EP0000060A1 - Procédé de préparation de bis-carbonates de diphénols et de polyoxyalkylèneglycols allongés par des groupes carbonates; leur application à la préparation de polyéthers polycarbonates thermoplastiques à blocs de haut poids moléculaire. - Google Patents

Procédé de préparation de bis-carbonates de diphénols et de polyoxyalkylèneglycols allongés par des groupes carbonates; leur application à la préparation de polyéthers polycarbonates thermoplastiques à blocs de haut poids moléculaire. Download PDF

Info

Publication number
EP0000060A1
EP0000060A1 EP78100103A EP78100103A EP0000060A1 EP 0000060 A1 EP0000060 A1 EP 0000060A1 EP 78100103 A EP78100103 A EP 78100103A EP 78100103 A EP78100103 A EP 78100103A EP 0000060 A1 EP0000060 A1 EP 0000060A1
Authority
EP
European Patent Office
Prior art keywords
bis
polyalkylene oxide
weight
carbonate
diphenol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP78100103A
Other languages
German (de)
English (en)
Other versions
EP0000060B1 (fr
Inventor
Manfred Dr. Schreckenberg
Dieter Dr. Freitag
Christian Dr. Lindner
Carlhans Dr. Süling
Herbert Dr. Bartl
Klaus Dr. König
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0000060A1 publication Critical patent/EP0000060A1/fr
Application granted granted Critical
Publication of EP0000060B1 publication Critical patent/EP0000060B1/fr
Expired legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C08G64/183—Block or graft polymers containing polyether sequences

Definitions

  • German patent application P 2 650 533.9 claims a process for the production of carbonic acid aryl esters of polyalkylene oxide diols made from polyalkylene oxide diols which are extended by carbonate groups M n over 135, preferably over 800, and carbonic acid bisaryl esters, which is characterized in that polyalkylene oxide diols with molecular weights Rn (number average) over 135, preferably at temperatures between 100 ° C. and 200 ° C. in a vacuum below 35 torr together with carbonic acid bis- aryl esters heated in the presence of catalysts, less than one mole of carbonic acid bis-aryl ester being used per OH group, and the hydroxylaryl compound formed being distilled off.
  • the present invention now relates to the use of the carbonic acid aryl esters obtainable according to the above-mentioned German patent application P 2 650 533.9 for the preparation of polyalkylene oxide di-bis-diphenol carbonates extended by carbonate groups;
  • Another object of the present invention are the polyalkylene oxide di-bis-diphenol carbonates obtained via carbonate groups-elongated and their use for the production of polyether polycarbonates.
  • Another object of the present invention are the polyether polycarbonates obtained according to the invention with an improved phase separation between the soft segment and the hard segment, which leads to better performance properties of the corresponding polycarbonate elastomers.
  • polyalkylene oxide is extended via carbonate groups diol-bis-aryl carbonates, which are obtainable according to German patent application P 2 650 533.9 in that polyalkylene oxide diols with molecular weights Rn (number average) over 135, preferably over 8 00 , with carbonic acid bis-aryl esters at temperatures between 100 ° C.
  • the present invention thus relates to polyalkylene oxide di-bis-diphenol carbonates which are extended by carbonate groups and obtained by this process according to the invention.
  • Suitable catalysts for the preparation according to the invention of the polyalkylene oxide di-bis-diphenol carbonates which are extended via carbonate groups are basic transesterification catalysts such as alkali metal or alkaline earth metal phenolates, alkali metal or alkaline earth metal alcoholates, tertiary amines such as triethylenediamine, morpholine, pyrrolidine, triethylamine and tribamine and tribamine Metal compounds such as antimony trioxide, zinc chloride, titanium tetrachloride and titanium tetrabutyl ester.
  • basic transesterification catalysts such as alkali metal or alkaline earth metal phenolates, alkali metal or alkaline earth metal alcoholates, tertiary amines such as triethylenediamine, morpholine, pyrrolidine, triethylamine and tribamine and tribamine
  • Metal compounds such as antimony trioxide, zinc chloride, titanium tetrachloride and titanium
  • the catalyst is used in amounts between 10 ppm and 200 ppm, based on the total weight of the polyalkylene oxide di-bis-aryl carbonate which is extended via carbonate groups and the diphenol used in each case.
  • the process according to the invention for the preparation of the polyalkylene oxide di-bis-diphenol carbonates extended via carbonate groups is preferably carried out in the absence of solvents for the reactants, in particular in bulk.
  • solvents which are inert under the reaction conditions such as, for example, aliphatic hydrocarbons, aromatic hydrocarbons which are unsubstituted or substituted, for example, by nitro groups can be used.
  • the reaction time for the transesterification process for the preparation of the polyalkylene oxide di-bis-diphenol carbonates extended via carbonate groups is between 1/2 and 24 hours, depending on the reaction temperature and the type and amount of the catalyst.
  • the polyalkylene oxide di-bis-diphenol carbonates extended via carbonate groups are prepared, for example, by obtaining a mixture of polyalkylene oxide di-bis-phenyl carbonate extended via carbonate groups, in accordance with German patent application P 2 650 533.9 (Le A 17 516) a diphenol and catalyst in a vacuum to temperatures between 100 ° C and 200 ° C, preferably between 110 ° C and 180 ° C, and the phenol formed with the progress of the reaction is distilled off from the reactor.
  • the diphenol is used in excess, more than 1 mol of diphenol, preferably between 1.1 mol and 2 mol of diphenol, being used per carbonic acid phenyl ester group of the polyalkylene oxide di-bisphenyl carbonate.
  • the reaction from a polyalkylene oxide di-bis-phenyl carbonate extended by carbonate groups obtained according to P 2 650 533.9 (Le A 17 516), and bisphenol A in a molar ratio Bis-phenyl carbonate to bisphenol A of 1: 3 at 150 ° C in a vacuum between 25 and 0.1 Torr implemented.
  • P 2 650 533.9 also relates to the aryl bis-carboxylates obtained from polyalkylene oxide diols which are extended by -OCOO groups.
  • poly (ethylene oxide) glycols poly (1,2-propylene) glycols, poly (1,3-propylene oxide) glycols, 'poly- (1,2-butylene oxide) in P glycols, poly (tetrahydrofuran) glycols, the corresponding poly (pentylene oxide) glycols, poly (hexamethylene oxide) glycols, poly (heptamethylene oxide) glycols, poly (octamethylene oxide) glycols, poly ( called nonamethylene oxide) glycols and the copolymers or block copolymers of, for example, ethylene oxide and propylene oxide.
  • Suitable substituents are in particular C 1 -C 4 alkyls and nitro, halogen, such as chlorine or bromine.
  • Examples include diphenyl carbonate, alkyl-substituted diphenyl carbonates such as the di-toluyl carbonates, halogen-substituted diphenyl carbonates such as the di-chlorophenyl carbonates, dinaphthyl carbonate and alkyl-substituted and halogen-substituted dinaphthyl carbonates; the nitro, alkyl or halogen substituents on both phenyl nuclei or on both naphthyl nuclei of the diaryl carbonates can be the same or different or symmetrical or asymmetrical to one another be.
  • phenyltoluyl carbonate phenyl chlorophenyl carbonate, 2-tolyl-4-toluyl carbonate or 4-toluyl-4-chlorophenyl carbonate are also suitable for the process according to the invention.
  • Bis-aryl carbonates of polyalkylene oxide diols extended by -OCOO groups according to P 2 650 533.9 are thus in particular those of the formula III, wherein Ar, R ', R ", a and b have the meaning given above and n is an integer from 2 to 20, preferably 2 to 10.
  • Suitable catalysts for the process according to P 2 650 533.9 are dalkaliphenolate basic transesterification catalysts such as alkali or E r, Alakli- or alkaline earth metal and tertiary amines such as triethylenediamine, morpholine, pyrrolidine, pyridine, triethylamine or metal compounds such as antimony trioxide, zinc chloride, titanium tetrachloride and titanic .
  • dalkaliphenolate basic transesterification catalysts such as alkali or E r, Alakli- or alkaline earth metal and tertiary amines such as triethylenediamine, morpholine, pyrrolidine, pyridine, triethylamine or metal compounds such as antimony trioxide, zinc chloride, titanium tetrachloride and titanic .
  • the catalyst is used in amounts between 20 ppm and 200 ppm, based on the total weight of the polyalkylene oxide polyol and carbonic acid bis-aryl ester used.
  • catalysts can, if appropriate, be undercut if the starting products do not contain any basic impurities when using the acidic catalysts and if they do not contain any acidic impurities when using the basic catalysts. In the interest of one if possible low intrinsic color of the carbonic acid esters of polyalkylene oxide polyols produced according to the invention, the smallest possible amounts of catalyst are preferred.
  • the process according to P 2 650 533.9 is preferably carried out in bulk, ie in the absence of solvent. If appropriate, however, solvents which are inert under the reaction conditions, such as aliphatic hydrocarbons or aromatic hydrocarbons, which may contain nitro groups, for example, can also be used.
  • the reaction time depends on the reaction temperature and the type and amount of the catalyst used and is 1 to 20 hours.
  • the hydroxyaryl compounds formed in the process according to P 2 650 533.9 can be removed after the reaction has ended by separating the hydroxyaryl compounds by distillation during the reaction in a batchwise procedure. If the transesterification reaction is carried out according to a continuous procedure, the hydroxyaryl compounds are separated from the reaction mixture by fractional distillation.
  • polyalkylene oxide diol and carbonic acid bis-aryl ester are reacted with sodium phenolate as catalyst in a mixture at 110 ° C. to 150 ° C., with less than one mole of carbonic acid per OH group of the polyalkylene oxide diol. bis-aryl ester is used.
  • the process according to P 2 650 533.9 can thus be used to prepare bis-carbonic acid monoaryl esters of polyalkylene oxide diols which are extended by -OCOO bridges; it showed up Surprisingly, the extension runs smoothly, with a quantitative esterification of the terminal hydroxyl groups taking place at the same time. It was also surprising that the molecular non-uniformity of the starting polyalkylene oxide diols remains practically unchanged during the elongation with simultaneous esterification.
  • Figure 1 shows the gel permeation chromatograms of some of these bis-carbonic acid monoaryl esters and their starting products: curve (1) shows the gel permeation chromatogram (GPC) of polytetrahydrofuran diol with a molecular weight Mn of 2000. Curve (2) shows its GPC after doubling Mn of 4000 and esterification of the terminal OH groups with diphenyl carbonate. Curve (3) shows the GPC of polytetrahydrofuran diol with a molecular weight M n of 1000; Curves (4), (5) and (6) show its GPC's after doubling, quadrupling and six-fold increase to molecular weights Mn of 2000, 4000 and 6000 and esterification of the terminal OH groups. It can be seen that the molecular non-uniformity, which is determined by the half-width of the GPC curves, remains practically constant.
  • GPC gel permeation chromatogram
  • the desired molecular weight Mn of an extended and esterified polyalkylene oxide diol III is determined by the amount of the diaryl carbonate II reacted with the polyalkylene oxide diol I; it generally applies that n moles I have to be reacted with (n + 1) moles II in order to obtain an n-fold polyalkylene oxide diol with terminal aryl carbonate groups which is extended by -OCOO groups (n has the formula III specified values).
  • known polyalkylene oxide tri can be used in addition to the polyalkylene oxide diols ole and / or known polyalkylene oxide tetraols M n over 135, preferably over 800 in molar amounts, based on moles, of polyalkylene oxide diol used, up to about 50 mol%.
  • the resulting carbonic acid aryl esters according to P 2 650 533.9 have a branched structure.
  • the resulting carbonic acid aryl esters according to P 2 650 533.9 therefore have special end groups.
  • carbonic acid aryl esters obtainable by these variations of the process according to P 2 650 533.9 with the use of polyalkylene oxide mono-ols and / or polyalkylene oxide triols and / or polyalkylene oxide tetrols can, analogously to the invention, only from over -Extended polyalkylene oxide diols manufactured carbonic acid aryl esters are used commercially.
  • the average molecular weights listed in the examples below are number average Rn, which were determined by osmometry.
  • the OH number is zero.
  • the GPC curve of this product is shown as curve (6) in Fig. 1.
  • the diphenols suitable according to the invention can be used both alone and in groups.
  • Polyalkylene oxide di-bis-diphenol carbonates extended by carbonate groups according to the invention are thus, for example, those of the formulas Va-Vh: R ', R ", n, a and b have the meanings given for the formulas I and III in the formulas Va to Vh .
  • polyalkylene oxide di-bis-diphenol-darbonates extended by carbonate groups according to the invention can be used as starting bisphenols in the production of polycarbonates by the known two-phase interfacial polycondensation process. This gives polyether polycarbonates of a certain structure.
  • the process according to the invention for the production of these polyether polycarbonates is characterized in that the polyalkylene oxide diol diols extended by carbonate groups according to the invention are bis-diphenol carbonates, in particular those of formula V, with other diphenols, in particular with those of formula IV, and with phosgene according to the two-phase interfacial polycondensation process known for polycarbonate production at pH values between 9 and 14 and temperatures between 0 ° C. and 80 ° C, preferably between 15 ° C and 40 ° C.
  • the polyether polycarbonates obtained according to the invention are characterized by the presence of an amorphous (soft) polyether phase and a crystalline (hard) polycarbonate phase or an amorphous-crystalline (hard) polycarbonate phase.
  • the polyether polycarbonates have two different, spatially separated phases, i.e. Areas composed of a continuous amorphous polyether phase and a crystalline or amorphous-crystalline polycarbonate phase.
  • polyether polycarbonates made from polyalkylene oxide di-bis-diphenol carbonates which are extended via carbonate groups, show additional advantages over other polyether polycarbonates, for example also those of German Offenlegungsschrift No. 2,636,784 (Le A 17 025) , such as an even better phase separation, which leads to better performance properties of the corresponding polyether polycarbonates.
  • the polyether polycarbonates according to the invention have better heat resistance than comparable single-phase polyether polycarbonates.
  • Single-phase polyether polycarbonates are described, for example, in U.S. Patent 3,151,615. They can be obtained by various processes, but preferably by the "pyridine process" known from polycarbonate production.
  • polyalkylene oxide di-bis-diphenol carbonates extended via carbonate groups has the advantage over the use of corresponding bischloroformic acid esters that they are insensitive to hydrolysis and thus have better storage stability and clearly bifunctional reactivity.
  • the polyether polycarbonates according to the invention have improved heat resistance, in particular because of their crystalline polycarbonate phase.
  • the different phases of the polyether polycarbonates according to the invention can be identified with the aid of differential thermal analysis, for example the polyether phase having a glass transition temperature ⁇ 20 ° C, the amorphous fraction in the polycarbonate phase having a glass transition temperature between 100 ° C and 150 ° C and the crystalline fraction Polycarbonate phase has a crystallite melting point between 170 o C and 250 ° C.
  • 2,2-Bis- (4-hydroxyphenyl) propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) propane, 2,2 are preferred as other diphenols for the production of the polyether polycarbonates according to the invention -Bis (3,5-dibromo-4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclohexane are used. Any mixtures of these other diphenols can also be used.
  • trifunctional or more than trifunctional compounds in particular those with three or more than three phenolic hydroxyl groups, preferably between 0.05-2 mol% (based on the diphenols used), branched products are obtained better flow behavior during processing.
  • the polyether polycarbonates according to the invention can also be branched via the polyether component, specifically by using the carboxylate aryl esters of polyether polyols with three or four aryl groups which are available according to patent application P 2 650 533.9 (Le A 17 516) the above-mentioned di-, tri- and / or tetraphenols to corresponding polyether polyol polyphenol carbonates according to the process of the present invention, and the polyphenols thus obtained in molar amounts up to 50 mol.-96, based on mol of polyether diol bis used diphenol carbonates, also used in the polyether-polycarbonate synthesis according to the present invention.
  • the chain length of the polyether polycarbonates can be increased by adding a chain terminator, e.g. a monofunctional phenol such as phenol, 2,6-dimethylphenol, p-bromophenol or p-tert-butylphenol can be set, it being possible to use between 0.1 and 10 mol% of chain terminator per mole of diphenol used.
  • a chain terminator e.g. a monofunctional phenol such as phenol, 2,6-dimethylphenol, p-bromophenol or p-tert-butylphenol can be set, it being possible to use between 0.1 and 10 mol% of chain terminator per mole of diphenol used.
  • the chain length of the polyether polycarbonates can be added, for example, by adding polyether monool monodiphenol carbonates in molar amounts, based on moles used carbonate group-extended polyetherdiol-bis-diphenol carbonates, up to about 50 mol%.
  • the high-molecular, segmented, thermoplastically processable polyether polycarbonates are produced according to the invention by the two-phase interface polycondensation process.
  • one of the aforementioned other diphenols or mixtures of the aforementioned other diphenols are dissolved in an alkaline aqueous solution.
  • the polyalkylene oxide di-bis-diphenyol carbonates, in particular those of the formula V, or their mixtures thereof, which are extended by carbonate grouppen are dissolved and added in an inert organic solvent which is immiscible with water. Then at a temperature between 0 ° C and 80 ° C, preferably between 15 ° C and 40 ° C and a pH between 9 and 14 phosgene.
  • the polycondensation is carried out by adding 0.2-10 mol% of tertiary aliphatic amine, based on mol of diphenol. Times between 5 minutes and 90 minutes are required for phosgenation and times between 3 minutes and 3 hours for polycondensation.
  • the present invention thus relates to the preparation of polyether polycarbonates, which is characterized in that the polyalkylene oxide di-bis-diphenol carbonates, in particular those of the formula V, which are extended via carbonate groups, with other diphenols, in particular those of the formula IV, and with phosgene in a liquid mixture of inert organic solvent and alkaline aqueous solution at temperatures between 0 ° C and 80 o C, preferably reacted between 15 ° C and 40 ° C, at a pH value between 9 and 14, and after the phosgene addition by addition of 0.2 mol% to 10 mol% of tertiary aliphatic amine, based on the molar amount of diphenol, polycondensed, the weight ratio Ratio of polyalkylene oxide di-bis-diphenol carbonate extended to carbonate groups to other diphenol is determined by the polycarbonate content and the polyether content of the polyether polycarbonates.
  • the present invention thus relates to polyether polycarbonates obtained by this process according to the invention.
  • Suitable inert organic solvents for the production process of the polyether polycarbonates according to the invention are water-immiscible aliphatic chlorinated hydrocarbons such as methylene chloride, chloroform and 1,2-dichloroethane, or chlorinated aromatics such as chlorobenzene, dichlorobenzene and chlorotoluene or mixtures of these solvents.
  • Solutions of Li OH, NaOH, KOH, Ca (OH) 2 and / or Ba (OH) 2 in water are suitable as alkaline aqueous solutions for the process according to the invention.
  • the gelation of the polyether polycarbonates produced by the process according to the invention is carried out by cooling the high-percentage polymer solution, depending on the gelation Polyether or polycarbonate content times between 5 minutes and 12 hours at temperatures between 0 ° C and 40 ° C are required.
  • the gelled product can be worked up to a powder grain mixture, the polyether polycarbonate obtained being dried in vacuo for 48 hours at 50 ° C. and for 24 hours at 100 ° C.
  • Organic solvents such as methylene chloride, benzene, toluene or xylene are suitable as solvents for the separate gelation of the isolated polyether polycarbonates.
  • the insulated polyether polycarbonates are tempered between 5 minutes and 24 hours at temperatures between 40 ° C and 170 ° C.
  • the action of shear forces on the isolated polyether polycarbonates takes place between 0.5 and 30 minutes, at temperatures between 130 and 240 o C and under shear forces between 0.2 and 0.7 KWh per kg polymer.
  • the amount of phosgene depends on the diphenol used, the stirring action and the reaction temperature, which can be between about 0 ° C. and about 80 ° C., and is generally 1.1-3.0 mol of phosgene per mol of diphenol.
  • the proportion of polycarbonate in the polyether polycarbonates produced by the process according to the invention is, depending on the desired property profile, approximately between 30 and 95, preferably approximately between 35 and 80% by weight, the hardness and heat resistance increasing with increasing polycarbonate content, and the elasticity and elongation at break decreases.
  • the polycarbonate content of the polyether polycarbonates according to the invention is the amount by weight of aromatic polycarbonate structural units of the following formula VI where D stands for the diphenolate residues in the polyether polycarbonate, in particular to understand aromatic polycarbonate structural units of the formula IVa wherein X and Y 1 to Y 4 have the meaning given for formula IV.
  • the polyether fraction of the polyether polycarbonates according to the invention is therefore to be understood as the amount by weight of polyalkylene oxide diolate block units which are extended by carbonate groups, in particular those of the formula VII, wherein R ', R ", a, b have the meaning given for the formula I and n is an integer from 2 to 20, preferably 2-10.
  • the present invention thus also relates to polyether polycarbonates which are characterized in that they contain from approximately 30 to 95% by weight, preferably approximately from 35 to 80% by weight, of aromatic polycarbonate structural units of the formula VI, in particular those of the formula IVa, and approximately 70 to 5% by weight, preferably approximately 65 to 20% by weight, of polyalkylene oxide diolate block units extended by carbonate groups, in particular those of the formula VII.
  • the polyether polycarbonates according to the invention should have average molecular weights Mw (weight average) of 25,000 to 250,000, preferably from 40,000 to 150,000, determined by the light scattering method with the scattered light photometer.
  • the relative solution viscosities ⁇ rel. (measured on 0.5 g in 100 ml of CH 2 C1 2 at 25 ° C.) of the polyether polycarbonates according to the invention are between 1.3 and 3.0, preferably between 1.4 and 2.6.
  • the high molecular weight, segmented, thermoplastically processable polyether polycarbonates produced by the process according to the invention are characterized in that, measured by means of differential thermal analysis, the polyether content is amorphous and a freezing temperature between -100 ° C. and + 100 ° C., preferably between -80 ° C. and + 20 ° C, and that the polycarbonate portion is partially crystalline with a crystallite melting temperature of the crystalline polycarbonate portion of at least 160 ° C, preferably between 165 ° C and 250 ° C, and that the glass transition temperature of the amorphous polycarbonate portion is over 80 ° C, preferably over 100 ° C.
  • This differentiation of the freezing temperature of the polyether fraction from the freezing temperature and the crystallite melting temperature of the polacarbonate fraction is characteristic of the phase separation of the polyether and polycarbonate fraction.
  • the partial crystallinity detectable by a measurable heat of fusion of the crystalline polycarbonate portion of the erfindungsgemüssen polyether polycarbonates, containing at least 1 - is 8 cal / g of polymer, can be prepared by stretching and by the mentioned post-annealing (5 min to 24 hours.) At 40-170 0 C or by the aforementioned action of shear forces during the thermoplastic processing in a multi-screw extruder can be increased by 50%, whereby the heat resistance of the products increases, the appearance changes from transparent to opaque to opaque.
  • the partially crystalline elastic polyether polycarbonates can in each case below or in the region of the crystallite melting point of the crystalline polycarbonate component at temperatures from 130 ° C. to max. 250 0 C are processed thermoplastic, whereby a substantial proportion of the crystallinity is not lost. At processing temperatures above the crystalline melting point of the crystalline polycarbonate content, amorphous, transparent products are obtained.
  • the crystalline fraction of the polycarbonate fraction of the polyether polycarbonates according to the invention can thus be varied, the enthalpy of fusion of the crystalline polycarbonate fraction, in order to have good heat resistance of the polyether polycarbonates in practice, at about 1-8 cal / g polymer, preferably at 2, 5-5.5 cal / g polymer is.
  • the processing and isolation of the polyether polycarbonates according to the invention takes place without annealing and without gelling and without the action of shear forces, one obtains single-phase polyether polycarbonates, that is to say products with only a freezing temperature which can be measured by means of differential thermal analysis.
  • the UV stability and hydrolysis stability of the polyether polycarbonates according to the invention can be improved by the amounts of UV stabilizing agents which are customary for thermoplastic polycarbonates, such as, for example, substituted “benzophenones” or “benzotriazoles”, by hydrolysis protective agents, such as, for example, mono- and especially polycarbodiimides (cf. W. Neumann, J. Peter, H. Holtschmidt and W. Kallert, Proceeding of the 4th Rubber Technology Conference, London, May 22-25, 1962, pp. 738-751) in amounts of 0.2-5 wt. -%, based on the weight of the polyether polycarbonates, and by anti-aging agents known in the chemistry of thermoplastic polyethers and thermoplastic polycarbonates.
  • UV stabilizing agents which are customary for thermoplastic polycarbonates, such as, for example, substituted “benzophenones” or “benzotriazoles”
  • hydrolysis protective agents such as, for example, mono- and especially polycarbodiimides (cf.
  • substances such as carbon black, kieselguhr, kaolin, clays, CaF 2 , CaC0 3 , aluminum oxides and conventional glass fibers in amounts of 2 to 40% by weight, based in each case on the total weight of the molding composition and inorganic pigments, can be used both as Fillers as well as nucleating agents are added.
  • Be flame-resistant products desired about 5 to 15 wt .-%, each based on the weight of the polyether polycarbonates, known in the chemistry of thermoplastic polyethers and thermoplastic polycarbonates flameproofing - medium, such as antimony trioxide, tetrabromophthalic anhydride, hexabromocyclododecane, tetrachlorophthalic or tetrabromobisphenol-A or tris (2,3-dichloropropyl) phosphate are added, with the polycarbonate fractions of those according to the invention Polycarbonate statistically incorporated tetrachloro- and tetrabromobisphenols also show flame retardant properties.
  • polyether polycarbonates known in the chemistry of thermoplastic polyethers and thermoplastic polycarbonates flameproofing - medium, such as antimony trioxide, tetrabromophthalic anhydride, hexabromocyclododecane, tetrachloro
  • thermoplastic polyethers and thermoplastic polycarbonates can be used effectively.
  • polyethers obtained by the process according to the invention.
  • Polycarbonates can advantageously be used wherever a combination of hardness and elasticity, in particular cold flexibility, is desired, e.g. in body construction, for the production of low-pressure tires for vehicles, for wrapping hoses, plates, pipes and for flexible drive pulleys.
  • the average molecular weights listed in the examples below are number average Rn and determined by determining the OH number.
  • the Staudinger index [ ⁇ ] given in example A was measured in THF at 25 ° C and in g specified.
  • the relative solution viscosity ⁇ rel of Examples C 1 -C 6 is defined by the viscosity of 0.5 g of polyether polycarbonate in 100 ml of methylene chloride at 25 ° C.
  • the tensile strength and the elongation at break were measured according to DIN 53 455 and 53 457, respectively.
  • the differential thermal analysis (DTA) was carried out with the device "DuPont, model 900". To interpret the freezing temperature, the approximate middle of the softening range was chosen according to the tangent method and the approximate center of the endothermic peak of the melting curve for the crystallite melting point.
  • a finely divided solid product is obtained by distilling off the solvent, drying in a vacuum drying cabinet at about 80-110 ° C. and 15 torr and then grinding.
  • the polyether polycarbonate shows a maximum at 40,000. It has 50% by weight of polyether and 50% by weight of polycarbonate.
  • Some mechanical properties of a film cast from methylene chloride are: tear strength 45.9 (MPA) (measured according to DIN 53 455), elongation at break 483% (measured according to DIN 53 455).
  • the granulated polyether polycarbonate shows a glass transition temperature of the polyether portion of -75 ° C, a glass transition temperature of the polycarbonate of 145 ° C and a crystallite melting point of the polycarbonate portion of approx. 215 ° C.
  • the granulated polyether polycarbonate shows a glass transition temperature of the polyether portion of -57 ° C, a glass transition temperature of the polycarbonate of 145 ° C and a crystallite melting point of the polycarbonate portion of approx. 195 ° C.
EP78100103A 1977-06-11 1978-06-06 Procédé de préparation de bis-carbonates de diphénols et de polyoxyalkylèneglycols allongés par des groupes carbonates; leur application à la préparation de polyéthers polycarbonates thermoplastiques à blocs de haut poids moléculaire. Expired EP0000060B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772726416 DE2726416A1 (de) 1977-06-11 1977-06-11 Verfahren zur herstellung von kohlensaeure-bis-diphenol-estern von ueber carbonat-gruppen-verlaengerten polyalkylenoxiddiolen und ihre verwendung zur herstellung von hochmolekularen, segmentierten, thermoplastisch verarbeitbaren polyaether-polycarbonaten
DE2726416 1977-06-11

Publications (2)

Publication Number Publication Date
EP0000060A1 true EP0000060A1 (fr) 1978-12-20
EP0000060B1 EP0000060B1 (fr) 1980-08-06

Family

ID=6011311

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100103A Expired EP0000060B1 (fr) 1977-06-11 1978-06-06 Procédé de préparation de bis-carbonates de diphénols et de polyoxyalkylèneglycols allongés par des groupes carbonates; leur application à la préparation de polyéthers polycarbonates thermoplastiques à blocs de haut poids moléculaire.

Country Status (5)

Country Link
US (1) US4217437A (fr)
EP (1) EP0000060B1 (fr)
JP (2) JPS545943A (fr)
DE (2) DE2726416A1 (fr)
IT (1) IT1105136B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0213465A2 (fr) * 1985-08-22 1987-03-11 General Electric Company Copolymères blocs polycarbonate-polyether, mélanges de polymère contenant ceux-ci et intermédiaires pour leur production
EP0584740A1 (fr) * 1992-08-21 1994-03-02 Hodogaya Chemical Co., Ltd. Résine de polycarbonate souple
WO2000023498A1 (fr) * 1998-10-22 2000-04-27 General Electric Company Preparation de copolycarbonate par polymerisation a l'etat solide
US6143859A (en) * 1999-08-09 2000-11-07 General Electric Company Copolycarbonate preparation by solid state polymerization

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2930787A1 (de) 1979-07-28 1981-02-12 Bayer Ag Vernetzbare polycarbonat-elastomere, ein verfahren zu ihrer herstellung und ihre verwendung fuer medizinische verpackungen nach erfolgter vernetzung
US4476293A (en) * 1981-11-30 1984-10-09 E. I. Du Pont De Nemours And Company Polymeric carbonate diols of copolyether glycols and polyurethanes prepared therefrom
US4463141A (en) * 1981-11-30 1984-07-31 E. I. Du Pont De Nemours And Company Polyether carbonate diols and polyurethanes prepared therefrom
EP0135760A1 (fr) * 1983-08-19 1985-04-03 Bayer Ag Polyéther-polycarbonates pour membranes de dialyse
DE3408804A1 (de) * 1983-09-30 1985-04-18 Bayer Ag, 5090 Leverkusen Polyether-copolycarbonate fuer dialysemembranen
US4642321A (en) * 1985-07-19 1987-02-10 Kollmorgen Technologies Corporation Heat activatable adhesive for wire scribed circuits
US4657977A (en) * 1985-10-04 1987-04-14 General Electric Company Poly(etherimide-carbonate) block copolymers and polymer blends containing same
US4806599A (en) * 1987-12-21 1989-02-21 The Dow Chemical Company Polyolefin/polycarbonate/polyolefin triblock copolymers
US4812530A (en) * 1987-12-28 1989-03-14 The Dow Chemical Company Polyether-polycarbonate-polyether triblock copolymers
DE4004882A1 (de) * 1990-02-16 1991-08-22 Basf Ag Polyetherpolycarbonatdiole
DE4004881C1 (fr) * 1990-02-16 1991-02-07 Basf Ag, 6700 Ludwigshafen, De
DE4232416A1 (de) * 1992-09-28 1994-03-31 Basf Ag Schlagzähe Polyoxymethylenformmassen
US6333394B1 (en) * 1999-08-09 2001-12-25 General Electric Company Copolycarbonate preparation by solid state polymerization
DE10219028A1 (de) * 2002-04-29 2003-11-06 Bayer Ag Herstellung und Verwendung von hochmolekularen aliphatischen Polycarbonaten
US7230066B2 (en) * 2004-12-16 2007-06-12 General Electric Company Polycarbonate—ultem block copolymers
BR112020018358A2 (pt) * 2018-03-09 2020-12-29 Evonik Canada Inc. Macromoléculas modificadoras de superfície ligadas a carbonato

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2650533A1 (de) * 1976-11-04 1978-05-18 Bayer Ag Verfahren zur herstellung von kohlensaeurearylestern von ueber carbonat- gruppen-verlaengerten polyalkylenoxiddiolen

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3069385A (en) * 1962-12-18 Chain extending polycarbonate
US3161615A (en) * 1957-02-05 1964-12-15 Gen Electric Resinous copolymeric polycarbonate of a mixture of dihydric phenols
US3030331A (en) * 1957-08-22 1962-04-17 Gen Electric Process for preparing copolyesters comprising reacting a carbonyl halide with a dicarboxylic acid and a dihydroxy compound in the presence of a tertiary amine
BE570531A (fr) * 1957-08-22
BE570530A (fr) * 1957-08-22
US3030335A (en) * 1959-01-02 1962-04-17 Gen Electric Aromatic polycarbonate reaction products
DE1495626B1 (de) * 1960-03-30 1971-06-09 Bayer Ag Verfahren zum herstellen von polyestern
US3207814A (en) * 1961-01-03 1965-09-21 Gen Electric Carbonate-polyester copolymer resinous compositions
US3290409A (en) * 1962-03-08 1966-12-06 Gen Electric Preparation of polycarbonate resins
US3287442A (en) * 1962-10-18 1966-11-22 Eastman Kodak Co Polycarbonate elastomers
US3449467A (en) * 1965-06-03 1969-06-10 Union Carbide Corp Hydroxyl terminated polyester oligomers
US3461187A (en) * 1965-12-02 1969-08-12 Gen Electric Graft copolymers of polycarbonate on an addition polymer backbone
DE1493757A1 (de) * 1965-12-29 1969-01-30 Bayer Ag Verfahren zur Herstellung von gemischten Kohlensaeureestern
US3843708A (en) * 1969-01-17 1974-10-22 Union Carbide Corp Extended polylactone diol compositions
JPS495630B1 (fr) * 1970-03-19 1974-02-08
DE2217470A1 (de) * 1971-04-13 1972-11-02 Denki Onkyo Co. Ltd., Tokio Block-Copolymerisate
US4105633A (en) * 1977-05-11 1978-08-08 The Dow Chemical Company Alternating copolyestercarbonate resins

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2650533A1 (de) * 1976-11-04 1978-05-18 Bayer Ag Verfahren zur herstellung von kohlensaeurearylestern von ueber carbonat- gruppen-verlaengerten polyalkylenoxiddiolen

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0213465A2 (fr) * 1985-08-22 1987-03-11 General Electric Company Copolymères blocs polycarbonate-polyether, mélanges de polymère contenant ceux-ci et intermédiaires pour leur production
EP0213465A3 (en) * 1985-08-22 1987-12-16 General Electric Company Polycarbonate-polyether block copolymers, polymer blends containing same and intermediates for the production thereof
EP0584740A1 (fr) * 1992-08-21 1994-03-02 Hodogaya Chemical Co., Ltd. Résine de polycarbonate souple
US5360889A (en) * 1992-08-21 1994-11-01 Hodogaya Chemical Co., Ltd. Soft polycarbonate resin
WO2000023498A1 (fr) * 1998-10-22 2000-04-27 General Electric Company Preparation de copolycarbonate par polymerisation a l'etat solide
US6143859A (en) * 1999-08-09 2000-11-07 General Electric Company Copolycarbonate preparation by solid state polymerization

Also Published As

Publication number Publication date
JPS545943A (en) 1979-01-17
US4217437A (en) 1980-08-12
EP0000060B1 (fr) 1980-08-06
JPH0231100B2 (fr) 1990-07-11
IT7849789A0 (it) 1978-06-09
DE2860110D1 (en) 1980-11-27
DE2726416A1 (de) 1978-12-21
JPS6211724A (ja) 1987-01-20
JPH022887B2 (fr) 1990-01-19
IT1105136B (it) 1985-10-28

Similar Documents

Publication Publication Date Title
EP0000060B1 (fr) Procédé de préparation de bis-carbonates de diphénols et de polyoxyalkylèneglycols allongés par des groupes carbonates; leur application à la préparation de polyéthers polycarbonates thermoplastiques à blocs de haut poids moléculaire.
EP0006516B1 (fr) Procédé de préparation de polycarbonates aromatiques-aliphatiques à terminaison diphénylcarbonate, les polycarbonates ainsi obtenus et leur utilisation dans un procédé de préparation de polycarbonates segmentés élastoméres et les élastomères ainsi obtenus
EP0025937B1 (fr) Polycarbonates thermoplastiques, procédé pour leur préparation, bis-halo-formates d'hexahydro-furo (3,2-b) furane-3,6-dioles, et compositions à base de polycarbonates
US4297455A (en) Process for the preparation of carbonic acid aryl esters of polyester-diols lengthened via carbonate groups and their use for the preparation of polyester-diol bis-diphenol carbonates and polyester/polycarbonates
DE2702626C2 (fr)
DE2636783C2 (de) Verfahren zur Herstellung von hochmolekularen, segmentierten, thermoplastisch verarbeitbaren Polyester-Polycarbonaten
EP0004020B1 (fr) Masses à mouler à ténacité améliorée à base de polycarbonates
DE4419229A1 (de) Neue Polyester aus Dimerfettsäure und Dimerfettdiol und ihre Verwendung zur Herstellung von Polyestercarbonaten
EP0033089A2 (fr) Oligocarbonates hétérocycliques-aromatiques, leur préparation, leur utilisation pour la fabrication de copolycarbonates hétérocycliques-aromatiques à haut poids moléculaire, ces copolycarbonates et leurs mélanges avec d'autres thermoplastiques
EP2336245A1 (fr) Compositions de polycarbonate dotées d'une dureté de surface améliorée
US4216298A (en) Process for the preparation of carbonic acid bis-diphenol esters of polyester-diols and their use for the preparation of high-molecular segmented polyester/polycarbonates which can be processed as thermoplastics
DE2712435C2 (fr)
DE2651639A1 (de) Verfahren zur herstellung von kohlensaeureestern von polyesterpolyolen
EP0097861B1 (fr) Polyestercarbonate aromatique ayant une résistance au choc et procédé pour sa préparation
EP0201830B1 (fr) Procédé pour la préparation de copolyphosphonates ayant une haute résistance au choc sur barreau entaillé
DE2636784A1 (de) Verfahren zur herstellung von kohlensaeure-bis-diphenolestern von polyalkylenoxiddiolen und ihre verwendung zur herstellung von hochmolekularen, segmentierten, thermoplastisch verarbeitbaren polyaether-polycarbonaten
EP0065728B1 (fr) Copolyestercarbonates et leur mélange avec des polycarbonates connus pour former des masses à mouler thermoplastiques
DE2726417C2 (fr)
EP0024672A1 (fr) Polycarbonates segmentés, aromatiques, thermoplastiques à haut poids moléculaire préparés par condensation d'esters d'acides gras dimérisés, leur préparation et utilisation
DE2650533A1 (de) Verfahren zur herstellung von kohlensaeurearylestern von ueber carbonat- gruppen-verlaengerten polyalkylenoxiddiolen
WO2008119485A1 (fr) Polycarbonates, carbonates de polyester modifiés possédant un comportement de dilatation et de résistance à la flamme améliorés
DE2726376C2 (fr)
DE2619831A1 (de) Verfahren zur herstellung von kohlensaeurearylestern von polyalkylenoxidpolyolen
EP0077415B1 (fr) Compositions à base de polycarbonates élastomères, contenant sous forme condensée des esters d'acides gras dimères hydrogénés, et de polyoléfines et, éventuellement, d'autres polycarbonates
EP0442062B1 (fr) Polyacrylate monofonctionnelle, sa préparation et l'application à la préparation de polycarbonates

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB

17P Request for examination filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

REF Corresponds to:

Ref document number: 2860110

Country of ref document: DE

Date of ref document: 19801127

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19930526

Year of fee payment: 16

Ref country code: FR

Payment date: 19930526

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19940516

Year of fee payment: 17

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19940606

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19940606

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19950228

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19960301

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT