Classifications

• • 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
  • C08J5/18—Manufacture of films or sheets
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
  • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
  • C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
  • C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
  • C08G18/3868—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide group
• • 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
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

• the present invention relates to new polyurethane plastics which have been produced using optionally substituted, thio group-containing araliphatic diamines as chain extenders.
• the present invention is based on the object of avoiding the disadvantages of the known aromatic diamine chain extenders described above - such as toxicity and easy reductive or oxidative cleavage of the SS grouping - or of the polyurethane elastomers which can be prepared therefrom, and, moreover, of making available polyurethane reactive systems who have the advantage of solvent-free processing, longer pot life and shorter mold life.
• Products in which the urea group is in the ortho or meta position, particularly preferably in the ortho position, to the sulfur are preferred according to the invention.
• the present invention also has a process for the production of optionally cellular polyurethane plastics by reacting polyhydroxyl compounds of molecular weight 400 to 10,000 and optionally low molecular weight polyhydroxyl compounds with polyisocyanates and araliphatic diamines as chain extenders, if appropriate in the presence of catalysts, blowing agents and other additives known per se to the subject, which is characterized in that diamines of the general formula are used in which R 'and R "have the meaning given above.
• the araliphatic diamines in particular in which the amino group is in the o-position to the sulfur, can also be used in cast elastomer systems and foaming processes without the addition of organic solvents and thereby enable excellent processing conditions, both in the production of elastomers and during foaming .
• chain extenders to be used according to the invention are their easy accessibility and their generally liquid state or their low melting point at room temperature, which simplifies their use particularly since the diamines do not have to be melted before they are added to the reaction mixture, which additionally saves energy costs and the extraordinarily long pot life of the reacting PUR systems.
• araliphatic diamines in which the aromatic amino group is in the o-position to the sulfur.
• Diamines in which R "is H or methyl, in particular hydrogen, are also preferred.
• A denotes a straight-chain or branched aliphatic hydrocarbon radical with 2-20, preferably 2-12, particularly preferably 2-6 C atoms or an araliphatic hydrocarbon radical with 8 C atoms.
• X denotes Cl or Br, preferably Cl, while A has the meaning mentioned above.
• benzothiazole is heated with an at least stoichiometric amount (preferably an excess of 0-10 mol%) of an alkali or alkaline earth metal solution - preferably sodium or potassium hydroxide solution, very particularly preferably sodium hydroxide solution - and the haloalkylamine or that is added Derivative thereof then, preferably in the form of a solution in a suitable solvent, to the reaction mixture.
• the reactants are preferably reacted with one another in stoichiometric amounts. However, you can also work with an up to 10-fold excess of benzothiazole.
• Preferred solvents are water and lower alcohols; water and mixtures of water with methyl, ethyl or isopropyl alcohol are very particularly preferred.
• 200 to 5000 ml of solvent preferably 200 to 2000 ml of solvent, are generally used per mole of benzothiazole.
• the reaction temperature is in the range from 20 to 180 ° C., preferably in the range from 50 to 140 ° C., the range from 70 to 120 ° C. being very particularly preferred.
• the reaction time is in the range of 30 minutes to 10 hours. The range from 1 hour to 6 hours is preferred.
• the reaction pressure is 1 bar to 10 bar. Is preferably carried out at normal pressure; however, it may also be advantageous to operate at elevated pressure to accelerate the reaction.
• haloalkylamines of the above formula (II) in the preparation of compounds of the formula (I) are, on the one hand, the ammonium salts with mineral or organic acids and, on the other hand, amides with carboxylic acids or urethanes of the general formula
• R is an optionally branched alkyl radical having 1 to 6 carbon atoms.
• Preferred ammonium salts are those of hydrochloric, sulfuric, acetic and oxalic acid or hydrogen bromide (particularly preferably of hydrochloric acid and acetic acid), preferably urethane that of tert-butyl alcohol.
• Polyhydroxyl compounds suitable for the process according to the invention have a molecular weight of approximately 400 to 10,000, preferably 600-4000. These are at least two, preferably 2 to 4, hydroxyl-containing polyesters, polyethers, polythioethers, polyacetals, polycarbonates and polyesteramides, such as the ones described are known per se for the production of homogeneous and cellular polyurethanes.
• the polyesters containing hydroxyl groups are, for example, reaction products of polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polyhydric, preferably two valuable carboxylic acids.
• polyhydric preferably dihydric and optionally additionally trihydric alcohols with polyhydric, preferably two valuable carboxylic acids.
• the corresponding polycarboxylic anhydrides or corresponding polycarboxylic esters of lower alcohols or mixtures thereof can also be used to produce the polyesters.
• the polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally substituted, for example by halogen atoms, and / or unsaturated.
• Examples include: succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic acid anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, tetrachlorophthalic acid anhydride, malomic acid anhydride, endomide maleinic acid anhydride, endomide dimeric acid anhydride, endomethylene uric acid anhydride, endomide dimeric acid anhydride, endomethylene uric acid anhydride, endomide dimeric acid anhydride, endomethylene uric acid, in a mixture with monomeric fatty acids, terephthalic acid dimethyl ester and terephthalic acid bis-glycol ester.
• Polyhydric alcohols include, for example, ethylene glycol, propylene glycol (1,2) and - (1,3), butylene glycol (1,4) and - (2,3), hexanediol (1,6), octanediol (1, 8), neopentyl glycol, cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol, glycerin, trimethylolpropane, hexanetriol- (1,2,6), butanetriol- (1,2,4 ), Trimethylolethane, pentaerythritol, quinite, mannitol and sorbitol, methylglycoside, also diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycols in question.
• the at least two, generally two to eight, preferably two to three, hydroxyl-containing polyethers which are suitable according to the invention are also of the type known per se and are obtained, for example, by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or Epichlorohydrin with itself, for example in the presence of BF 3 , or by addition of these epoxides, if appropriate in a mixture or in succession, to starting components with reactive hydrogen atoms such as water, alcohols, ammonia or amines, for example ethylene glycol, propylene glycol (1,3) or - (1,2), trimethylolpropane, 4,4'-dihydroxy-diphenylpropane, aniline, ethanolamine or ethylenediamine.
• epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene
• Sucrose polyethers such as are described, for example, in German publications 1 176 358 and 1 064 938, are also suitable according to the invention.
• Polyethers are preferred which predominantly (up to 90% by weight, based on all OH groups present in the polyether) have primary OH groups.
• Polyethers modified by vinyl polymers such as those obtained by polymerizing styrene and acrylonitrile in the presence of polyethers (American patents 3 383 351, 3 3 0 4 273, 3 523 093, 3 110 695, German patent 1 152 536) are suitable, as are polybutadienes containing OH groups.
• the condensation products of thiodiglycol with themselves and / or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols should be mentioned in particular.
• the products are polythio ether, polythio ether ester or polythio ether ester amide.
• polyacetals e.g. the compounds which can be prepared from glycols, such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxydiphenyldimethylmethane, hexanediol and formaldehyde.
• glycols such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxydiphenyldimethylmethane, hexanediol and formaldehyde.
• Appropriate polyacetals can also be prepared according to the invention by polymerization of cyclic acetals.
• Suitable polycarbonates containing hydroxyl groups are those of the type known per se, which e.g. by reacting diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6), diethylene glycol, triethylene glycol or tetraethylene glycol with diaryl carbonates, e.g. Diphenyl carbonate, or phosgene can be produced.
• diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6)
• diethylene glycol triethylene glycol or tetraethylene glycol
• diaryl carbonates e.g. Diphenyl carbonate, or phosgene
• polyester amides and polyamides include e.g. the predominantly linear condensates obtained from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, diamines, polyamines and their mixtures.
• Polyhydroxyl compounds already containing urethane or urea groups and optionally modified natural polyols such as castor oil, carbohydrates or starch can also be used.
• Addition products of alkylene oxides on phenol-formaldehyde resins or also on urea-formaldehyde resins can also be used according to the invention.
• Examples of such compounds are: ethylene glycol, propylene glycol (1,2) and - (1,3), butylene glycol (1,4) and - (2,3), pentanediol- (1,5), hexanediol- (1,6), octanediol- (1,8), neopentyl glycol, 1,4-bishydroxymethyl-cyclohexane, 2-methyl-1,3-propanediol, glycerin, trimethylolpropane, hexanetriol- (1,2,6), tri methylolethane, pentaerythritol, quinite, mannitol and sorbitol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols with a molecular weight of up to 400, dipropylene glycol, polypropylene glycols with a molecular weight of up to 400, dibutylene glycol, polybutylene glycol
• mixtures of different compounds with at least two hydroxyl groups with a molecular weight of 32-400 can be used.
• polyhydroxyl compounds can also be used in which high molecular weight polyadducts or polycondensates are contained in finely dispersed or dissolved form.
• modified polyhydroxyl compounds are obtained if polyaddition reactions (for example reactions between polyisocyanates and amino-functional compounds) or polycondensation reactions (for example between formaldehyde and phenols and / or amines) are carried out directly in situ in the above-mentioned compounds containing hydroxyl groups.
• aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates are described, for example, by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example ethylene diisocyanate, 1, 4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3 , 5-trimethyl-5-isocyanatomethyl-cyclohexane (DAS 1 202 785, American patent specification 3 401 190), 2,4- and 2,6-hexahydrotoluenediisocyanate and any mixtures of these isomers, he
• diisocyanates as described in US Pat. No. 3,492,330, polyisocyanates containing allophanate groups, e.g. in the British patent specification 994 890, the Belgian patent specification 761 626 and the published Dutch patent application 7 102 524, polyisocyanates containing isocyanurate groups, e.g. in the American patent specification 3 001 973, in the German patent specifications 1 022 789, 1 222 067 and 1 027 394 as well as in the German patent publications 1 929 034 and 2 004 048, polyisocyanates containing urethane groups, such as those e.g.
• distillation residues obtained in the industrial production of isocyanate and containing isocyanate groups optionally dissolved in one or more of the aforementioned polyisocyanates. It is also possible to use any mixtures of the aforementioned polyisocyanates.
• polyisocyanates for example 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers (“TDI”), polyphenyl-polymethylene polyisocyanates, such as those obtained from aniline, are generally particularly preferred.
• TDI 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers
• polyphenyl-polymethylene polyisocyanates such as those obtained from aniline
• polyurethane foams are to be produced by the process according to the invention, then water and / or volatile organic substances are also used as blowing agents.
• organic blowing agents examples include acetone, ethyl acetate, Alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane, butane, hexane, heptane or diethyl ether are also suitable.
• a blowing effect can also be achieved by adding compounds which decompose at temperatures above room temperature with the elimination of gases, for example nitrogen, for example azo compounds such as azoisobutyronitrile.
• propellants as well as details on the use of propellants can be found in the Plastics Handbook, Volume VII, published by Vieweg and Höchtlen, Carl-Hanser-Veriag, Kunststoff 1966, e.g. on pages 108 and 109, 453 to 455 and 507 to 510 described.
• catalysts are often also used.
• Suitable catalysts to be used are those of the type known per se, for example tertiary amines, such as triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N-cocomorpholine, N, N, N ', N'-tetramethyl-ethylenediamine , 1,4-diaza-bicyclo- (2,2,2) -octane, N-methyl-N'-dimethyl- aminoethyl-piperazine, N, N-dimethylbenzylamine, bis (N, N-di-ethylaminoethyl) adipate, N, N-diethylbenzylamine, pentamethyldiethylenetriamine, N, N-dimethylcyclohexylamine, N, N, N ', N'-tetramethyl- 1,3-butanediamine, N, N-dimethyl-ß-
• Suitable catalysts are also Mannich bases known per se from secondary amines such as dimethylamine and aldehydes, preferably formaldehyde, or ketones such as acetone, methyl ethyl ketone or cyclohexanone and phenols such as phenol, nonylphenol or bisphenol.
• Tertiary amines which have hydrogen atoms active against isocyanate groups as catalysts are e.g. Triethanolamine, triisopropanolamine, N-methyl-diethanolamine, N-ethyl-diethanolamine, N, N-dimethyl-ethanolamine, and their reaction products with alkylene oxides, such as propylene oxide and / or ethylene oxide.
• Silaamines with carbon-silicon bonds such as those e.g. in German Patent 1,229,290 (corresponding to American Patent 3,620,984) are in question, e.g. 2,2,4-trimethyl-2-silamorpholine 1,3-diethylaminomethyl-tetramethyl-disiloxane.
• Suitable catalysts are also nitrogen-containing bases such as tetraalkylammonium hydroxides, alkali metal hydroxides such as sodium hydroxide, alkali phenolates such as sodium phenolate or alkali metal alcoholates such as sodium methylate. Hexahydrotriazines can also be used as catalysts.
• organic metal compounds in particular organic tin compounds, can also be used as catalysts.
• Preferred organic tin compounds are tin (II) salts of carboxylic acids such as tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and tin (II) laurate and the tin (IV) compounds, e.g. Dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate or dioctyltin diacetate.
• tin (II) salts of carboxylic acids such as tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and tin (II) laurate
• the tin (IV) compounds e.g. Dibutyltin oxide, dibutyltin dichloride, di
• the catalysts are generally used in an amount between about 0.001 and 10% by weight, based on the amount of compounds having at least two isocyanate-reactive hydrogen atoms with a molecular weight of 400 to 10,000.
• surface-active additives such as emulsifiers and foam stabilizers
• emulsifiers are the sodium salts of castor oil sulfonates or salts of fatty acids with amines such as oleic acid diethylamine or stearic acid diethanolamine.
• Alkali or ammonium salts of sulfonic acids such as dodecylbenzenesulfonic acid or dinaphthylmethane disulfonic acid or of fatty acids such as ricinoleic acid or of polymeric fatty acids can also be used as surface-active additives.
• Polyether siloxanes are particularly suitable as foam stabilizers. These compounds are generally constructed in such a way that a copolymer is formed from Ethylene oxide and propylene oxide is linked to a polydimethylsiloxane residue. Such foam stabilizers are described, for example, in US Pat. Nos. 2,834,748, 2,917,480 and 3,529,308.
• reaction retarders e.g. acidic substances such as hydrochloric acid or organic acid halides, further cell regulators of the type known per se such as paraffins or fatty alcohols or dimethylpolysiloxanes as well as pigments or dyes and flame retardants of the type known per se, e.g. Tris-chloroethyl phosphate, tricresyl phosphate or ammonium phosphate and polyphosphate, furthermore stabilizers against aging and weather influences, plasticizers and fungistatic and bacteriostatic substances as well as fillers such as barium sulfate, diatomaceous earth, soot or sludge chalk are also used.
• acidic substances such as hydrochloric acid or organic acid halides
• cell regulators of the type known per se
• pigments or dyes and flame retardants e.g. Tris-chloroethyl phosphate, tricresyl phosphate or ammonium phosphate and polyphosphate
• surface-active additives and foam stabilizers to be used according to the invention as well as cell regulators, reaction retarders, stabilizers, flame-retardant substances, plasticizers, dyes and fillers, as well as fungistatic and bacteriostatic substances, and details on the use and action of these additives are given in the Plastics Manual, Volume VII by Vieweg and Höchtlein, Carl-Hanser-Verlag, Kunststoff 1966, e.g. described on pages 103 to 113.
• the reaction components are reacted according to the one-step process, the prepolymer process or the semi-prepolymer process, which are known per se, machine equipment often being used, for example those which are described in US Pat. No. 2,764,565. Details of processing devices that are also suitable according to the invention are published in the Plastics Manual, Volume VII Vieweg and Höchtlen, Carl-Hanser-Verlag, Kunststoff 1966, for example on pages 121 to 205.
• foaming is often carried out in molds according to the invention.
• the reaction mixture is introduced into a mold.
• Metal e.g. Aluminum, or plastic, e.g. Epoxy resin, in question.
• the foamable reaction mixture foams in the mold and forms the shaped body.
• the foaming of the mold can be carried out in such a way that the molded part has a cell structure on its surface, but it can also be carried out in such a way that the molded part has a compact skin and a cellular core. According to the invention, one can proceed in this connection in such a way that so much foamable reaction mixture is introduced into the mold that the foam formed just fills the mold.
• Cold-curing foams can also be produced according to the invention (cf. British patent specification 1 162 517, German patent application specification 2 153 086).
• foams can also be produced by block foaming or by the double conveyor belt process known per se.
• the amounts of the reaction components in the process according to the invention are preferably chosen so that the molar ratio of polyisocyanates to compounds having reactive OH and NH 2 groups - regardless of the processing method used in each case - generally between 0.9: 1 and 1.5: 1 is preferably between 1.05: 1 and 1.25: 1.
• the percentage of NCO in the prepolymer, if the prepolymer stage is used, can be, for example, 1 to 6% by weight.
• the molar ratio of reactive hydrogen of the chain extender to reactive OH groups can vary within wide limits, preferably it should be between 0.4: 1 and 1.5: 1, resulting in soft to hard types of polyurethane.
• diamines to be used according to the invention can also be used in part as chain extenders, for example those as mentioned above in the preparation of the polyhydroxyl compounds.
• the mole fraction of the amine according to the invention in the chain extender should be between 1 and 0.5, preferably between 1 and 0.8.
• Another embodiment consists in having the higher molecular compound with at least two hydroxyl groups in a mixture with the chain extender general transportation.
• the foams can either be produced by the molded foaming process or can be obtained from block-foamed material by assembly.
• 270 parts of benzothiazole and 160 parts of sodium hydroxide are refluxed in 400 parts of water for 3 hours. After cooling to 70 ° C., 250 parts of methanol are added and a solution of 260 parts of 3-chloropropylamine-HCl in 500 parts of water is added dropwise to the mixture at 70 ° C. in the course of 2 hours. After stirring for a further 3 hours at 100 ° C., the mixture is cooled and a solution of 100 parts of sodium hydroxide in 200 parts of water is added. The organic phase is separated off, the aqueous phase is washed twice with 200 parts of toluene and the combined organic phases are evaporated.
• NCO / NH 2 1.1
• the mixture is homogenized within 30 seconds and poured into a preheated mold. The reacting mixture remains pourable for 7 minutes. After an annealing time of 24 h at 110 ° C, a casting with the following mechanical properties is obtained:
• Examples 1 and 2 are repeated with the same approach in each case; however, the mixing with the diamines was carried out at room temperature. The mixtures remain pourable for several hours and are then poured into preheated molds. The moldings obtained have the same mechanical properties as in Examples 1 and 2.
• the dispersion can be used, for example, as an adhesive coating on a wide variety of materials such as textiles or leather.
• a finely divided dispersion is obtained which has a Tyndall effect in the translucent light.
• the dispersion has a pH of 7.5.
• the Ford cup run-out time (4 mm nozzle) is 35.3 seconds with a solids content of 35.3%.
• the film from the dispersion is tack-free and hard.

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• 1977
  • 1977-07-30 DE DE19772734574 patent/DE2734574A1/de not_active Withdrawn
• 1978
  • 1978-07-20 DE DE7878100451T patent/DE2860577D1/de not_active Expired
  • 1978-07-20 EP EP78100451A patent/EP0000551B1/fr not_active Expired
  • 1978-07-28 IT IT7850514A patent/IT7850514A0/it unknown
• 1979
  • 1979-12-26 US US06/106,976 patent/US4254229A/en not_active Expired - Lifetime

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