EP0000551B1 - Résines de polyuréthanes contenant des groupes thio et leur procédé de préparation - Google Patents

Résines de polyuréthanes contenant des groupes thio et leur procédé de préparation Download PDF

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Publication number
EP0000551B1
EP0000551B1 EP78100451A EP78100451A EP0000551B1 EP 0000551 B1 EP0000551 B1 EP 0000551B1 EP 78100451 A EP78100451 A EP 78100451A EP 78100451 A EP78100451 A EP 78100451A EP 0000551 B1 EP0000551 B1 EP 0000551B1
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Prior art keywords
molecular weight
diamines
optionally
nco
compounds
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English (en)
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EP0000551A1 (fr
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Jürgen Dr. Schwindt
Gerhard Dr. Grögler
Paul Dr. Uhrhan
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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
    • 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.
  • aromatic diamines as chain extenders in the production of polyurethanes.
  • the technically most commonly used reactive aromatic isocyanates are expediently reacted with slow-reacting diamines.
  • Aromatic diamines whose inertness and thus also reactivity to isocyanates has been reduced by introducing halogen or carboxy substituents have proven to be particularly useful as slow reacting diamines.
  • An example is the 3,3'-dichloro-4,4'-diaminodiphenyimethane (MOCA), which has been used the most so far.
  • MOCA 3,3'-dichloro-4,4'-diaminodiphenyimethane
  • Japanese laid-open specification 9195/70 describes a concentrated polyurethane solution which can be used to produce fibers, films and synthetic leather with good light stability.
  • Proportionally (9.5-60 mol%) of a diamine of the formula H 2 NR- (SR) n- NH 2 is used , where R is in the same or different aliphatic, aromatic, alicyclic or heterocyclic radical (in examples H2N ( CH2) 3-S- (CH2) 3-NHy or used) in addition to other chain extenders with 2 active hydrogen atoms (in the example 1,2-propylenediamine) in highly polar solvents such as dimethylformamide, with an NCO prepolymer.
  • 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.
  • the present invention also has a process for the production of optionally cellular polyurethane plastics by reacting polyhydroxyl compounds with a molecular weight of 400 to 10,000 and optionally low molecular weight polyhydroxyl compounds with a molecular weight of 32 to 400 and at least two hydroxyl groups with polyisocyanates and araliphatic diamines as chain extenders, if appropriate in the presence of catalysts, Blowing agents and other additives known per se, which is characterized in that diamines are those of the general formula are used in which R 'and R "have the meaning given above.
  • the araliphatic diamines 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 in foaming .
  • chain extenders to be used according to the invention are their easy accessibility and their generally liquid state at room temperature or their low melting point, 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.
  • the diamines particularly preferably used according to the invention correspond to the formula
  • 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 CI 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 Subsequently, derivative thereof, 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 200-2000 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 (11) come in the preparation of compounds of the formula (I) 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 hydrochloric acid and acetic acid), preferred urethane is that of tert-butyl alcohol.
  • Polyhydroxyl compounds suitable for the process according to the invention have a molecular weight of 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, as are known per se for the production of homogeneous and cellular polyurethanes.
  • the hydroxyl group-containing polyesters are e.g. Reaction products of polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polyhydric, preferably dihydric, carboxylic acids.
  • polyhydric preferably dihydric and optionally additionally trihydric alcohols
  • polyhydric preferably dihydric, 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, e.g. by halogen atoms, substituted and / or unsaturated.
  • the polyesters can have a proportion of terminal carboxyl groups.
  • Polyesters of lactones for example E- caprolactone or hydroxycarboxylic acids, for example ro-hydroxycaproic acid, can also be used.
  • the at least two, usually 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, for example, obtained 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, optionally 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 oxide
  • those polyethers are preferred which predominantly (up to 90% by weight, based on all the OH groups present in the polyether) have primary OH groups.
  • Polyethers modified by vinyl polymers such as those produced by polymerizing styrene and acrylonitrile in the presence of polyethers (American Patents 3383351, 3304273, 3523093, 3110695, German patent 1152536) are suitable, as are polybutadienes containing OH groups.
  • polyhydroxyl compounds are polythioethers, polyacetals, polycarbonates, polyesteramides, polyamides and also polyhydroxyl compounds already containing urethane or urea groups, and optionally modified natural polyols, such as castor oil, carbohydrates or starch. Also addition products of alkylene oxides onto phenol-formaldehyde resins or else Urea-formaldehyde resins for the construction of the polyurethanes are suitable.
  • mixtures of the above compounds with at least two isocyanate-reactive hydrogen atoms with a molecular weight of 400-10000 e.g. Mixtures of polyethers and polyesters can be used.
  • Examples of such compounds are: ethylene glycol, (1,2) and - (1,3) propylene glycol, (1,4) and - (2,3) butylene glycol, neopentyl glycol, 1,4-bis-hydroxymethyl- cyclohexane, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, quinite, mannitol and sorbitol, triethylene 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 glycols with a molecular weight di-bisphenol, bis-diol-di-bisphenol Di-hydroxymethyl hydroquinone, diethanolamine and triethanolamine.
  • 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 described, for example, in German Auslegeschrift 1168075 and 1260142, and in German Offenlegungsschriften 2324134, 2423984, 2512385, 2513815, 2 550 796, 2 550 797, 2 550 833, 2 550 862, US Patent 3869413 and DE-OS 2550860.
  • aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates such as those e.g. by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136-, for example 1,6-hexai methylene diisocyanate, 1,12-dodecane diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane, 2,4- and 2,6-hexahydrotoluenediisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or 1, 4-phenylene diisocyanate, perhydro-2,4'- and / or -4,4'-diphenylmethane diiso
  • m- and p-isocyanatophenylsulfonyl isocyanates are also suitable.
  • perchlorinated aryl polyisocyanates are also suitable.
  • polyisocyanates containing carbodiimide groups are also suitable.
  • polyisocyanates containing allophanate groups are also suitable.
  • Polyisocyanates containing urethane groups are also suitable.
  • polyisocyanates containing acylated urea groups such as those e.g.
  • distillation residues 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 e.g. 2,4- and 2,6-tolylene diisocyanate as well as any mixtures of these isomers ( «TDI»), polyphenyl-polymethylene polyisocyanates, such as those produced by aniline-formaldehyde condensation and subsequent phosgenation ( «raw MDI») and Polyisocyanates containing carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups (“modified polyisocyanates”).
  • Polyisocyanates containing carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups (“modified polyisocyanates”).
  • polyurethane foams are to be produced by the processes according to the invention, then water and / or slightly liquid organic substances are also used as blowing agents.
  • organic blowing agents come e.g. Acetone, halogen-substituted alkanes such as methylene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichloride fluoromethane, butane or hexane 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.
  • Azo compounds such as azoisobutyronitrile can be achieved.
  • propellants as well as details on the use of propellants can be found in the Kunststoff-Handbuch, Volume VII, published by Vieweg and Höchtlep, Carl-Hanser-Verlag, Kunststoff 1966, e.g. on pages 108 and 109, 453 to 455 and 507 to 510.
  • catalysts are also often used. Suitable catalysts to be used include those of the type known per se, e.g. tertiary amines or also known Mannich bases from secondary amines and aldehydes or ketones in question. 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 e.g. in German patent specification 1229290 (corresponding to American patent specification 3620984), in question, e.g. 2,2,4-trimethyl-2-silamorpholine.
  • 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.
  • catalysts can be used as mixtures. Further representatives of catalysts to be used according to the invention and details of the mode of action of the catalysts are in the plastics manual, volume VII, edited by Vieweg and Höchtlen, Carl-Hanser-Verlag, Kunststoff 1966, e.g. described on pages 96 to 102.
  • 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 can also be used.
  • the emulsifiers are e.g.
  • sodium salts of castor oil sulfonates or salts of fatty acids with amines such as oleic acid diethylamine or stearic acid diethanolamine in question.
  • 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 of ethylene oxide and propylene oxide is linked to a polydimethylsiloxane radical.
  • foam stabilizers are e.g. in U.S. Patents 2834748, 2917480 and 3529308.
  • reaction retarders e.g. acidic substances such as hydrochloric acid or organic acid halides
  • 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.
  • 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, e.g. those described in U.S. Patent No. 2764565. Details on processing devices that are also suitable according to the invention are given in the plastics manual, volume VII, published by Vieweg and Höchtlen, Carl-Hanser-Verlag, Kunststoff 1966, e.g. described on pages 121 to 205.
  • foam production is often carried out in molds.
  • the reaction mixture is introduced into a mold.
  • Metal for example aluminum, or plastic, for example epoxy resin, can be used as the molding material.
  • the foamable reaction mixture foams in the mold and forms the shaped body.
  • the molding 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.
  • one can proceed in such a way that one enters so much foamable reaction mixture 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 1162517, German laid-open specification 2153086).
  • 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 selected such that the molar ratio of polyisocyanates to compounds having reactive OH and NH2 groups - regardless of the processing method used in each case - is generally between 0.9: 1 and 1.5: 1 , preferably between 1.05: 1 and 1.25: 1.
  • the percentage of NCO in the prepolymer, if the prepolymer stage is used, can e.g. 1 to 6 wt .-%.
  • 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, e.g. those as mentioned above in the preparation of the polyhydroxy compounds.
  • chain extenders e.g. those as mentioned above in the preparation of the polyhydroxy 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.
  • a further embodiment consists in reacting the higher molecular compound with at least two hydroxyl groups in a mixture with the chain extender with an excess of diisocyanate and deforming the reaction product after the granulation in the heat under pressure.
  • polyurethane plastics with different hardnesses and different types of elasticity can be obtained. In this way you can also produce plastics that can be processed like thermoplastics.
  • a further embodiment consists in reacting the higher molecular compound with at least two hydroxyl groups in a mixture with chain extenders to be used according to the invention with a deficit of diisocyanate, a rollable skin being obtained which then, e.g. by crosslinking with other diisocyanate, can be converted into a rubber-elastic polyurethane plastic.
  • Elastomers produced according to the invention have a variety of uses, e.g. for molded parts subject to high mechanical loads, such as rollers, V-belts or seals, which are subjected to high thermal or chemical loads (e.g. for hot water pipes or in engines) or for the production of foils, textile coatings and polyurethane powders.
  • the chain extension can also be carried out in the presence of the blowing agents and additives described above, preferably in closed molds, foams having a cellular core and a compact surface being formed.
  • the elastic and semi-elastic foams obtainable by the process according to the invention are used, for example, as cushioning materials, mattresses, packaging material and, because of their flame resistance, also in those areas where these properties are particularly important, such as e.g. in automotive and aircraft construction and in 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 at 70 ° C within 2 hours. HCl dropped into the batch in 500 parts of water. 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.
  • test method was the Salmonella / microsome test, “Ames test”, according to B.N. Ames et al., Mutation Res. 31,347-364, 1975.
  • NCO / NH 2 1.1
  • the mixture is homogenized within 30 seconds and pre-mixed poured heated mold. The reacting mixture remains pourable for 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 polyester and the adduct are dewatered at 110 ° C. with stirring in a water jet vacuum.
  • the mixture is cooled to 80 ° C. and the butanediol is stirred in.
  • the diisocyanate is added and the mixture is stirred at 80 ° C. until an NCO value of 2.8 is reached (about 2 hours).
  • the diamine is added at 60 ° C. and the mixture is stirred at 60 ° C. until the melt is free of NCO (approx. 30 minutes).
  • the solid can be easily converted into a fine-particle dispersion with water, which has a Ford cup viscosity with a solids content of 30.4% (4 mm nozzle) of 12 seconds.
  • the average molecular weight of the solid is 3280.
  • the solid contains 23.6 milliequivalents per 100 g (1.89%) of SO 3 ⁇ groups.
  • a bisepoxide of the formula are added to 601 g of the dispersion from Example 8a dissolved in 50 g acetone, added at room temperature. The mixture is then heated to 80 ° C. and stirred at this temperature for 4 hours. The small amount of acetone is drawn off in a water jet vacuum. A centrifuge-stable dispersion (15 minutes at 3500 rpm) with a Ford cup run-out time (4 mm nozzle) of 14.4 seconds with a solids content of 39.5% is obtained. The pH is 4.5.
  • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Claims (7)

1. Résines synthétiques de polyuréthannes à base de polyisocyanates, de composés polyhy- droxylés à haut poids moléculaire et éventuellement à bas poids moléculaire et de diamines contenant du soufre, caractérisées en ce qu'elles contiennent des motifs de structure de formule générale
Figure imgb0028
dans laquelle
R' représente un reste aliphatique, cycloalipha- tique ou araliphatique divalent éventuellement ramifiée en C2-C20, R' étant relié au groupe -NH- par une liaison aliphatique, et
R" représente l'hydrogène, un reste alkyle éventuellement ramifié en Cl-C6, un reste aryle en C6-C15' un reste cycloalkyle en C4-C12' un halogène, un groupe -N02,-CN, -OR"' ou un groupe
Figure imgb0029
R"' représentant un reste alkyle éventuellement ramifié en C1-C6.
2. Résines synthétiques de polyuréthannes selon la revendication 1, caractérisées en ce qu'elles contiennent des motifs de structure de formule
Figure imgb0030
dans laquelle
R' et R" ont les significations indiquées dans la revendication 1.
3. Résines synthétiques de polyuréthannes selon les revendications 1 et 2, caractérisées en ce que R" représente l'hydrogène.
4. Procédé de préparation de résines synthétiques de polyuréthannes éventuellement alvéolaires à partir de:
a) des polyisocyanates
b) des composés portant au moins deux groupes hydroxy et présentant un poids moléculaire de 400 à 10000, éventuellement
c) des composés à bas poids moléculaire portant au moins deux groupes hydroxy et présentant un poids moléculaire de 32 à 400, et
d) des amines contenant du soufre en tant qu'agents d'allongement des chaînes, ce procédé se caractérisant en ce que l'on utilise en tant que diamines des diamines répondant à la formule générale
Figure imgb0031
dans laquelle R' et R" ont les significations indiquées dans la revendication 1.
5. Procédé selon la revendication 4, caractérisé en ce que l'on utilise des diamines répondant à la formule
Figure imgb0032
6. Procédé selon la revendication 4, caractérisé en ce que l'on utilise des diamines répondant à la formule
Figure imgb0033
EP78100451A 1977-07-30 1978-07-20 Résines de polyuréthanes contenant des groupes thio et leur procédé de préparation Expired EP0000551B1 (fr)

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Application Number Priority Date Filing Date Title
DE2734574 1977-07-30
DE19772734574 DE2734574A1 (de) 1977-07-30 1977-07-30 Thiogruppenhaltige polyurethankunststoffe

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EP0000551A1 EP0000551A1 (fr) 1979-02-07
EP0000551B1 true EP0000551B1 (fr) 1981-04-01

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EP (1) EP0000551B1 (fr)
DE (2) DE2734574A1 (fr)
IT (1) IT7850514A0 (fr)

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DE3932949A1 (de) * 1989-10-03 1991-04-11 Bayer Ag Elasthanfasern hoher dehnbarkeit und festigkeit und ein verfahren zu ihrer herstellung
TW209231B (fr) * 1990-10-29 1993-07-11 Akzo Nv
DE19718065A1 (de) * 1997-04-29 1998-11-05 Henkel Kgaa Reinigungsmittel für nachvernetzende Polyurethan-Hotmelts
US6111052A (en) * 1997-04-30 2000-08-29 Medtronic, Inc. Polyurethane and polyurea biomaterials for use in medical devices
DE10053890A1 (de) * 2000-10-31 2002-05-16 Basf Coatings Ag Sulfidgruppen enthaltende Polyurethane und Polymergemische auf dieser Basis sowie ihre Herstellung und ihre Verwendung
US8822623B2 (en) * 2001-11-14 2014-09-02 Essilor International (Compagnie Generale D'optique) High index and high impact resistant poly(thio)urethane/urea material, method of manufacturing same and its use in the optical field
US7767779B2 (en) * 2001-11-14 2010-08-03 Essilor International Compagnie Generale D'optique High index and high impact resistant polythiourethane/urea material, method of manufacturing same and its use in the optical field

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FR92377E (fr) * 1966-12-26 1968-10-31 Kuhlmann Ets Composition de polyuréthane-polyurée conduisant en un seul stade à un produit cellulaire et à un élastomère compact
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EP0000551A1 (fr) 1979-02-07
DE2734574A1 (de) 1979-02-08
DE2860577D1 (en) 1981-04-23
IT7850514A0 (it) 1978-07-28
US4254229A (en) 1981-03-03

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