EP0000060B1 - Verfahren zur Herstellung von Kohlensäure-bis-diphenol-estern von über Carbonat-Gruppen-verlängerten Polyalkylenoxiddiolen und ihre Verwendung zur Herstellung von hochmolekularen, segmentierten, thermoplastisch verarbeitbaren Polyäther-Polycarbonaten. - Google Patents

Verfahren zur Herstellung von Kohlensäure-bis-diphenol-estern von über Carbonat-Gruppen-verlängerten Polyalkylenoxiddiolen und ihre Verwendung zur Herstellung von hochmolekularen, segmentierten, thermoplastisch verarbeitbaren Polyäther-Polycarbonaten. Download PDF

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Publication number
EP0000060B1
EP0000060B1 EP78100103A EP78100103A EP0000060B1 EP 0000060 B1 EP0000060 B1 EP 0000060B1 EP 78100103 A EP78100103 A EP 78100103A EP 78100103 A EP78100103 A EP 78100103A EP 0000060 B1 EP0000060 B1 EP 0000060B1
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bis
polyalkylene oxide
polyether
diphenol
weight
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German (de)
English (en)
French (fr)
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EP0000060A1 (de
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Manfred Dr. Schreckenberg
Dieter Dr. Freitag
Christian Dr. Lindner
Carlhans Dr. Süling
Herbert Dr. Bartl
Klaus Dr. König
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Bayer AG
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Bayer AG
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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
    • C08G64/18—Block or graft polymers
    • C08G64/183—Block or graft polymers containing polyether sequences

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  • DE-A 2 650 533 claims a process for the clarification of carbonic acid aryl esters of polyalkylene oxide diols made from polyalkylene oxide diols with Mn over 135, preferably over 800, and carbonate group-elongated carbonic acid-bisaryl esters, which is characterized in that polyalkylene oxide diols with molecular weights Mn over 135, at temperatures between 100 ° C and 200 ° C in a vacuum below 35 torr together with carbonic acid bis-aryl esters in the presence of catalysts, with less than one mole of carbonic acid bis-aryl ester being used per OH group, and the hydroxylaryl compound formed being distilled off becomes.
  • the present invention now relates to the use of the carbonic acid aryl esters obtainable according to DE-A 2 650 533 mentioned above 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.
  • the process according to the invention is characterized in that polyalkylene oxide diol bis-aryl carbonates which are extended by carbonate groups and are obtainable according to DE-A 2 650 533 by polyalkylene oxide diols with molecular weights Mn (number average) above 135, preferably above 800, with carbonic acid bis-aryl esters at temperatures between 100 ° C and 200 ° C, preferably between 110 ° C and 180 ° C, in a vacuum below 35 torr, preferably between 25 torr and 0.1 torr, in the presence of catalysts, where less than one mole of carbonic acid bis-aryl ester is used per OH group of the polyalkylene oxide diol, and the resulting hydroxyaryl compound is distilled off, with diphenols 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 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 pyridine or 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 pyridine or metal compounds such as antimony trioxide, zinc chloride, titanium tetrachloride and titanium tetrabutyl ester.
  • 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 may be 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 by carbonate groups are prepared, for example, by obtaining a mixture of polyalkylene oxide di-bis-phenyl carbonate extended by carbonate groups in accordance with German patent application P 2 650 533.9 ( Le A 17 516) a diphenol and catalyst are heated in a vacuum to temperatures between 100 ° C. and 200 ° C., preferably between 110 ° C. and 180 ° C., and the phenol formed as the reaction progresses is distilled off from the reactor.
  • the diphenol is used in excess, with 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-bis-phenyl carbonate.
  • polyalkylene oxide di-bis-diphenol carbonates which are lengthened via carbonate groups and which are lengthened via carbonate groups and which are lengthened polyalkylene oxide di-bis-aryl carbonates which are lengthened by carbonate groups are prepared in accordance with DE-A 2 650 533.
  • 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 111 in the formulas Va to Vh.
  • polyalkylene oxide di-bis-diphenol carbonates 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 preparation of these polyether polycarbonates is characterized in that the polyalkylene oxide di-bis-diphenol carbonates according to the invention which are extended via carbonate groups, in particular those of the formula V, with other diphenols, in particular with those of the formula IV, and with Reacts phosgene according to the two-phase interfacial polycondensation process known for polycarbonate production at pH values between 9 and 14 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 2,636,784, e.g. 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.
  • the use according to the invention of the polyalkylene oxide di-bis-diphenol carbonates extended by carbonate groups according to the invention 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 ° C and 250 ° C.
  • the high molecular weight, segmented, thermoplastically processable polyether polycarbonates, produced by the process according to the invention show not only the special thermal resistance, but also good transparency, highly elastic behavior and excellent tear resistance of > 400%.
  • 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, in that the aryl esters of carbonic acid aryl esters of polyether polyols having three or four aryl groups, which are extended by carbonate groups and extended according to DE-A 2 650 533, can be branched with the di-, Tri- and / or tetraphenols to corresponding polyether polyol polyphenol carbonates according to the process of the present invention, and the resulting polyphenols in molar amounts up to 50 mol%, based on moles of polyether diol bis-diphenol carbonates used the polyether-polycarbonate synthesis used in accordance with 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 adjusted, for example, by adding polyether monool monodiphenol carbonates in molar amounts, based on moles of carbonate group-extended polyether diol bis-diphenol carbonates, to 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 polyakylene oxide di-bis-diphenyol carbonates extended by carbonate groups according to the invention, in particular those of formula V, or their mixtures are dissolved and added in an inert organic solvent which is not miscible 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 ° C, preferably between 15 ° C and 40 ° C, at a pH between 9 and 14, and after the phosgene is polycondensed by adding 0.2 mol% to 10 mol% of tertiary aliphatic amine, based on the molar amount of diphenol, the weight ratio of polyalkylene oxide diol bis-diphenol carbonate extended to carbonate groups to other diphenol of the polycarbonate content and the polyether content of the polyether polycarbonates is determined.
  • 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-dichloroethene, 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, whereby for the gelation each Depending on the amount of polyether or polycarbonate, 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 ° 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 reaction according to the invention of the polyalkylene oxide di-bis-diphenol carbonates according to the invention extended via carbonate groups with diphenols and with phosgene is carried out quantitatively; the respective reactant ratio of polyalkylene oxide di-bis-diphenol carbonate extended via carbonate groups to other diphenol is thus determined from the polycarbonate fraction and the polyether fraction to be synthesized in each case polyether polycarbonates.
  • 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 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 formula 1 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 about 30 to 95% by weight, preferably about 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 which are extended by carbonate groups, in particular those of the formula VII.
  • the polyether polycarbonates according to the invention should have average molecular weights Nlw (weight average) of 25,000 to 250,000, preferably from 40,000 to 150,000, determined by the light scattering method using the scattered light photometer.
  • the relative solution viscosities q rel. (measured on 0.5 g in 100 ml CH 2 Cl 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 portion from the freezing temperature and the crystallite melting temperature of the polycarbonate portion is characteristic of the phase separation of the polyether and polycarbonate portion.
  • the partial crystallinity which can be demonstrated by a measurable enthalpy of fusion of the crystalline polycarbonate portion of the polyether polycarbonates according to the invention, which is at least 1-8 cal / g polymer, can be achieved by stretching and by the subsequent post-annealing (5 minutes to 24 hours) at 40-170 ° 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 ° 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 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 polycarbodumides (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% by weight. %, 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 polycarbodumides (cf. W. Neumann
  • 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.
  • flame-retardant products are desired, about 5 to 15% by weight, based on the weight of the polyether polycarbonates, of flame retardants known in the chemistry of thermoplastic polyethers and thermoplastic polycarbonates, such as e.g. Antimony trioxide, tetrabromophthalic anhydride, hexabromocyclododecane, tetrachloro- or tetrabromobisphenol-A or tris (2,3-dichloropropyl) phosphate are admixed, with statistically incorporated tetrachloro- and tetrabromobisphenols also showing flame retardant properties in the polycarbonate fractions of the polycarbonates according to the invention.
  • flame retardants known in the chemistry of thermoplastic polyethers and thermoplastic polycarbonates, such as e.g. Antimony trioxide, tetrabromophthalic anhydride, hexabromocyclododecane, tetrach
  • thermoplastic polyethers and thermoplastic polycarbonates can be used effectively.
  • the polyether polycarbonates obtained by the process according to the invention can advantageously be used wherever a combination of hardness and elasticity, in particular low-temperature 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 following examples are number average Mn and determined by determining the OH number.
  • the Staudinger index [ 1]] given in example A was measured in THF at 25 ° C and in 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.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP78100103A 1977-06-11 1978-06-06 Verfahren zur Herstellung von Kohlensäure-bis-diphenol-estern von über Carbonat-Gruppen-verlängerten Polyalkylenoxiddiolen und ihre Verwendung zur Herstellung von hochmolekularen, segmentierten, thermoplastisch verarbeitbaren Polyäther-Polycarbonaten. Expired EP0000060B1 (de)

Applications Claiming Priority (2)

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DE2726416 1977-06-11
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

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EP0000060A1 EP0000060A1 (de) 1978-12-20
EP0000060B1 true EP0000060B1 (de) 1980-08-06

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US (1) US4217437A (enrdf_load_stackoverflow)
EP (1) EP0000060B1 (enrdf_load_stackoverflow)
JP (2) JPS545943A (enrdf_load_stackoverflow)
DE (2) DE2726416A1 (enrdf_load_stackoverflow)
IT (1) IT1105136B (enrdf_load_stackoverflow)

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FR2235965A1 (en) 1973-06-15 1975-01-31 Ugine Kuhlmann Sequenced polycarbonate-polycaprolactone copolymers - prepd. from oligomers with reactive end gps
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Also Published As

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JPH0231100B2 (enrdf_load_stackoverflow) 1990-07-11
DE2860110D1 (en) 1980-11-27
JPH022887B2 (enrdf_load_stackoverflow) 1990-01-19
EP0000060A1 (de) 1978-12-20
IT1105136B (it) 1985-10-28
DE2726416A1 (de) 1978-12-21
JPS545943A (en) 1979-01-17
JPS6211724A (ja) 1987-01-20
US4217437A (en) 1980-08-12
IT7849789A0 (it) 1978-06-09

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