due to the heat of reaction is 50 C.
Directly after the diphenylamine solution has been pumped in, the progress of the reaction is checked by means of gas chromatography (GC) at the intermediate stage before the cyclization (molecular weight 259.69 g/mol; conversion 98.4 area%;
determination of the retention time by prior GC-MS). To carry out the cyclization, g of dry aluminium chloride are added. The mixture is then heated up to the reflux temperature. The temperature is maintained for 3 hours, the HCI gas formed 10 being passed into an alkaline destruction reservoir.
After the end of the reaction, a reaction progress of greater than 90 area% of the desired end product N-phenylisatin (molecular weight 223.23 g/mol) is determined by means of GC.
Working up:
The reaction mixture is precipitated in water, the crude product is filtered off with suction and washed 3 times with distilled water, filtered off under high suction again and then dried at 70 C in a vacuum drying cabinet.
Yield:
977.1 g of an orange-coloured solid (92.7 % of theory) having a melting point of 138 C are obtained (GC purity of 98.7 %).
Analysis:
- GC-MS: molecular weight 223 g/mol BMS 06 1 120- WO-nat - 'H-NMR (400 MHz, TMS CDC13) 8=7.71-7.69 (d, IH), 7.58-7.52 (m, 3H), 7.47-7.41 (m, 3H), 7.19-7.15 (t, IH), 6.91-6.88 (d, 1 H).
Example 2 Bisphenol of the formula (1) Preparation of 3,3-bis(4-hydroxyphenyl)-1-phenyl-1 H-indol-2-one HO
O
~ HCI
Ir~O + OH
2 II , / cH
mercaptopropionic acid /-O
~
N-phenylisatin 1,400 g (6.27 mol) N-phenylisatin from Example 1, 3,541 g (37.6 mol) molten, freshly distilled phenol and 7 g (0.66 mol) 3-mercaptopropionic acid (cocatalyst) are initially introduced into the apparatus, which has been rendered inert, and are heated to 40 - 45 C.
Hydrogen chloride gas is now cautiously passed into this red-brown homogeneous solution for 25 minutes, with moderate stirring, during which the temperature rises to 67 C.
The dark brown batch is then cooled to room temperature and the beige suspension formed is filtered with suction.
BMS 06 1 120- WO-nat Analysis of the product formed:
1 st GC control:
4.0 area% phenol 14.2 area% of a product isomer 2,2-bis(4-hydroxyphenyl)-l -phenyl-1 H-indol-2-one 81.1 area% of the product 3,3-bis(4-hydroxyphenyl)-1-phenyl-lH-indol-2-one Washing the crude product 8 times with I litre of methylene chloride each time leads to the following product:
0.03 area% phenol 2.5 area% of the isomer 2,2-bis(4-hydroxyphenyl)-1-phenyl-l H-indol-3 -one 97.2 area% of the product 3,3-bis(4-hydroxyphenyl)-l -phenyl-l H-indol-2-one Yield after drying:
830 g of a slightly yellowish solid (33.6 % of theory).
Analysis:
- GC-MS: in each case molecular weight 537 g/mol after derivatization as a trimethylsilyl adduct -'H-NMR (400 MHz, TMS, DMSO) 5=9.47 (s, 2H), 7.60-7.57 (t, 2H), 7.50-7.45 (m, 3H), 7.30-7.35 (d, 1 H), 7.28-7.20 (t, 1 H), 7.15-7.10 (t, 1 H), 7.09-7.04 (d, 4H), 6.81-6.79 (d, 1 H), 6.77-6.71 (d, 4H).
BMS 06 1 120- WO-nat *) Isomer reaction:
The compound 2,2-bis(4-hydroxyphenyl)-1-phenyl-lH-indol-3-one is formed as a secondary component by condensation of N-phenylisatin with phenol.
HO
` ` /
mercaptopropionic 0 + 2 OH HCI OH
O~-N acid a_5~~
N (2a) N-phenylisatin b 3,3-bis(4-hydroxyphenyl)-1 phenyl-1 H-indol-2-one OH
0 ~ ~
C~5_ -N I ~
/
O
H (2b) b\-"
2,2-bis(4-hydroxyphenyl)-1-phenyl-1 H-indol-3-one Analysis The analytical determination of the structure of the product obtained (Example 2) after preparation of the sample (conversion into the trimethylsilyl derivative) was carried out by means of gas chromatography-mass spectrometry (GC-MS).
The compound (2a) as the trimethylsilyl derivative has a molecular weight of 537 g/mol. In the GC a further peak is found at a shorter retention time, which according to analysis by means of gas spectrometry likewise has, as the trimethylsilyl derivative, the molecular weight of 537 g/mol. This isomer has the structure according to Example (2b). Furthermore, it was possible to demonstrate by BMS 06 1 120- WO-nat different fragmentation in the mass spectrum that this structure is unambiguously the structure (2b) and not the structure of the bisphenol of the formula (2c).
O
N
` I \
OH
HO (2c) B) Preparation of polycarbonate Example 3 Preparation of a copolycarbonate (50/50 mol%) from bisphenol A (BPA) and the bisphenol according to the invention according to Example 2(3,3-bis(4-hydroxyphenyl)-1-phenyl-lH-indol-2-one (97.2 % according to GC), 2,2-bis(4-hydroxyphenyl)-1-phenyl-1 H-indol-3-one (2.5 % according to GC)).
In order to obtain sufficient amounts of bisphenol of the example for a continuous process, the batch of Example 2 was repeated several times.
A copolycarbonate was obtained by the phase interface process by means of a laboratory continuous unit. The following synthesis conditions and reaction parameters/meterings (in each case the amount per hour) were maintained:
= 15 % strength sodium bisphenolate solution containing a mixture of bisphenol A and the isomer mixture from Example 2(50/50 mol%) = 2.1 mol sodium hydroxide solution per mol bisphenol in the sodium bisphenolate solution BMS 06 1 120- WO-nat = 1.40 mol phosgene per mol bisphenol (or 1.382 mol phosgene per mol bisphenol + 0.5 mol chain terminator) = temperature 30 C during the phosgenation = p-tert-butylphenol (BUP) as the chain terminator = 3.6 mol% chain terminator per mol bisphenol = 1 mol% N-ethylpiperidine (EPP) per mol bisphenol as a catalyst (7.4 %
strength solution in the solvent mixture methylene chloride/chlorobenzene (50/50 wt.%) = 15.0 % strength polycarbonate solution in the solvent mixture methylene chloride/chlorobenzene (50/50) as the desired organic phase = weight of the copolycarbonate formed 156 g/h The following amounts per hour are reacted in this context:
943.3 g of a 15 % strength solution consisting of 52.0 g bisphenol A, 89.5 g bisphenol from Example 5, dissolved in an alkaline aqueous phase of 720 g water and 81.8 g concentrated sodium hydroxide solution (46.7 % strength), are combined together with 736.9 g of a solvent mixture consisting of methylene chloride/chlorobenzene (50/50) which contain 63.0 g phosgene. To regulate the molecular weight, after the phosgenation 2.461 g BUP in 140.6 g of the solvent mixture methylene chloride/chlorobenzene (50/50) are added. To maintain the alkaline pH of approx. 12 - 13, 66.0 g concentrated sodium hydroxide solution (46.7 % strength) are moreover metered in. At the rear end of the dwell zone of the apparatus, 0.515 g EPP, dissolved in 6.44 g of the solvent mixture methylene chloride/chlorobenzene (50/50), is added.
BMS 06 1 120- WO-nat Reaction eguation /'f .~..~r ~.'.`/' j'4```,, }_.. _v x y -'t Or OH Q
HC ~c OH
NaOH 1 water MC/MCB
phosgene NaOH / water o 0 /~ ~~=~a , 0 r o O~~
0"
y x=0.5 y = 0.5 Due to the isomer 2,2-bis(4-hydroxyphenyl)-1-phenyl-lH-indol-3-one formed during the preparation of Example 2, the corresponding content of the isomer is contained in y = 0.5.
After the organic copolycarbonate solution obtained has been washed, the solvent mixture is evaporated off in vacuo, a solid thereby being obtained, which is comminuted and homogenized.
BMS 06 1 120- WO-nat Analysis Relative solution viscosity in methylene chloride at 25 C (concentration 5 g/I):
1.168 Gel permeation chromatography (GPC, calibration by means of BPA polycarbonate, UV detector 254 nm):
Mn = 8,417 g/mol Mw = 18,666 g/mol D = 2.22 (polydispersity) Oligomer content in the range of 300 - 1,500 g/mol: 2.08 %
Glass transition temperature (DSC after 2nd heating up of 50 - 280 C, 20 C/min heating up rate): 210 C
Examples 4 - 8 In order to obtain sufficient amounts of polycarbonate in a laboratory continuous unit (limited capacity), the process according to Example 3 was carried out several times. The polycarbonates obtained therefrom are characterized as follows:
Example 4 Relative solution viscosity in methylene chloride at 25 C (concentration 5 g/1):
1.202 BMS 06 1 120- WO-nat Gel permeation chromatography (GPC, calibration by means of BPA polycarbonate, UV detector 254 nm):
Mn = 10,497 g/mol Mw = 22,972 g/mol D=2.19 Oligomer content in the range of 300 - 1,500 g/mol: 1.41 %
Glass transition temperature (DSC after 2nd heating up of 50 - 280 C, 20 C/min heating up rate): 210 C
Example 5 Relative solution viscosity in methylene chloride at 25 C (concentration 5 g/1):
1.215 Gel permeation chromatography (GPC, calibration by means of BPA polycarbonate, UV detector 254 nm):
Mn = 10,052 g/mol Mw = 24,666 g/mol D = 2.23 Oligomer content in the range of 300 - 1,500 g/mol: 1.41 %
= ' BMS 06 1 120- WO-nat Glass transition temperature (DSC after 2nd heating up of 50 - 280 C, 20 C/min heating up rate): 212 C
Example 6 Relative solution viscosity in methylene chloride (concentration 5 g/1):
1.162 / 1.162 (duplicate determination) Gel permeation chromatography (GPC, calibration by means of BPA polycarbonate, UV detector 254 nm):
Mn = 8,280 g/mol Mw = 16,777 g/mol D = 2.03 Oligomer content in the range of 300 - 1,500 g/mol: 1.82 %
Glass transition temperature (DSC after 2nd heating up of 50 - 280 C, 20 C/min heating up rate): 207 C
In order to obtain sufficient amounts of polycarbonate in a laboratory continuous unit (limited capacity), the process according to Example 3 was carried out several times. The polycarbonates obtained therefrom are characterized as follows:
= BMS 06 1 120- WO-nat Example 7 Relative solution viscosity in methylene chloride (concentration 5 g/1):
1.165 / 1.166 (duplicate determination) Gel permeation chromatography (GPC, calibration by means of BPA polycarbonate, UV detector 254 nm):
Mn = 8,633 g/mol Mw = 17,407 g/mol D = 2.02 Oligomer content in the range of 300 - 1,500 g/mol: 1.65 %
Glass transition temperature (DSC after 2nd heating up of 50 - 280 C, 20 C/min heating up rate): 204 C
Example 8 Relative solution viscosity in methylene chloride (concentration 5 g/1):
1.166 / 1.165 (duplicate determination) Gel permeation chromatography (GPC, calibration by means of BPA polycarbonate, UV detector 254 nm):
Mn = 8,251 g/mol BMS 06 1 120- WO-nat Mw = 17,023 g/mol D = 2.06 Oligomer content in the range of 300 - 1,500 g/mol: 1.86 %
Glass transition temperature (DSC after 2nd heating up of 50 - 280 C, 20 C/min heating up rate): 204 C
Example 9 All the copolycarbonate fractions from Example 3-8 are combined. The copolycarbonate obtained in this way is characterized as follows:
Relative solution viscosity in methylene chloride (concentration 5 g/1): 1.174 Gel permeation chromatography (GPC, calibration by means of BPA polycarbonate, UV detector 254 nm):
Mn = 9,004 g/mol Mw = 18,029 g/mol D = 2.00 Oligomer content in the range of 300 - 1,500 g/mol: 1.44 %
Glass transition temperature (DSC after 2nd heating up of 50 - 280 C, 20 C/min heating up rate): 207 C
BMS 06 1 120- WO-nat C) Testinp, of the metal adhesion of the copolycarbonate accordinl! to Example 9 The copolycarbonate according to Example 9 is extruded to granules and, after predrying at 130 C for 4 hours, subsequently injection moulded to circular test specimens (diameter: 2 cm, thickness 3 mm). A layer of 200 nm aluminium is sputtered on to the test specimens obtained in this way. An adhesive tape type 853 from 3M is applied to this metal layer. To test the metal adhesion, this adhesive tape is peeled off again immediately after application.
Compared with an analogously metallized specimen of injection-moulded copolycarbonate of 65 mol% bisphenol A and 35 mol% bisphenol TMC having a relative solution viscosity of 1.26, measured in methylene chloride at 25 C
and a concentration of 5 g/l, an improved adhesion of the aluminium to the copolycarbonate surface is found here.
Test specimens according to the invention: after peeling off the adhesive tape, 19 %
of the original aluminium area remains on the polycarbonate substrate Comparison test specimens: On the comparison specimen, after peeling off the adhesive tape no residue at all of the aluminium sputtered on is to be detected. The aluminium deposit hangs completely on the adhesive tape.
BMS 06 1 120- WO-nat Examples A) Preparation of bisphenol of the formula (1) Example 1:
Preparation of N-phenylisatin ONH + CI O A
x toluene N O
\
diphenylamine oxalyl chloride toluene AIC13 T = 114 C
- HCI
O
N
o N-phenyfisatin 660 g (5.20 mol) oxalic acid dichloride, dissolved in 1,600 ml anhydrous toluene, are initially introduced into a previously heated apparatus at room temperature.
798 g (4.72 mol) diphenylamine, likewise dissolved in 1,200 mi anhydrous toluene, are pumped in by means of a Telab pump (setting: 10 strokes/minute at 30 %) in the course of 1.5 hours under intensive stirring. During this procedure, the reaction BMS 06 1 120- WO-nat batch is thermostatically controlled at 45 C. The maximum temperature reached due to the heat of reaction is 50 C.
Directly after the diphenylamine solution has been pumped in, the progress of the reaction is checked by means of gas chromatography (GC) at the intermediate stage before the cyclization (molecular weight 259.69 g/mol; conversion 98.4 area%;
determination of the retention time by prior GC-MS). To carry out the cyclization, g of dry aluminium chloride are added. The mixture is then heated up to the reflux temperature. The temperature is maintained for 3 hours, the HCI gas formed 10 being passed into an alkaline destruction reservoir.
After the end of the reaction, a reaction progress of greater than 90 area% of the desired end product N-phenylisatin (molecular weight 223.23 g/mol) is determined by means of GC.
Working up:
The reaction mixture is precipitated in water, the crude product is filtered off with suction and washed 3 times with distilled water, filtered off under high suction again and then dried at 70 C in a vacuum drying cabinet.
Yield:
977.1 g of an orange-coloured solid (92.7 % of theory) having a melting point of 138 C are obtained (GC purity of 98.7 %).
Analysis:
- GC-MS: molecular weight 223 g/mol BMS 06 1 120- WO-nat - 'H-NMR (400 MHz, TMS CDC13) 8=7.71-7.69 (d, IH), 7.58-7.52 (m, 3H), 7.47-7.41 (m, 3H), 7.19-7.15 (t, IH), 6.91-6.88 (d, 1 H).
Example 2 Bisphenol of the formula (1) Preparation of 3,3-bis(4-hydroxyphenyl)-1-phenyl-1 H-indol-2-one HO
O
~ HCI
Ir~O + OH
2 II , / cH
mercaptopropionic acid /-O
~
N-phenylisatin 1,400 g (6.27 mol) N-phenylisatin from Example 1, 3,541 g (37.6 mol) molten, freshly distilled phenol and 7 g (0.66 mol) 3-mercaptopropionic acid (cocatalyst) are initially introduced into the apparatus, which has been rendered inert, and are heated to 40 - 45 C.
Hydrogen chloride gas is now cautiously passed into this red-brown homogeneous solution for 25 minutes, with moderate stirring, during which the temperature rises to 67 C.
The dark brown batch is then cooled to room temperature and the beige suspension formed is filtered with suction.
BMS 06 1 120- WO-nat Analysis of the product formed:
1 st GC control:
4.0 area% phenol 14.2 area% of a product isomer 2,2-bis(4-hydroxyphenyl)-l -phenyl-1 H-indol-2-one 81.1 area% of the product 3,3-bis(4-hydroxyphenyl)-1-phenyl-lH-indol-2-one Washing the crude product 8 times with I litre of methylene chloride each time leads to the following product:
0.03 area% phenol 2.5 area% of the isomer 2,2-bis(4-hydroxyphenyl)-1-phenyl-l H-indol-3 -one 97.2 area% of the product 3,3-bis(4-hydroxyphenyl)-l -phenyl-l H-indol-2-one Yield after drying:
830 g of a slightly yellowish solid (33.6 % of theory).
Analysis:
- GC-MS: in each case molecular weight 537 g/mol after derivatization as a trimethylsilyl adduct -'H-NMR (400 MHz, TMS, DMSO) 5=9.47 (s, 2H), 7.60-7.57 (t, 2H), 7.50-7.45 (m, 3H), 7.30-7.35 (d, 1 H), 7.28-7.20 (t, 1 H), 7.15-7.10 (t, 1 H), 7.09-7.04 (d, 4H), 6.81-6.79 (d, 1 H), 6.77-6.71 (d, 4H).
BMS 06 1 120- WO-nat *) Isomer reaction:
The compound 2,2-bis(4-hydroxyphenyl)-1-phenyl-lH-indol-3-one is formed as a secondary component by condensation of N-phenylisatin with phenol.
HO
` ` /
mercaptopropionic 0 + 2 OH HCI OH
O~-N acid a_5~~
N (2a) N-phenylisatin b 3,3-bis(4-hydroxyphenyl)-1 phenyl-1 H-indol-2-one OH
0 ~ ~
C~5_ -N I ~
/
O
H (2b) b\-"
2,2-bis(4-hydroxyphenyl)-1-phenyl-1 H-indol-3-one Analysis The analytical determination of the structure of the product obtained (Example 2) after preparation of the sample (conversion into the trimethylsilyl derivative) was carried out by means of gas chromatography-mass spectrometry (GC-MS).
The compound (2a) as the trimethylsilyl derivative has a molecular weight of 537 g/mol. In the GC a further peak is found at a shorter retention time, which according to analysis by means of gas spectrometry likewise has, as the trimethylsilyl derivative, the molecular weight of 537 g/mol. This isomer has the structure according to Example (2b). Furthermore, it was possible to demonstrate by BMS 06 1 120- WO-nat different fragmentation in the mass spectrum that this structure is unambiguously the structure (2b) and not the structure of the bisphenol of the formula (2c).
O
N
` I \
OH
HO (2c) B) Preparation of polycarbonate Example 3 Preparation of a copolycarbonate (50/50 mol%) from bisphenol A (BPA) and the bisphenol according to the invention according to Example 2(3,3-bis(4-hydroxyphenyl)-1-phenyl-lH-indol-2-one (97.2 % according to GC), 2,2-bis(4-hydroxyphenyl)-1-phenyl-1 H-indol-3-one (2.5 % according to GC)).
In order to obtain sufficient amounts of bisphenol of the example for a continuous process, the batch of Example 2 was repeated several times.
A copolycarbonate was obtained by the phase interface process by means of a laboratory continuous unit. The following synthesis conditions and reaction parameters/meterings (in each case the amount per hour) were maintained:
= 15 % strength sodium bisphenolate solution containing a mixture of bisphenol A and the isomer mixture from Example 2(50/50 mol%) = 2.1 mol sodium hydroxide solution per mol bisphenol in the sodium bisphenolate solution BMS 06 1 120- WO-nat = 1.40 mol phosgene per mol bisphenol (or 1.382 mol phosgene per mol bisphenol + 0.5 mol chain terminator) = temperature 30 C during the phosgenation = p-tert-butylphenol (BUP) as the chain terminator = 3.6 mol% chain terminator per mol bisphenol = 1 mol% N-ethylpiperidine (EPP) per mol bisphenol as a catalyst (7.4 %
strength solution in the solvent mixture methylene chloride/chlorobenzene (50/50 wt.%) = 15.0 % strength polycarbonate solution in the solvent mixture methylene chloride/chlorobenzene (50/50) as the desired organic phase = weight of the copolycarbonate formed 156 g/h The following amounts per hour are reacted in this context:
943.3 g of a 15 % strength solution consisting of 52.0 g bisphenol A, 89.5 g bisphenol from Example 5, dissolved in an alkaline aqueous phase of 720 g water and 81.8 g concentrated sodium hydroxide solution (46.7 % strength), are combined together with 736.9 g of a solvent mixture consisting of methylene chloride/chlorobenzene (50/50) which contain 63.0 g phosgene. To regulate the molecular weight, after the phosgenation 2.461 g BUP in 140.6 g of the solvent mixture methylene chloride/chlorobenzene (50/50) are added. To maintain the alkaline pH of approx. 12 - 13, 66.0 g concentrated sodium hydroxide solution (46.7 % strength) are moreover metered in. At the rear end of the dwell zone of the apparatus, 0.515 g EPP, dissolved in 6.44 g of the solvent mixture methylene chloride/chlorobenzene (50/50), is added.
BMS 06 1 120- WO-nat Reaction eguation /'f .~..~r ~.'.`/' j'4```,, }_.. _v x y -'t Or OH Q
HC ~c OH
NaOH 1 water MC/MCB
phosgene NaOH / water o 0 /~ ~~=~a , 0 r o O~~
0"
y x=0.5 y = 0.5 Due to the isomer 2,2-bis(4-hydroxyphenyl)-1-phenyl-lH-indol-3-one formed during the preparation of Example 2, the corresponding content of the isomer is contained in y = 0.5.
After the organic copolycarbonate solution obtained has been washed, the solvent mixture is evaporated off in vacuo, a solid thereby being obtained, which is comminuted and homogenized.
BMS 06 1 120- WO-nat Analysis Relative solution viscosity in methylene chloride at 25 C (concentration 5 g/I):
1.168 Gel permeation chromatography (GPC, calibration by means of BPA polycarbonate, UV detector 254 nm):
Mn = 8,417 g/mol Mw = 18,666 g/mol D = 2.22 (polydispersity) Oligomer content in the range of 300 - 1,500 g/mol: 2.08 %
Glass transition temperature (DSC after 2nd heating up of 50 - 280 C, 20 C/min heating up rate): 210 C
Examples 4 - 8 In order to obtain sufficient amounts of polycarbonate in a laboratory continuous unit (limited capacity), the process according to Example 3 was carried out several times. The polycarbonates obtained therefrom are characterized as follows:
Example 4 Relative solution viscosity in methylene chloride at 25 C (concentration 5 g/1):
1.202 BMS 06 1 120- WO-nat Gel permeation chromatography (GPC, calibration by means of BPA polycarbonate, UV detector 254 nm):
Mn = 10,497 g/mol Mw = 22,972 g/mol D=2.19 Oligomer content in the range of 300 - 1,500 g/mol: 1.41 %
Glass transition temperature (DSC after 2nd heating up of 50 - 280 C, 20 C/min heating up rate): 210 C
Example 5 Relative solution viscosity in methylene chloride at 25 C (concentration 5 g/1):
1.215 Gel permeation chromatography (GPC, calibration by means of BPA polycarbonate, UV detector 254 nm):
Mn = 10,052 g/mol Mw = 24,666 g/mol D = 2.23 Oligomer content in the range of 300 - 1,500 g/mol: 1.41 %
= ' BMS 06 1 120- WO-nat Glass transition temperature (DSC after 2nd heating up of 50 - 280 C, 20 C/min heating up rate): 212 C
Example 6 Relative solution viscosity in methylene chloride (concentration 5 g/1):
1.162 / 1.162 (duplicate determination) Gel permeation chromatography (GPC, calibration by means of BPA polycarbonate, UV detector 254 nm):
Mn = 8,280 g/mol Mw = 16,777 g/mol D = 2.03 Oligomer content in the range of 300 - 1,500 g/mol: 1.82 %
Glass transition temperature (DSC after 2nd heating up of 50 - 280 C, 20 C/min heating up rate): 207 C
In order to obtain sufficient amounts of polycarbonate in a laboratory continuous unit (limited capacity), the process according to Example 3 was carried out several times. The polycarbonates obtained therefrom are characterized as follows:
= BMS 06 1 120- WO-nat Example 7 Relative solution viscosity in methylene chloride (concentration 5 g/1):
1.165 / 1.166 (duplicate determination) Gel permeation chromatography (GPC, calibration by means of BPA polycarbonate, UV detector 254 nm):
Mn = 8,633 g/mol Mw = 17,407 g/mol D = 2.02 Oligomer content in the range of 300 - 1,500 g/mol: 1.65 %
Glass transition temperature (DSC after 2nd heating up of 50 - 280 C, 20 C/min heating up rate): 204 C
Example 8 Relative solution viscosity in methylene chloride (concentration 5 g/1):
1.166 / 1.165 (duplicate determination) Gel permeation chromatography (GPC, calibration by means of BPA polycarbonate, UV detector 254 nm):
Mn = 8,251 g/mol BMS 06 1 120- WO-nat Mw = 17,023 g/mol D = 2.06 Oligomer content in the range of 300 - 1,500 g/mol: 1.86 %
Glass transition temperature (DSC after 2nd heating up of 50 - 280 C, 20 C/min heating up rate): 204 C
Example 9 All the copolycarbonate fractions from Example 3-8 are combined. The copolycarbonate obtained in this way is characterized as follows:
Relative solution viscosity in methylene chloride (concentration 5 g/1): 1.174 Gel permeation chromatography (GPC, calibration by means of BPA polycarbonate, UV detector 254 nm):
Mn = 9,004 g/mol Mw = 18,029 g/mol D = 2.00 Oligomer content in the range of 300 - 1,500 g/mol: 1.44 %
Glass transition temperature (DSC after 2nd heating up of 50 - 280 C, 20 C/min heating up rate): 207 C
BMS 06 1 120- WO-nat C) Testinp, of the metal adhesion of the copolycarbonate accordinl! to Example 9 The copolycarbonate according to Example 9 is extruded to granules and, after predrying at 130 C for 4 hours, subsequently injection moulded to circular test specimens (diameter: 2 cm, thickness 3 mm). A layer of 200 nm aluminium is sputtered on to the test specimens obtained in this way. An adhesive tape type 853 from 3M is applied to this metal layer. To test the metal adhesion, this adhesive tape is peeled off again immediately after application.
Compared with an analogously metallized specimen of injection-moulded copolycarbonate of 65 mol% bisphenol A and 35 mol% bisphenol TMC having a relative solution viscosity of 1.26, measured in methylene chloride at 25 C
and a concentration of 5 g/l, an improved adhesion of the aluminium to the copolycarbonate surface is found here.
Test specimens according to the invention: after peeling off the adhesive tape, 19 %
of the original aluminium area remains on the polycarbonate substrate Comparison test specimens: On the comparison specimen, after peeling off the adhesive tape no residue at all of the aluminium sputtered on is to be detected. The aluminium deposit hangs completely on the adhesive tape.
Claims (15)
1. (Co)polycarbonate containing bisphenols of the formulae (1a1), (1b1) (isomer mixture) as a recurring monomer unit in which R1 independently of one another represents hydrogen or C1-C10-alkyl and R2 represents C1-C10-alkyl, or phenyl or benzyl in each case optionally substituted by hydrogen and/or C1-C10-alkyl.
2. (Co)polycarbonate according to claim 1, containing up to 95 mol% (based on the amount of diphenols employed) of diphenols of the formula (2) in which R3 and R4 independently of one another represent hydrogen, C1-C18-alkyl, C1-C18-alkoxy, halogen or in each case optionally substituted aryl or aralkyl, and X represents a single bond, -SO2-. -CO-, -O-, -S-, C1- to C6-alkylene, C2- to C5-alkylidene or C5- to C6-cycloalkylidene, which can be substituted by C1- to C6-alkyl, or C6- to C12-arylene, which can optionally be fused with further aromatic rings containing hetero atoms.
3. (Co)polycarbonate according to claim 1, containing up to 80 mol% (based on the amount of diphenols employed) of diphenols of the formula (2).
4. (Co)polycarbonate according to claim 3, containing 40 - 60 mol% of diphenol of the formula (1) and 60 to 40 mol% of diphenol of the formula (2).
5. (Co)polycarbonate according to claim 3, containing 45 - 55 mol% of diphenol of the formula (1) and 55 to 45 mol% of diphenol of the formula (2).
6. (Co)polycarbonate according to claim 1, wherein in the formulae (1a1) and (1b1) R1 denotes hydrogen and R2 denotes phenyl.
7. (Co)polycarbonate according to claim 2, wherein diphenols of the formula (2) are chosen from at least one from the group consisting of bisphenol A, 4,4'-dihydroxybiphenyl, bisphenol M and bisphenol TMC.
8. Use of (co)polycarbonates according to claim 1 for the production of mouldings.
9. Mouldings obtainable from (co)polycarbonates according to claim 1.
10. Products from injection moulding or extrusion processes, such as e.g.
automobile screens, optical data storage media, sheets, films and bottles, comprising (co)polycarbonates according to claim 1.
automobile screens, optical data storage media, sheets, films and bottles, comprising (co)polycarbonates according to claim 1.
11. Metallized mouldings comprising (co)polycarbonates according to claim 1.
12. Blends of the (co)polycarbonates according to claim 1 with thermoplastic polymers.
13. Process for the preparation of (co)polycarbonates according to claim 1 by the phase interface process, characterized in that compounds of the formula (1a) are employed as the bisphenol.
14. Compound of the formulae (1a) and (1b) in which R1 independently of one another represents hydrogen or C1-C10-alkyl and R2 represents C1-C10-alkyl or in each case optionally unsubstituted or substituted phenyl or benzyl, the radicals mentioned for R1 being preferred substituents for phenyl and benzyl.
15. Use of the compounds according to claim 14 for the preparation of (co)polycarbonates.
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DE102006046330.7 | 2006-09-28 | ||
DE102006046330A DE102006046330A1 (en) | 2006-09-28 | 2006-09-28 | Polycarbonates and copolycarbonates with improved metal adhesion |
PCT/EP2007/008048 WO2008037364A1 (en) | 2006-09-28 | 2007-09-15 | Polycarbonates and copolycarbonates with improved metal adhesion |
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Families Citing this family (64)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080118729A1 (en) * | 2006-11-16 | 2008-05-22 | General Electric Company | Thermoplastic composition, method of making, and articles formed therefrom |
US20090186966A1 (en) * | 2008-01-22 | 2009-07-23 | Sabic Innovative Plastics Ip B.V. | Thermoplastic polyestercarbonate composition |
DE102008036406A1 (en) * | 2008-08-05 | 2010-02-11 | Bayer Materialscience Ag | Modified polycarbonates with improved surface properties |
EP2459627B1 (en) | 2009-07-29 | 2016-06-29 | Covestro Deutschland AG | Multi-layer products comprising acrylate containing coatings |
JP5562605B2 (en) * | 2009-09-30 | 2014-07-30 | 大阪ガスケミカル株式会社 | Novel aromatic compound and method for producing the same |
WO2011067282A1 (en) | 2009-12-05 | 2011-06-09 | Bayer Materialscience Ag | Polycarbonate compositions with a phenolically substituted triazine derivative |
DE102009059771A1 (en) * | 2009-12-21 | 2011-06-22 | Bayer MaterialScience AG, 51373 | Polycarbonate with improved thermal and mechanical properties and reduced thermal expansion coefficient |
US8779162B2 (en) | 2010-01-20 | 2014-07-15 | Mitsubishi Gas Chemical Company, Inc. | Cyanate ester compounds and cured products thereof |
EP2447236A1 (en) | 2010-10-12 | 2012-05-02 | Bayer MaterialScience AG | Special UV absorber for hardening UV protection coatings |
DE102010042939A1 (en) | 2010-10-26 | 2012-04-26 | Bayer Materialscience Aktiengesellschaft | Jointless tailgate |
CN103391970B (en) | 2010-11-05 | 2015-03-25 | 拜耳知识产权有限责任公司 | Flame-proofed, UV-protected polycarbonate molding compounds having low molecular weight degradation |
EP2635629A1 (en) | 2010-11-05 | 2013-09-11 | Bayer Intellectual Property GmbH | Uv-protected polycarbonate molding materials equipped so as to be flame-retardant and having a low molecular weight decrease |
ES2663841T3 (en) | 2010-11-24 | 2018-04-17 | Covestro Deutschland Ag | Procedure for the manufacture of optical molded bodies |
ITRM20100667A1 (en) | 2010-12-17 | 2012-06-18 | Bayer Materialscience Ag | COMPOSITION OF POLYMERS WITH HIGH STABILITY HEAT ABSORPTION CHARACTERISTICS TO THE ATMOSPHERIC AGENTS. |
IT1403380B1 (en) | 2010-12-17 | 2013-10-17 | Bayer Materialscience Ag | COMPOSITION OF POLYMERS WITH HIGH STABILITY HEAT ABSORPTION CHARACTERISTICS TO THE ATMOSPHERIC AGENTS. |
ITRM20100670A1 (en) | 2010-12-17 | 2012-06-18 | Bayer Materialscience Ag | ORGANIC COLORING AND COLORED POLYMER COMPOSITIONS WITH HIGH STABILITY TO THE ATMOSPHERIC AGENTS. |
ITRM20100668A1 (en) | 2010-12-17 | 2012-06-18 | Bayer Materialscience Ag | SUBSTRATO-LED WITH STABLE COLOR. |
US9441106B2 (en) | 2011-11-11 | 2016-09-13 | Sabic Global Technologies B.V. | Composition, multilayer sheets made therefrom, and methods for making and using the same |
CN103946310B (en) | 2011-11-30 | 2016-03-02 | 拜耳知识产权有限责任公司 | The multi-layer product with dark luster effect be made up of polycarbonate |
KR102001699B1 (en) | 2011-11-30 | 2019-07-18 | 코베스트로 도이칠란드 아게 | Multi-layer bodies made of polycarbonate with a deep gloss effect |
US20130216859A1 (en) | 2012-02-20 | 2013-08-22 | Bayer Materialscience Ag | Multilayer assembly as reflector |
ES2640919T3 (en) | 2012-06-01 | 2017-11-07 | Covestro Deutschland Ag | Multilayer structure as reflector |
EP2700455A1 (en) | 2012-08-23 | 2014-02-26 | Bayer MaterialScience AG | Wet varnish application to plastic substrates with plasma hardening |
EP2888058A1 (en) | 2012-08-23 | 2015-07-01 | Bayer Materialscience AG | Vapour deposition of organic uv absorbers onto plastic substrates |
ITRM20120656A1 (en) | 2012-12-20 | 2014-06-21 | Bayer Materialscience Ag | MULTI-LAYER POLYCARBONATE-BASED ARTICLE WITH STRONG RESISTANCE TO ATMOSPHERIC AGENTS. |
CN104995247B (en) | 2012-12-20 | 2018-05-08 | 科思创德国股份有限公司 | Toner and the coloured polymer composition with well processed property |
ES2720925T3 (en) | 2012-12-20 | 2019-07-25 | Covestro Deutschland Ag | Opaque colored polycarbonate molding masses containing IR reflective pigments |
US9127119B2 (en) | 2013-01-11 | 2015-09-08 | Sabic Global Technologies B.V. | Polycarbonate compositions having improved thermal dimensional stability and high refractive index |
WO2014111473A1 (en) | 2013-01-18 | 2014-07-24 | Bayer Materialscience Ag | Bird protection glazing |
US9718951B2 (en) | 2013-04-04 | 2017-08-01 | Covestro Deutschland Ag | High-temperature (co)polycarbonates containing phthalimide and having improved rheological properties |
CN105408430B (en) | 2013-06-14 | 2018-11-27 | 科思创德国股份公司 | The film of the micro-structural specific coating of free from glare |
EP3008137B1 (en) | 2013-06-14 | 2019-08-14 | Covestro Deutschland AG | Radiation-curable coating composition |
KR20160026891A (en) | 2013-06-27 | 2016-03-09 | 코베스트로 도이칠란트 아게 | Metallizable, scratch-resistant and solvent-resistant film |
JP6155999B2 (en) * | 2013-09-13 | 2017-07-05 | Jsr株式会社 | Resin molded body, film / lens, transparent conductive film, resin composition, polymer |
WO2015144680A2 (en) | 2014-03-27 | 2015-10-01 | Bayer Materialscience Ag | Coating agent and films having increased mechanical and chemical resistance and sufficient deformability in 2-d film insert molding methods |
JP6206445B2 (en) * | 2014-07-25 | 2017-10-04 | Jsr株式会社 | Circuit board resin substrate, circuit board resin composition, and circuit board |
JP6672275B2 (en) | 2014-09-11 | 2020-03-25 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトCovestro Deutschland Ag | Bezel for automotive glass mounting system |
JP6778213B2 (en) * | 2016-01-08 | 2020-10-28 | 本州化学工業株式会社 | Bisphenol compounds and aromatic polycarbonate |
WO2017170096A1 (en) * | 2016-03-28 | 2017-10-05 | 本州化学工業株式会社 | Method for producing novel dihydroxy compound |
KR102350817B1 (en) * | 2016-03-28 | 2022-01-13 | 혼슈우 카가쿠고교 가부시키가이샤 | Novel dihydroxy compound |
KR102263143B1 (en) * | 2016-03-28 | 2021-06-08 | 혼슈우 카가쿠고교 가부시키가이샤 | Novel dihydroxy compound |
KR102351908B1 (en) * | 2016-05-04 | 2022-01-18 | 코베스트로 도이칠란트 아게 | Copolycarbonate as support material in 3-D printing |
EP3519217B1 (en) | 2016-09-27 | 2021-06-30 | Covestro Intellectual Property GmbH & Co. KG | Vehicle with two a-pillars and a windscreen |
WO2018073111A1 (en) | 2016-10-18 | 2018-04-26 | Covestro Deutschland Ag | Method for producing a plastic body suitable as a decorative element |
JP7163287B2 (en) | 2016-11-17 | 2022-10-31 | コベストロ、ドイチュラント、アクチエンゲゼルシャフト | Opaque multi-layer body of polycarbonate for thermal management |
US11440382B2 (en) | 2016-11-17 | 2022-09-13 | Covestro Deutschland Ag | Transparent multilayer structure for thermal management |
JP2020501944A (en) | 2016-12-15 | 2020-01-23 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトCovestro Deutschland Ag | Transparent coated polycarbonate parts, their manufacture and use |
EP3395875B2 (en) | 2017-04-24 | 2023-01-25 | Covestro Deutschland AG | Laser beam-permeable substrate material for sensor applications |
WO2018202707A1 (en) | 2017-05-03 | 2018-11-08 | Basf Se | Nucleating agents, methods for their production, and associated polymer compositions |
TW201906882A (en) | 2017-05-09 | 2019-02-16 | 德商科思創德意志股份有限公司 | Film structure containing a photopolymer layer for holographic illumination and a highly resistant lacquer layer |
TW201906730A (en) | 2017-05-09 | 2019-02-16 | 德商科思創德意志股份有限公司 | Plastic film containing UV curable adhesive layer for protecting the hologram in the photopolymer film composite |
KR20200006988A (en) | 2017-05-09 | 2020-01-21 | 코베스트로 도이칠란트 아게 | System consisting of two dry-applicable UV-curable lacquer layers for protection of holograms in photopolymer film composites |
KR20200103035A (en) | 2017-12-21 | 2020-09-01 | 코베스트로 도이칠란트 아게 | Devices including multilayer bodies and LiDAR sensors |
AU2019248578A1 (en) | 2018-04-04 | 2020-10-01 | Basf Se | Use of an ultraviolet radiation absorbing composition as a light stabilizer for a shaped artificial polymer article |
CN112334306B (en) | 2018-05-29 | 2023-04-07 | 科思创知识产权两合公司 | Opaque multilayer articles made of polycarbonate with high weathering stability |
AU2020239186A1 (en) | 2019-03-12 | 2021-09-09 | Basf Se | Shaped artificial polymer articles |
KR20220103104A (en) | 2019-11-14 | 2022-07-21 | 코베스트로 인텔렉쳐 프로퍼티 게엠베하 운트 콤파니 카게 | Thermoplastic composition for LIDAR sensor systems with improved absorption properties |
WO2022037950A1 (en) | 2020-08-18 | 2022-02-24 | Covestro Deutschland Ag | Systems of coating agents, consisting of a base coat and a top coat, and semi-finished product based thereon and production of same |
KR20230130036A (en) | 2021-01-05 | 2023-09-11 | 바스프 에스이 | Stabilization of molded polymer articles against degradation induced by artificial UV-C light |
KR20230022700A (en) * | 2021-08-09 | 2023-02-16 | 주식회사 엘지화학 | Polycarbonate copolymer |
WO2023141091A1 (en) | 2022-01-18 | 2023-07-27 | Basf Se | Shaped artificial polymer articles with closed-cell metal oxide particles |
WO2023141089A1 (en) | 2022-01-18 | 2023-07-27 | Basf Se | Shaped artificial polymer articles with hybrid metal oxide particles |
WO2024002735A1 (en) | 2022-06-29 | 2024-01-04 | Basf Se | Stabilizing a shaped polymer article against degradation induced by artificial uv-c light |
WO2024068415A1 (en) | 2022-09-29 | 2024-04-04 | Basf Se | Co-stabilizers for hydroxyphenyl triazine stabilized polymers |
Family Cites Families (112)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US624969A (en) * | 1899-05-16 | Peter peterson | ||
US1484348A (en) * | 1914-12-17 | 1924-02-19 | Aldendorff Fritz | Machine-switching telephone system |
US1153797A (en) * | 1915-04-29 | 1915-09-14 | Jules Emile Kegreisz | Expansion-anchor. |
US1330987A (en) * | 1917-03-31 | 1920-02-17 | Runyen Mfg Co | Grease container and dispenser |
US1302169A (en) * | 1917-10-03 | 1919-04-29 | Underwood Typewriter Co | Type-writing machine. |
DE488760C (en) | 1925-03-26 | 1930-01-10 | I G Farbenindustrie Akt Ges | Process for the preparation of diphenolisatins |
US2077804A (en) * | 1936-05-19 | 1937-04-20 | Morrison Gordon Monroe | Device for treating fractures of the neck of the femur |
US2299308A (en) * | 1941-08-15 | 1942-10-20 | Russell A Creighton | Self-locking spike |
US2485531A (en) * | 1948-01-13 | 1949-10-18 | Dzus William | Surgical toggle bolt |
US2607370A (en) * | 1948-07-13 | 1952-08-19 | Oscar F Anderson | Pipe plug |
US2685877A (en) * | 1952-03-20 | 1954-08-10 | Dobelle Martin | Femoral head prosthesis |
US2799948A (en) * | 1955-11-17 | 1957-07-23 | Whirlpool Seeger Corp | Clothes drier |
US3426364A (en) * | 1966-08-25 | 1969-02-11 | Colorado State Univ Research F | Prosthetic appliance for replacing one or more natural vertebrae |
US4274324A (en) * | 1978-04-18 | 1981-06-23 | Giannuzzi Louis | Hollow wall screw anchor |
US4289123A (en) * | 1980-03-31 | 1981-09-15 | Dunn Harold K | Orthopedic appliance |
GB2083754B (en) * | 1980-09-15 | 1984-04-26 | Rezaian Seyed Mahmoud | Spinal fixator |
US4646998A (en) * | 1981-11-20 | 1987-03-03 | Clairson International Corporation | Wall-mounted shelf support clip |
US4519100A (en) * | 1982-09-30 | 1985-05-28 | Orthopedic Equipment Co. Inc. | Distal locking intramedullary nail |
US4822226A (en) * | 1983-08-08 | 1989-04-18 | Kennedy Arvest G | Wing nut retainer and extractor |
US4611582A (en) * | 1983-12-27 | 1986-09-16 | Wisconsin Alumni Research Foundation | Vertebral clamp |
US4636217A (en) * | 1985-04-23 | 1987-01-13 | Regents Of The University Of Minnesota | Anterior spinal implant |
US4599086A (en) * | 1985-06-07 | 1986-07-08 | Doty James R | Spine stabilization device and method |
US4662808A (en) * | 1985-10-02 | 1987-05-05 | Lee-Rowan Company | Wall anchor |
CA1283501C (en) * | 1987-02-12 | 1991-04-30 | Thomas P. Hedman | Artificial spinal disc |
US4892545A (en) * | 1988-07-14 | 1990-01-09 | Ohio Medical Instrument Company, Inc. | Vertebral lock |
IT215084Z2 (en) * | 1988-08-03 | 1990-07-30 | Torino A | VARIABLE EXCURSION CAMBRA |
US4834600A (en) * | 1988-08-25 | 1989-05-30 | Lemke Stuart H | Fastener assembly |
AU630122B2 (en) * | 1988-11-15 | 1992-10-22 | Abbott Laboratories | N-arylation of isatins |
US4932975A (en) * | 1989-10-16 | 1990-06-12 | Vanderbilt University | Vertebral prosthesis |
US5454365A (en) * | 1990-11-05 | 1995-10-03 | Bonutti; Peter M. | Mechanically expandable arthroscopic retractors |
SU1757216A1 (en) * | 1990-10-18 | 1996-08-27 | Научно-исследовательский институт пластических масс | Statistically branched polycarbonate for structural and optical article at enhanced thermostability |
DE4128332A1 (en) * | 1991-08-27 | 1993-03-04 | Man Ceramics Gmbh | SPINE BONE REPLACEMENT |
US5290312A (en) * | 1991-09-03 | 1994-03-01 | Alphatec | Artificial vertebral body |
DE4208116C2 (en) * | 1992-03-13 | 1995-08-03 | Link Waldemar Gmbh Co | Intervertebral disc prosthesis |
US5312405A (en) * | 1992-07-06 | 1994-05-17 | Zimmer, Inc. | Spinal rod coupler |
FR2695026B1 (en) * | 1992-08-25 | 1994-10-28 | Alexandre Worcel | Device for maintaining compression of a fractured bone. |
US5562735A (en) * | 1992-11-09 | 1996-10-08 | Hospital For Joint Diseases | Spinal stabilization system and improved method |
US5527314A (en) * | 1993-01-04 | 1996-06-18 | Danek Medical, Inc. | Spinal fixation system |
US5344910A (en) * | 1993-03-23 | 1994-09-06 | General Electric Company | Heat-resistant polycarbonate resins containing 2-alkyl-3,3-bis(p-hydroxyphenyl)phthalimide |
EP0621020A1 (en) * | 1993-04-21 | 1994-10-26 | SULZER Medizinaltechnik AG | Intervertebral prosthesis and method of implanting such a prosthesis |
DE69415594T2 (en) * | 1993-07-09 | 1999-08-12 | Gen Electric | Siloxane polyester carbonate block polymer compositions and heat resistant polycarbonate |
US5458641A (en) * | 1993-09-08 | 1995-10-17 | Ramirez Jimenez; Juan J. | Vertebral body prosthesis |
US5439463A (en) * | 1993-11-12 | 1995-08-08 | Lin; Chih-I | Spinal clamping device |
US5403316A (en) * | 1993-12-02 | 1995-04-04 | Danek Medical, Inc. | Triangular construct for spinal fixation |
US5653762A (en) * | 1994-03-18 | 1997-08-05 | Pisharodi; Madhavan | Method of stabilizing adjacent vertebrae with rotating, lockable, middle-expanded intervertebral disk stabilizer |
DE9413471U1 (en) * | 1994-08-20 | 1995-12-21 | Schaefer Micomed Gmbh | Ventral intervertebral implant |
DE69519151T2 (en) * | 1994-12-28 | 2001-05-23 | Gen Electric | Copolycarbonate |
JPH08183853A (en) * | 1994-12-28 | 1996-07-16 | Nippon G Ii Plast Kk | Polycarbonate, polycarbonate composition and production thereof |
JPH08183900A (en) * | 1994-12-28 | 1996-07-16 | Nippon G Ii Plast Kk | Copolycarbonate, copolycarbonate composition, and their production |
FR2730158B1 (en) * | 1995-02-06 | 1999-11-26 | Jbs Sa | DEVICE FOR MAINTAINING A NORMAL SPACING BETWEEN VERTEBRES AND FOR THE REPLACEMENT OF MISSING VERTEBRES |
US5658335A (en) * | 1995-03-09 | 1997-08-19 | Cohort Medical Products Group, Inc. | Spinal fixator |
US5630816A (en) * | 1995-05-01 | 1997-05-20 | Kambin; Parviz | Double barrel spinal fixation system and method |
WO1996039090A1 (en) * | 1995-06-06 | 1996-12-12 | Sdgi Holdings, Inc. | Device for linking adjacent rods in spinal instrumentation |
DE19609057A1 (en) * | 1996-03-08 | 1997-09-11 | Bayer Ag | Process for the preparation of diaryl carbonates and the polycarbonates obtainable therefrom |
US5653763A (en) * | 1996-03-29 | 1997-08-05 | Fastenetix, L.L.C. | Intervertebral space shape conforming cage device |
WO1997048352A1 (en) * | 1996-06-18 | 1997-12-24 | Mehran Kasra | Bone prosthesis fixation device and methods of using same |
US5746762A (en) * | 1996-06-24 | 1998-05-05 | Bass; Lawrence S. | Device and method for surgical flap dissection |
DE19638888A1 (en) * | 1996-09-23 | 1998-03-26 | Bayer Ag | Production of cyclic aromatic bis:phenol compounds |
US5893850A (en) * | 1996-11-12 | 1999-04-13 | Cachia; Victor V. | Bone fixation device |
US7101375B2 (en) * | 1997-01-02 | 2006-09-05 | St. Francis Medical Technologies, Inc. | Spine distraction implant |
US5725341A (en) * | 1997-01-08 | 1998-03-10 | Hofmeister; Oskar | Self fusing fastener |
DE19816782A1 (en) * | 1998-04-16 | 1999-10-28 | Ulrich Gmbh & Co Kg | Implant for insertion between the vertebral body of the spine |
DE19818143A1 (en) * | 1998-04-23 | 1999-10-28 | Medinorm Ag | Device for connecting vertebrae of the spine |
US6264658B1 (en) * | 1998-07-06 | 2001-07-24 | Solco Surgical Instruments Co., Ltd. | Spine fixing apparatus |
US7029473B2 (en) * | 1998-10-20 | 2006-04-18 | St. Francis Medical Technologies, Inc. | Deflectable spacer for use as an interspinous process implant and method |
US6261289B1 (en) * | 1998-10-26 | 2001-07-17 | Mark Levy | Expandable orthopedic device |
ATE322868T1 (en) * | 1998-10-30 | 2006-04-15 | Ian Ross Griggs | FIXATION DEVICE |
US6770096B2 (en) * | 1999-07-01 | 2004-08-03 | Spinevision S.A. | Interbody spinal stabilization cage and spinal stabilization method |
US6336930B1 (en) * | 2000-03-07 | 2002-01-08 | Zimmer, Inc. | Polymer filled bone plate |
US6964667B2 (en) * | 2000-06-23 | 2005-11-15 | Sdgi Holdings, Inc. | Formed in place fixation system with thermal acceleration |
US6743257B2 (en) * | 2000-12-19 | 2004-06-01 | Cortek, Inc. | Dynamic implanted intervertebral spacer |
US20030040746A1 (en) * | 2001-07-20 | 2003-02-27 | Mitchell Margaret E. | Spinal stabilization system and method |
DE10142735A1 (en) * | 2001-08-31 | 2003-03-20 | Bayer Ag | Process for using polycarbonates |
US6630527B2 (en) | 2001-10-19 | 2003-10-07 | General Electric Company | UV stabilized, impact modified polyester/polycarbonate blends, articles, and methods of manufacture thereof |
US7227254B2 (en) * | 2002-04-02 | 2007-06-05 | Agilent Technologies, Inc. | Integrated circuit package |
US7827116B2 (en) * | 2002-08-20 | 2010-11-02 | Piccionelli Gregory A | Methods of producing and transmitting content based on compliance |
FR2850009B1 (en) * | 2003-01-20 | 2005-12-23 | Spine Next Sa | TREATMENT ASSEMBLY FOR THE DEGENERATION OF AN INTERVERTEBRAL DISC |
US7335203B2 (en) * | 2003-02-12 | 2008-02-26 | Kyphon Inc. | System and method for immobilizing adjacent spinous processes |
US7505151B2 (en) * | 2003-04-07 | 2009-03-17 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. | Arrangement for the optical distance determination of a reflecting surface |
US7377942B2 (en) * | 2003-08-06 | 2008-05-27 | Warsaw Orthopedic, Inc. | Posterior elements motion restoring device |
KR100914421B1 (en) * | 2004-03-04 | 2009-08-27 | 테이진 카세이 가부시키가이샤 | Optical recording medium |
US7365124B2 (en) * | 2004-03-31 | 2008-04-29 | General Electric Company | Flame retardant resin blends based on polymers derived from 2-hydrocarbyl-3,3-bis(4-hydroxyaryl)phthalimidine monomers |
US7277230B2 (en) | 2004-03-31 | 2007-10-02 | General Electric Company | Methods for producing and purifying 2-hydrocarbyl-3,3-bis(4-hydroxyaryl)phthalimidine monomers and polycarbonates derived therefrom |
FR2870107B1 (en) * | 2004-05-11 | 2007-07-27 | Spine Next Sa | SELF-LOCKING DEVICE FOR FIXING AN INTERVERTEBRAL IMPLANT |
US20060085073A1 (en) * | 2004-10-18 | 2006-04-20 | Kamshad Raiszadeh | Medical device systems for the spine |
US7763074B2 (en) * | 2004-10-20 | 2010-07-27 | The Board Of Trustees Of The Leland Stanford Junior University | Systems and methods for posterior dynamic stabilization of the spine |
US8409282B2 (en) * | 2004-10-20 | 2013-04-02 | Vertiflex, Inc. | Systems and methods for posterior dynamic stabilization of the spine |
US8241330B2 (en) * | 2007-01-11 | 2012-08-14 | Lanx, Inc. | Spinous process implants and associated methods |
US20060095136A1 (en) * | 2004-11-03 | 2006-05-04 | Mcluen Design, Inc. | Bone fusion device |
DE102005005694A1 (en) * | 2005-02-08 | 2006-08-17 | Henning Kloss | Spine vertebra support device for twpporting two sucessive vertebras, useful in implantation processes has two supoirts and two suppor holders |
US7998174B2 (en) * | 2005-02-17 | 2011-08-16 | Kyphon Sarl | Percutaneous spinal implants and methods |
US8096994B2 (en) * | 2005-02-17 | 2012-01-17 | Kyphon Sarl | Percutaneous spinal implants and methods |
US8007521B2 (en) * | 2005-02-17 | 2011-08-30 | Kyphon Sarl | Percutaneous spinal implants and methods |
US20060241757A1 (en) * | 2005-03-31 | 2006-10-26 | Sdgi Holdings, Inc. | Intervertebral prosthetic device for spinal stabilization and method of manufacturing same |
JP5345839B2 (en) * | 2005-04-08 | 2013-11-20 | パラダイム・スパイン・リミテッド・ライアビリティ・カンパニー | Interspinous vertebrae and lumbosacral stabilization device and method of use |
FR2884136B1 (en) * | 2005-04-08 | 2008-02-22 | Spinevision Sa | INTERVERTEBRAL SURGICAL IMPLANT FORMING BALL |
US7780709B2 (en) * | 2005-04-12 | 2010-08-24 | Warsaw Orthopedic, Inc. | Implants and methods for inter-transverse process dynamic stabilization of a spinal motion segment |
US7789898B2 (en) * | 2005-04-15 | 2010-09-07 | Warsaw Orthopedic, Inc. | Transverse process/laminar spacer |
US7753938B2 (en) * | 2005-08-05 | 2010-07-13 | Synthes Usa, Llc | Apparatus for treating spinal stenosis |
US7998173B2 (en) * | 2005-11-22 | 2011-08-16 | Richard Perkins | Adjustable spinous process spacer device and method of treating spinal stenosis |
JP2009525060A (en) * | 2005-12-06 | 2009-07-09 | グローバス メディカル インコーポレイティッド | Intervertebral joint prosthesis |
US20070191838A1 (en) * | 2006-01-27 | 2007-08-16 | Sdgi Holdings, Inc. | Interspinous devices and methods of use |
US20070233089A1 (en) * | 2006-02-17 | 2007-10-04 | Endius, Inc. | Systems and methods for reducing adjacent level disc disease |
US20070233068A1 (en) * | 2006-02-22 | 2007-10-04 | Sdgi Holdings, Inc. | Intervertebral prosthetic assembly for spinal stabilization and method of implanting same |
US7491788B1 (en) * | 2006-05-19 | 2009-02-17 | Sabic Innovative Plastics Ip B.V. | High heat polycarbonate compositions, methods for the preparation thereof, and articles derived therefrom |
US20080021457A1 (en) * | 2006-07-05 | 2008-01-24 | Warsaw Orthopedic Inc. | Zygapophysial joint repair system |
US20080183218A1 (en) * | 2007-01-31 | 2008-07-31 | Nuvasive, Inc. | System and Methods for Spinous Process Fusion |
US7799058B2 (en) * | 2007-04-19 | 2010-09-21 | Zimmer Gmbh | Interspinous spacer |
CN101861552B (en) * | 2007-07-17 | 2014-08-20 | 约翰逊控制技术公司 | Extremum seeking control with actuator saturation control |
US8892558B2 (en) * | 2007-09-26 | 2014-11-18 | International Business Machines Corporation | Inserting data into an in-memory distributed nodal database |
US20090098536A1 (en) * | 2007-10-12 | 2009-04-16 | C-A-I-R- Biosciences Gmbh | Method for subgroup analysis in subjects having or being suspected of having inflammatory disease, use of anti-p38MAPK antibodies, kits and their use |
TW200938157A (en) * | 2008-03-11 | 2009-09-16 | Fong-Ying Chuang | Interspinous spine fixing device |
-
2006
- 2006-09-28 DE DE102006046330A patent/DE102006046330A1/en not_active Withdrawn
-
2007
- 2007-09-15 CA CA002664397A patent/CA2664397A1/en not_active Abandoned
- 2007-09-15 JP JP2009529571A patent/JP5147847B2/en not_active Expired - Fee Related
- 2007-09-15 MX MX2009002643A patent/MX2009002643A/en unknown
- 2007-09-15 ES ES07802331T patent/ES2360149T3/en active Active
- 2007-09-15 WO PCT/EP2007/008048 patent/WO2008037364A1/en active Application Filing
- 2007-09-15 DE DE502007006560T patent/DE502007006560D1/en active Active
- 2007-09-15 CN CN2007800360325A patent/CN101516967B/en active Active
- 2007-09-15 RU RU2009115790/04A patent/RU2451035C2/en not_active IP Right Cessation
- 2007-09-15 KR KR1020097006361A patent/KR101487033B1/en active IP Right Grant
- 2007-09-15 AT AT07802331T patent/ATE499401T1/en active
- 2007-09-15 EP EP07802331A patent/EP2081974B1/en active Active
- 2007-09-24 US US11/903,733 patent/US7547755B2/en active Active
- 2007-09-27 TW TW096135878A patent/TWI415874B/en not_active IP Right Cessation
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WO2008037364A1 (en) | 2008-04-03 |
MX2009002643A (en) | 2009-03-24 |
TW200835718A (en) | 2008-09-01 |
DE102006046330A1 (en) | 2008-04-03 |
RU2009115790A (en) | 2010-11-10 |
US20080081896A1 (en) | 2008-04-03 |
RU2451035C2 (en) | 2012-05-20 |
JP5147847B2 (en) | 2013-02-20 |
CN101516967A (en) | 2009-08-26 |
EP2081974A1 (en) | 2009-07-29 |
TWI415874B (en) | 2013-11-21 |
ATE499401T1 (en) | 2011-03-15 |
KR20090057068A (en) | 2009-06-03 |
KR101487033B1 (en) | 2015-01-28 |
JP2010505011A (en) | 2010-02-18 |
ES2360149T3 (en) | 2011-06-01 |
EP2081974B1 (en) | 2011-02-23 |
US7547755B2 (en) | 2009-06-16 |
DE502007006560D1 (en) | 2011-04-07 |
CN101516967B (en) | 2012-07-18 |
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