DE2520814A1 - Light stabilisation of polyurethanes - using polymeric tert. amines from aliphatic diamines and (meth)acrylic esters or amides - Google Patents

Abstract

(A) Polyurethane compsns are stabilised against discolouration and decompsn by light by a stabiliser contg. >=3 structural units of the formula (I) between two aliphatically bound C atoms. R1 = H or CH3; R2 is 1 to 6 C alkyl, opt. substd by -OH, -CN or - CONH2 gps and opt. interrupted by -O- where R3 = H or as for R2 above, or R2 and R3 jointly may form a 5- or 6-membered heterocycle ring. (B) Stabiliser comprising a polyaddition and/or copolyaddition-condensation product of m wt 300-20000 is also claimed prepd by reacting (a) bi-secondary aliphatic amines of formula: R2-NH-M-NH-R3 (M, is opt. substd. alkylene or chain with (hydro) aromatic ring contg. one or more tert N or O atoms) and (b) acrylic and/or methacrylic acid esters of the formula: CH2 = C(R1)-COO-R6 (where R1 = H or CH3; and R6 = 1 to 12 C alkyl, pref, 2 to 4 C alkyl) and/or (c) N,N'-alkylenebisacrylamides and/or N,N'-alkylenebismethacry-lamides of formula (in which R1 is as above, R3 and R4 are 1 to 6 C alkyl, opt. substd by OH, CN or - CONH2, or opt. interrupted by -O-. or R3 and R4 jointly may represent a 5- or 6-membered ring; Y is an opt. substd. 1 to 6 C alkylene radical), and/or (d) alkylene-bisacrylic and/or alkylenebismethacrylic acid esters of the formula: CH2=C(R1)-COO-Z-OCO-C(R1)=CH2 (where z is opt. substd 2-6 C alkylene).

Description

Light stabilization of polyurethanes The present application relates to new, highly effective stabilizers and a method for light stabilization of polyurethane plastics. During or in particular after their production, preferably before or during their shaping, substances are added to the polyurethanes which contain at least three times the structural unit of the general formula having a tertiary nitrogen atom in the molecule contained between two aliphatically bonded carbon atoms. In the above general formula, R1 represents hydrogen or a methyl group, R2 represents a C1-C6-alkyl radical optionally substituted by a hydroxyl, cyano or carbonamide group and optionally interrupted by an oxygen atom, and X represents -0- or where R3 denotes hydrogen or a C1-C6-alkyl radical optionally substituted by a hydroxyl, cyano or carbonamide group, optionally interrupted by an oxygen atom, or together with R2 a 5-oaer group 6-L 2AJ gen forms heterocyclic ring.

It is known per se that the addition or incorporation of tertiary amines causes a certain stabilization of polyurethane ureas. So in THAT 1,126,603 primary, secondary or tertiary amines with a molecular weight of > 280 claimed as stabilizers. However, primary or secondary amines lead to a very rapid degradation of the polyurethane - especially at higher temperatures - and are therefore practically useless. Through the use of polymeric tertiary Amines, e.g. homo- or copolymers of (meth) acrylic acid esters of N, N-dialkylaminoalkanols (e.g. diethylaminoethanol) - especially for polyurethane threads - a certain albeit relatively little stabilization against degradation and discoloration under the action can be reached by daylight and UV rays, but is that which is effected at the same time Effect of better dyeability of such threads is technically more important. It was therefore previously necessary for stabilization due to the lack of sufficient effects of the known amines of polyurethanes against discoloration in (UV) light and against deterioration the mechanical properties of using highly effective stabilizers, e.g. mixtures of phenolic antioxidants and UV absorbers (such as 1,3,5-trimethyl-2,4,6-tris- (3, 5-di-tert-butyl-4-hydroxybenzene) and 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorotriazole) - see DOS 1 669 511.

Attempts have also been made by varying the N, N-dialkyl radical to achieve an improvement in the sun protection effect, but the effects are relative remained unsatisfactory. Also through the incorporation of diols or diamines with tertiary Amino groups (DOS 1 495 830, DOS 1 966 162, DOS 1 927 675, DOS 1 918 066, DOS 1 495 806) in the polyurethanes there is good dyeability, but only one relatively modest stabilization against light discoloration and degradation achieved.

Surprisingly, with the polymeric tertiary amines the Structure according to the invention found a class of substances whose effectiveness is well above which goes beyond the previously known tertiary amine derivatives and apparently on one previously unknown interaction of the tertiary amino group with that in the ß-position standing carbonyl group is based. The stabilization by these polymeric amines is even better than that due to the inherently quite effective combinations phenolic stabilizers and UV absorbers. (See comparative examples).

The polymeric tertiary amines of the invention are also wash and extraction resistant and improve, e.g. when installing in polyurethane elastomer threads, at the same time their colorability, so that one can rely on the modifying incorporation of do without tertiary nitrogen atoms containing diols or diamines in the Pdlyurethan can.

The improvement in properties is unexpected structure-specific. During e.g. very good stabilizations with the polyadduct N, N ', N "-trimethyl-diethylenetriamine and methylenebisacrylamide are obtained the incorporation of N, N ', N-trimethyl-diethylenetriamine as a chain extender in Polyurethanes practically no improvement in light resistance compared to ethylenediamine as a chain extender. The addition of such polyurethanes or also of polyamides obtained by polycondensation of the same triamine (N, N ', N "-trimethyldiethylenetriamine) made with adipic acid, there are no polyurethane elastomer solutions significant stabilizing effect. (See comparative experiments).

The additives according to the invention produce even in small concentrations also a noticeable improvement in the light resistance of elastomers, which already tertiary amino groups (e.g. as built-in N-methyl-di- (ß-hydroxypropyl) -amine) included. The effectiveness of the stabilizers according to the invention can be very increase significantly by increasing the amount added.

Generally 0.1 to 10 percent by weight, preferably 0.5 up to 5 percent by weight, particularly preferably 1.5 to 3.5 percent by weight, of the stabilizer used (based in each case on polyurethane solids).

The stabilizers according to the invention, which in the molecule at least three times the structural unit contain, can be relatively low molecular weight to high molecular weight (molecular weight from 300 to 20,000, preferably from 500 to 10,000, particularly preferably from 1,000 to 5,000); the characteristic structural units can preferably be distributed regularly or not regularly in the molecule. By and large, the stabilizing effect increases with the increase in the molecular weight of the substances, but above all with the increase in the number of structural units of the above general formula. According to the invention, for example 1,3,5-tri- (dimethylamino-propyl) -hexahydro-s-triazine is possible as a substance with a low molecular weight: Particularly suitable stabilizers, however, are substances whose structural units according to the invention form enlarged, repeating units together with other organic radicals, for example those of the following general formulas: but preferably: The structural unit according to the invention is underlined in the formula diagrams.

In the formulas I to VI, R and R 'independently of one another denote a group of the formula in which R1 represents hydrogen or a methyl group and R2 represents a C1-C8-alkyl radical optionally substituted by a hydroxy, cyano or carbonamide group and optionally interrupted by an oxygen atom, M an optionally substituted alkylene radical having from 2 to 10, preferably from 2 to 6 C. Atoms in whose chain one or more tertiary nitrogen, oxygen or sulfur atoms as well as aromatic or hydroaromatic rings can be contained, Y an optionally substituted C1-C6-alkylene radical, Z an optionally substituted C2-C6-alkyl radical, v an integer of at least 3, preferably 5 to 50, w an integer of at least 2, preferably 4 to 25 and R3 and R4 independently of one another a C1-C6-alkyl radical which is optionally substituted by a hydroxy, cyano or carbonamide group and interrupted by oxygen can, or jointly (ie

R3 with R together) a 5- or 6-membered 4 ring The stabilizers preferred according to the invention with the above general structural formulas I to VI, in which the structural unit according to the invention is contained more than twice, can be prepared by polyaddition or mixed-polyaddition-condensation of bisecondary amines with compounds that either multiply the acryloyl and / or methacryloyl radical (R1 = hydrogen or -CH3) or only once have an acryloyl or methacryloyl radical and in addition another group that is functional towards amino groups, such as a halogen atom or an ester, epoxide, hydroxymethyl or methoxymethylamide group. Suitable compounds of this type are, for example, the following (when they react with diamines, the corresponding structures of formulas I to VI are formed): (1) Diacrylamide CH2 = CH-CO-NH-CO-CH = CH2 (2) glycidyl acrylate or glycidyl methacrylate (3) Hydroxymethyl acrylic acid amide or methacrylic acid amide or

the associated methoxymethyl compounds but above all: (4) acrylic acid or methacrylic acid esters (5) N, N'-alkylenebisacrylamides or -bismethacrylamides or N, N'-alkylene-monoacrylamide-mono-methacrylamides (6) alkylene bisacrylates or -bismethacrylates or alkylene mono-acrylate-mono-methacrylates.

These unsaturated compounds with bis-secondary amines to the Light stabilizers according to the invention are implemented, except for the asymmetrical built N, N'-alkylene-monoacrylamide-mono-methacrylamides known. The latter receives one analogous to the production of the symmetrically built compounds, if of mixtures acrylic acid and methacrylic acid derivatives are assumed. e.g. one can use N, N'-methylene-mono-acrylamide-mono-methacrylamide CH2 = CH-CO-NH-CH2-NH-CO-C (CH3) = CH2 analogous to the representation of N, N'-methylenebismethacrylamide after H. fire and U.E. Lynch, Am. Soc. 75, 5027 to 5029, from one Mixture of acrylic acid and methacrylic acid amide by reaction with paraformaldehyde produce.

The reaction products of acrylic acid derivatives are often somewhat more effective Stabilizers than those from methacrylic acid derivatives.

Bisecondary amines that may be mentioned include: 1,4-bis- (N-methyl-aminomethyl) -cyclohexane, 1,4-bis- (N-ethyl-aminomethyl) -cyclohexane, 1,3-bis- (N-methylaminomethyl) ) -benzene, 1 3-bis- (N-butylaminomethylbenzene, 1-methylaminomethyl-5-methylamino-1, 3, 3-trimethyl-cyclohexane, benzyl-bis- (3-N-methyl-aminopropyl) -amine, bis- (N-methyl-aminoethyl) ether and piperazine, but especially the following compounds: a) Polyamines of the general formula in which R2 and R3 independently of one another a C1-C6-alkyl radical which is optionally substituted by a hydroxy, cyano or carbonamide group and which can be interrupted by oxygen, m is a number of at least 1, preferably 1 to 4, and n is a number of at least 2, preferably 2 to 6, mean.

Representatives of these polyamines are, for example, N, N'-dimethylethylenediamine, N-methyl-N'-ethyl-ethylenediamine, N, N'-diethyl-propylenediamine, N N1 N, N'-dimethyl-tetramethylenediamine, N, N'-dimethylhexamethylenediamine, N, N'-di-n-butylhexamethylenediamine, N, N'-Din-hexyl-ethylenediamine, N, N ', N "-trimethyl-diethylen-triamine, N, N', N", N "'- tetramethoxy-triethylenetetramine, N, N '-di-hydroxyethyl-ethylenediamine, N, N'-dicyanoethyl-ethylenediamine, N, N', N "-tri-n-butyl-dipropylenetriamine and N, N'-dicarbamidoethyl-ethylenediamine.

These bis-secondary amines can be converted into primary amines R2-NH2 and / or R3-NH2 with W, W'-dichloroalkanes Cl-CnH2n-Cl analogous to the formation of diprimary amines from ammonia and dichloroalkanes or by alkylation of the corresponding diprimary amines are prepared by methods known per se.

b) polyamines of the general formula in which Q for oxygen, sulfur or the residue of an aliphatic, cycloaliphatic, araliphatic or aromatic compound containing two hydroxyl and / or sulfhydryl groups, which remains after removal of the active hydrogen atoms, with R1 and R2 have the same meaning as above and u is an integer of at least 1 , preferably 1 to 3.

Representatives of these polyamines are, for example, bis (3-N-methylaminopropyl) -ether, bis- (3-N-methyl-aminopropyl) -sulfide, ethylene glycol bis (3-N-ethyl-aminopropyl) -ether, hexahydro-p -xylylene glycol bis (3-N-methyl-aminopropyl) -ether, hydroquinone-bis (3-N-methyl-aminopropyl) -ether and neopentylene glycol-bis (3-N-methyl-aminopropyl) -ether c) polyamines of the general formula in which R5 represents a C1-C18-alkyl radical optionally substituted by a hydroxyl group, R1 and R2 have the same meaning as above, and p and q represent integers from 1 to 20, preferably 1 to 5.

Representatives of these polyamines are, for example, ethylene-bis- (3-N-methyl-aminopropyl) -amine, stearyl-bis- (3-N-methyl-aminopropyl) -amine, 2-hydroxyethyl-bis- (3-N-ethyl-aminopropyl) -amine, n-Butylbis- (3-N-methoxyethyl-aminopropyl) -amine and especially methyl-bis- (3-N-methyl-aminopropyl) -amine, Ethyl-bis- (3-methyl-aminopropyl) -amine and n-butyl-bis- (3-N-methyl-aminopropyl) -amin.

The bisecondary amines b) and c) can be derived from the corresponding Prepare diprimary amines using known alkylation methods.

In many cases it is advantageous to use the light stabilizers according to the invention from mixtures of different bis-secondary amines or

to produce unsaturated compounds of type (1) to (6).

These copolymers are distinguished from the homopolymers greater solubility in organic solvents and better compatibility with the polyurethanes. Such copolymers can also be produced in such a way that that several bis-secondary amines or several of the unsaturated compounds in question separately from one another in reaction stages connected in series for implementation to be brought.

The implementation of the bisecondary amines with the unsaturated compounds to the either oligomeric or higher molecular weight light stabilizers can optionally also in the presence of solvents, in particular water, Alcohols, dimethylformamide or dimethylacetamide take place, with a concentration the reactant in the range of 10 to 100 percent by weight, especially from 20 to 60 percent by weight is recommended. As a reaction temperature for the polyaddition respectively.

Mixed-polyaddition-condensation comes in the range between 20 and 1500C in question, especially between 40 and 1200C. In general, the methacryloyl groups containing compounds are reacted at higher temperatures than those with Acryloyl groups.

Should only the double bonds in the case of compounds containing ester groups reacted, as is the case with alkylene bisacrylates or methacrylates, for example if it is desired, the temperature should not be significantly above 60 to 80.degree. On the other hand, it is advisable to use a reaction temperature of over 1000C, if the ester groups, such as when using acrylic or methacrylic acid esters, largely or completely should be implemented in a not very long time.

In many cases, a component is presented at the start of implementation and the other added in such a period that the heat of reaction occurring, can be discharged quickly enough, especially in the case of larger batches.

The polymer formation can be followed by measuring the viscosity. Since, according to the invention, preference is given to predominantly fully reacted polymers, the reaction is preferably stopped only when the viscosity maximum is reached.

In order to avoid self-polymerization of the unsaturated compounds is in some cases an addition of polymerization inhibitors known per se advantageous.

The molar ratio of the reaction components can be used within wide limits vary. A ratio of 0.8: 1.6 to 1.6: 0.8 is particularly favorable; in In many cases, maximum stabilization effects are achieved if the molar ratio from diamine to unsaturated compound is between 0.9: 1.1 and 1.1: 0.9.

Substances with structural units analogous to the formulas I to VI but without the radical (not essential according to the invention) in formulas I to IV or

the formulas V and VI can be obtained by using monoprimary amines instead of the bis-secondary amines with the above-mentioned compounds (1) to (6) implemented.

As primary amines, which are used for the production of the light stabilizers with the structural unit according to the invention can be used, for example: methyl, ethyl, n-propyl, n-butyl, methoxyethyl and 3-dimethylaminopropyl amine.

The implementation of monoprimary amines with the unsaturated compounds (1) to (6) can be carried out analogously to those with bis-secondary amines.

The incorporation of the basic light stabilizers according to the invention in polyurethanes can be used during or preferably after the production of the polyurethanes it can be done during or before its deformation.

The basic light stabilizers can be polyurethane solutions, e.g. in Dimethylformamide, methyl ethyl ketone, toluene, xylene, isopropanol, ethyl acetate, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, tetrahydrofuran, Acetone, methyl isobutyl ketone or their mixtures or polyurethane dispersions in Water can be added. But you can also use polyurethane solids, such as granules and foam batches, incorporated during or after the polyaddition reaction will.

The stabilized polyurethanes are used for technical purposes different areas, e.g. for the production of coated textiles such as fabrics, Knitted or nonwovens after the reverse or. Direct coating process or also the coagulation process, for the production of elastic fibers, for the production of paints and for the production of compact and foamed moldings.

The polyurethanes to be stabilized according to the invention are made according to known methods Methods from polyhydroxyl compounds, preferably polyhydroxy polyesters and / or Polyhydroxy polyethers, polyisocyanates and optionally chain extenders produced.

The starting components are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates into consideration, such as she z. B. von W. Siefken in Justus Liebigg Annalen der Chemie, 562, pages 75 bis 136, are described, for example ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1, 1 2-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, Cyclohexane-1,3- and 1,4-diisocyanate as well as any mixtures of these Isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (DAS 1 202 785, American Patent 3,401,190), 2,4- and 2,6-hexahydrotolylene diisocyanate as well as any mixtures of these isomers, hexahydro-1,3- and / or, 4-phenylene diisocyanate, Perhydro-2,4'- and / or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers, diphenylmethane-2,4'- and / or -4,4'-diisocyanate, naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ', 4 "-triisocyanate, Polyphenyl-polymethylene-polyisocyanates, as produced by aniline-formaldehyde condensation and subsequent phosgenation and e.g. in the British patents 874 430 and 848 671 are described, m- and p-Isocyanatophenylsulfonyl-isocyanate according to the American patent 3 454 606, perchlorinated aryl polyisocyanates, as it is e.g. in the German IMsiegeschrift 1 157 601 (American patent specification 3,277,138), polyisocyanates containing carbodiimide groups, such as they in German patent specification 1 092 007 (American patent specification 3 152 162), diisocyanates as they are in the American patent 3,492,330, polyisocyanates containing allophanate groups, such as for example in British patent specification 994 890, Belgian patent specification 761 626 and published Dutch patent application 7 102 524 are, isocyanurate groups containing polyisocyanates, such as those in the American Patent specification 3 001 973, in German patents 1 022 789, 1 222 067 and 1 027 394 and in the German Offenlegungsschriften 1 929 034 and 2 004 048 are, polyisocyanates containing urethane groups, as they are s.B.

in the Belgian patent 752 261 or in the American U.S. Patent 3,394,164, containing acylated urea groups Polyisocyanates according to German Patent 1,230,778, containing biuret groups Polyisocyanates, such as those described in German Patent 1 101 394 (American Patents 3,124,605 and 3,201,372) and in British Patent Specification 889 050 are described, prepared by telomerization reactions Polyisocyanates such as those described in US Pat. No. 3,654,106 are, tstergruppen-containing polyisocyanates, E e them for example in the British Patents 965,474 and 1,072,956, in American patent 3,567 763 and in German Patent 1,231,688 are reaction products of the above-mentioned isocyanates with acetals according to German Patent 1,072 385 as well as polyisocyanates containing polymeric fatty acid residues according to American U.S. Patent 3,455,883.

It is also possible to use the technical isocyanate production distillation residues containing isocyanate groups, if appropriate dissolved in one or more of the aforementioned polyisocyanates to be used. Further it is possible to use any mixtures of the aforementioned polyisocyanates.

Further starting components for the production of the polyurethanes are Compounds with at least two isocyanate-reactive hydrogen atoms with a molecular weight of 400-10,000 as a rule. This is understood to mean in addition to compounds containing amino groups, thiol groups or carboxyl groups preferably polyhydroxyl compounds, especially two to eight hydroxyl groups Compounds containing, especially those with a molecular weight of 800 to 10,000, are recommended 1000 to 6000, see B. at least two, usually 2 to 8, but preferably 2 to 4, polyesters containing hydropyl groups, polyethers, polythioethers, polyacetals, Polycarbonates and polyester amides, such as those used for the production of homogeneous and of sell-shaped polyurethanes are known per se.

The hydroxyl group-containing polyesters in question are E.g. conversion products of polyvalent, preferably divalent and possibly additionally trivalent Alcohols with polyhydric, preferably divalent, carboxylic acids. Instead of the free polycarboxylic acids, the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or their mixtures are used to produce the polyesters will. The polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally, e.g. by halogen atoms, substituted and / or unsaturated. Examples include: succinic acid, Adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, Trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, Maleic acid, maleic anhydride, fumaric acid, dimeric and trimeric fatty acids such as Oleic acid, optionally mixed with monomeric fatty acids, dimethyl terephthalate and terephthalic acid bis-glycol esters. The polyhydric alcohols are e.g. 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, glycerine, trimethylolpropane, hexanetriol- (1,2,6), butanetriol- (1,2,4), Trimethylolethane, pentaerythritol, quinitol, mannitol and sorbitol, methyl glycoside, and more Diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, Polypropylene glycols, dibutylene glycol and polybutylene glycols in question. The polyester may have a proportion of terminal carboxyl groups. Also polyester made from lactones, E.g. £ -caprolactone or hydroxycarboxylic acids, e.g.

w-Hydroxyeapronsälure can be used.

Also the at least two in question according to the invention in the Usually two to eight, preferably two to three, hydroxyl-containing polyethers are those of the type known per se and are e.g. Epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with itself, e.g. in the presence of BF3, or through the addition of these epoxides, optionally in a mixture or in succession, of starting components with reactive ones Hydrogen atoms such as water, alcohols or amines, e.g. ethylene glycol, propylene glycol- (1,3) or - (1,2), trimethylolpropane, 4,4'-dihydroxydiphenylpropane, aniline, ammonia, Ethanolamine or ethylenediamine produced. Also sucrose polyethers, as they are e.g. in the German Auslegeschriften 1 176 358 and 1 064 938 come according to the invention in question. In many cases such polyethers are prevented, the predominantly (up to 90% by weight, based on all OH groups present in the polyether) primary Have OH groups. Also modified by vinyl polymers polyethers, such as her 8.B. arise through polymerization of styrene, acrylonitrile in the presence of polyethers (American patents 3,383,351, 3,304,273, 3,523,093, 3,110,695, German Patent specification 1,152,536) are suitable, as are polybutadienes containing OH groups.

Among the polythioethers are in particular the condensation products of thiodiglycol with itself and / or with other glycols, dicarboxylic acids, Formaldehyde, aminocarboxylic acids or amino alcohols are listed. Depending on the co-components If the products are polythio mixed ethers, polythioether esters or Polythioether ester amides.

As polyacetals come e.g. those from glycols, such as diethylene glycol, Triethylene glycol, 4,4'-dioxethoxydiphenyldimethylmethane, hexanediol and formaldehyde possible connections in question. Also by polymerizing cyclic acetals suitable polyacetals can be produced according to the invention.

Polycarbonates containing hydroxyl groups are those of the known type into consideration, e.g. by reacting diols such as propanediolw ), Butanediol (1,4) and / or hexanediol - (1.6), diethylene glycol, Triethylene glycol or tetraethylene glycol with diaryl carbonates, e.g. diphenyl carbonate or phosgene.

The polyester amides and polyamides include, for example, those made of polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent ones saturated and unsaturated amino alcohols, diamines, polyamines and their mixtures recovered, predominantly linear condensates.

Also polyhydroxyl compounds already containing urethane or urea groups and optionally modified natural polyols, such as castor oil, carbohydrates or starch, can be used. Also adducts of alkylene oxides with phenol-formaldehyde resins or urea-formaldehyde resins can be used according to the invention.

Representatives of these compounds are e.g. in High Polymers, Vol.

XVI, "Polyurethanes, Chemistry and Technology", written by Saunders-Frisch, Interscience Publishers, New York, London, Volume 1 1962, pages 32 to 42 and pages 44 to 54 and Volume II, 1964, pages 5 to 6 and 198 to 199, as well as in the Kunststoff-Handbuch, Volume VII, Vieweg-Höchtlen, Carl-Hanser-Verlag, Munich, 1966, e.g. on the pages 45 to 71.

Mixtures of the abovementioned compounds can of course be used with at least two isocyanate-reactive hydrogen atoms with a molecular weight of 400 to 10,000, e.g. mixtures of polyethers and polyesters, can be used.

Compounds having at least two isocyanate-reactive hydrogen atoms and having a molecular weight of 32 to 400 may also be used as chain extenders. In this case too, this is understood to mean hydroxyl groups and / or amino groups and / or thiol groups and / or carboxyl groups and / or amino groups, preferably compounds having hydroxyl groups and / or amino groups. These compounds generally have 2 to 8 isocyanate-reactive hydrogen atoms, preferably 2 or 3 reactive hydrogen atoms. Examples of such compounds include: 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), neopentylglycol, 1,4-bis-hydroxymethyl-cyclohexane, 2-methyl-1,3-propanediol, glycerine, trimethylolpropane, hexanetriol- (1,2,6), Trimethylolethane, pentaerythritol, quinitol, 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, dihydric propylene glycol, polybutylene glycol with a molecular weight of up to 4.4, polybutylene glycol, dihydroxylene glycol, dihydroxylene glycol, dihydric hydroxide with a molecular weight of up to 4.4. Di-hydroxymethyl-hydroquinone, 1,4-phenylenebis (ß-hydroxyethyl ether), ethanolamine, N-methylethanolamine, diethanolamine, N-methyldiethanolamine, triethanolamine, 3-aminopropanol, ester diols of the general formulas HO- (CH2) X-CO-o - (CH2) y-OH and HO- (CH2) xO-CO-R-CO-O- (CH2) x-OH in which R is an alkylene or arylene radical with 1-10, preferably 2 - 6, carbon atoms, x = 2 - 6 and y = 3 - 5, e.g. # -hydroxybutyl - # - hydroxy-caproic acid ester, # -hydroxyhexyl-γ-hydroxybutyric acid ester, adipic acid bis (ß-hydroxyethyl) esters and terephthalic acid bis (ß-hydroxyethyl) esters; as well as diolurethanes of the general formula HO- (CH2) xO-CO-NH-R'-NH-CO-O- (CH2) x-OH in which R 'is an alkylene, cycloalkylene or arylene radical with 2-15, preferably 2 - 6, carbon atoms and x represent a number between 2 and 6, for example 1,6-hexamethylene-bis- (ß-hydroxyethyl urethane) or 4,4'-diphenylmethane-bis (# - hydroxybutyl urethane); Diol ureas of the general formula in which R "is an alkylene, cycloalkylene or arylene radical with 2-15, preferably 2-9, carbon atoms, R"'= H or CH3 and x = 2 or 3, for example 4,4'-diphenylmethane to - (ß-hydroxyethyl urea) or the compound g 3 HO-CH2-CHZ-NH-CO-NH-CO-NH-CH, -CH2-OH CH3 L Suitable aliphatic diamines are, for example, xthylenediamine, 1,4-tetramethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine and their mixtures, 1-amino-3,3, 5-trimethyl-5-aminomethylcyclohexane, 2,4- and 2 , 6-hexahydrotoluylenediamine and mixtures thereof, perhydro-2,4'- and 4,4'-diaminodiphenylmethane, p-xylylenediamine, bis- (3-aminopropyl) -methylamine, etc. Also hydrazine and substituted hydrazines, e.g. methylhydrazine, N, N'-dimethylhydrazine and its homologues, as well as acid dihydrazides, can be used as chain extenders, e.g. carbodihydrazide, oxalic acid dihydrazide, the dihydrazides of malonic acid, succinic acid, glutaric acid, adipic acid, β-methyladipic acid, sebacic acid, hydracrylic acid and terephthalic acid, e.g. Semicarbazido-propionic acid hydrazide (DOS 1 770 591), semicarbazido-alkylenecarbazine esters such as, for example, 2-semicarbazidoethyl carbazine ester (DOS 1 918 504) or amino-semicarbazide compounds such as, for example, β-aminoethyl semicarbazido carbonate (DOS 1 902 931).

Examples of aromatic diamines are bisanthranilic acid esters according to German Offenlegungsschriften 2,040,644 and 2,160,590, 3,5- and 2,4-diaminobenzoic acid esters according to DOS 2 025 900, which is in the German Offenlegungsschriften 1 803 635, 2 040 650 and 2160 589 described ester group-containing diamines, and 3,3'-dichloro-4,4'-diamino-diphenylmethane, Toluenediamine, 4,4'-diaminodiphenylmethane and 4,4'-diaminodiphenyl disulfide called.

Compounds such as 1-mercapto-3-aminopropane, optionally substituted amino acids, e.g., glycine, alanine, valine, serine and Lysine and optionally substituted dicarboxylic acids, for example succinic acid, Adipic acid, phthalic acid, 4-hydroxyphthalic acid and 4-aminophthalic acid are used will.

Compounds which are monofunctional with respect to isocyanates can also be used in proportions of 0.01 to 10 percent by weight, based on polyurethane solids, as so-called chain terminators are also used. Such monofunctional compounds are e.g. monoamines such as butylamine and dibutylamine, octylamine, stearylamine, N-methylstearylamine, Pyrrolidine, piperidine and cyclohexylamine, monoalcohols such as butanol, 2-ethylhexanol, Octanol, dodecanol, the various amyl alcohols, cyclohexanol, ethylene glycol monoethyl ether etc.

The basic light stabilizers according to the invention are used in polyurethane plastics both the lightfastness and the lightfastness are significantly increased.

The lightfastness is a measure of the yellowing and is based on the coloristic blue scale measured according to DIN 54 004. Under lightfastness is the change (decrease) in tensile strength and elongation at break when exposed to light Understood; both sizes are determined according to DIN 53 404.

The yellowing of polyurethanes observed under the action of light, which are built up using aromatic polyisocyanates is made by the addition of the light stabilizers according to the invention is considerably reduced. the Lightfastness increases from 3 to 4 to 5 to 6, often even to 6 to 7 or 7.

A deterioration in the mechanical properties when exposed to light is based on polyurethanes based on both aromatic and aliphatic polyisocyanates observed. The addition of the basic light stabilizers according to the invention is reduced these effects in both polyurethane types, thus improving the lightfastness.

The loss of tensile strength and elasticity due to exposure to light is particularly useful for polyurethanes made from polyhydroxy polyethers, such as dihydroxy propy lenglykolpolyäther n or dihydroxy-tetramethylene glycol polyethers, great. The invention Basic light stabilizers also stabilize such polyurethanes in a very unusual way Extent.

Those achieved with the aid of the basic light stabilizers according to the invention Stabilizing effects, such as improvement of lightfastness and lightfastness, were due to the lack of those commonly found in antioxidants and UV absorbers encountered sterically hindered phenol groups, benzotriazole, Indole, Benzophenone or cinnamic acid derivatives are not to be expected and are therefore particularly surprising.

In addition, the stability of polyurethane fibers is compared Chlorine bleaching improves and in some cases reduces thread adhesion. Since the new stabilizers have a sufficiently high molecular weight, they are and cleaning processes are not removed.

You can also add solutions to the stabilizers, which then follow are coagulated in the wet spinning process; they are also used as additives for stabilization of coagulable polyurethanes, which are suitable for the production of microporous synthetic leather be used.

The polyurethane elastomers stabilized according to the invention can additionally with known stabilizers for polyurethanes, e.g. phenolic antioxidants, UV absorbers and specific light protection agents, e.g. derivatives of the asymmetric Dimethylhydrazine, are added, whereby an even more extensive stabilization can reach.

The stabilizing effect is always in relation to the unstabilized Polyurethane substrate to be assessed, which - depending on the structure - at different speeds is discolored or degraded. Substrates are preferred for elastomer threads those based on polytetramethylene ethers or adipic acid polyesters (as soft segments) and diphenylmethane-4,4'-diisocyanate and ethylenediamine or bis-hydrazide derivatives (such as ß-semicarbazido-propionic acid hydrazide). Particularly sensitive to Degradation are polyether urethanes; diamine-extended polyurethanes are also in general more sensitive than hydrazide-extended substrates.

The following examples explain the process according to the invention. Unless otherwise stated, figures are given as parts by weight or percentages by weight to understand.

Preparation of the stabilizers according to the invention used in the examples 1 to 30 stabilizers 1 and 2 327 g of N, N'-methylenebisacrylamide are placed in a 2 liter three-necked flask (2.12 mol) submitted. After flushing with pure nitrogen, a is added with stirring about 15 to 250C warm solution of 176 g of N, N'-dimethyl-ethylenediamine (2.00 mol) and 16.2 g of N, N ', N "-trimethyl-diethylenetriamine (0.12 mol) in 363 g of dimethylformamide and Add 156 g of water quickly. The mixture is then heated under a very gentle stream of nitrogen slowly to 600C within an hour. During this time - after about three quarters of an hour, at 450C - a clear solution forms. After stirring at 60 ° C. for a further 18 hours and the solution becomes more and more viscous, the polyaddition is over. The so produced solution (50% in dimethylformamide / water = 7: 3) has a at 25 0C Viscosity of 2 290 mPas. (Stabilizer 1) Varying the amount of N, N'-methylene-bis-acrylamide in the above approach in the range of 308 to 348 g (2.00 to 2.23 moles) and leaves the amount of the amine components constant, polyadducts are obtained whose 50% solutions in DMF / H2O = 7: 3 have the following viscosities at 250C: N, N'-methylenebisacrylamide viscosity in mPas / 250C Stabili-amount moles DMF / H20 = 7: 3 sator 308 g 2.00 785 1a 320 g 2.08 1615 1b 344 g 2.23 1380 1c 348 g 2.26 998 1d One varies in the above approach the mixing ratio of the two amines in such a way that the triamine content increases, and leaves the amount of N, N'-methylenebisacrylamide constant, one obtains polyadducts, whose 50% solutions in DMF / H2 0 = 7: 3 at 250C have the following viscosities: N, N1-dimethyl- N, N ', N' -trimethyl viscosity Stabiliäthylenediamine diethylenetriamine mPas / 250C sator amount mole amount mole DMF / H20 = 7: 3 168.5 g 1.915 29.7 g 0.205 3350 2a 162.0 g 1.840 40.6 g 0.280 3710 2 155.0 g 1.762 51.9 g 0.358 3060 148.0 g 1.682 63.5 g 0.438 2610 2c 0.0 g 0. o 308.0 g 2.12 838 2d Stabilizer 3 and 3a At room temperature are added with stirring to 330 g of a 26.7% strength aqueous N, N'-dimethylethylenediamine solution (1.0 ttol) 154 g of N, N'-methylene-bis-acrylamide. As a result of the heat of reaction released the temperature rises to 590 ° C. within 5 minutes, with the methylene-bis-acrylamide goes into solution. The mixture is stirred for a further 4 hours at 60.degree. C. and then concentrated to in vacuo dry up. Finally, enough dimethylformamide is added to make up the total weight the solution is 2420 g. The 10% solution produced in this way has a viscosity of 4 mPas at 250C.

A solution of 90.5 g of N, N'-dimethylethylenediamine is added at 10 ° C. with stirring (1.03 mol) in 244.5 g of water was added to 154 g of N, N'-methylenebis-acrylamide. Within of 10 minutes the Temperature to 500C. The methylene-bis-acrylamide goes here in solution. The mixture is then stirred for a further 2 hours at this temperature. the viscous 50% solution obtained in this way has a viscosity of 3380 mPas. (Stabilizer 3a) Stabilizer 4 Put in a 4 liter three-necked flask Submitted 1050 g of water.

After heating to 50 ° C., 202 g of N, N'-methylenebisacrylamide are added with stirring (1.31 moles). 10 minutes later, a rapid addition of about 20 to 250C takes place warm solution of 200 g of N, N ', N "-trimethyl-diethylenetriamine (1.38 mol) in 500 g of water.

The internal temperature initially drops by 2 ° C - this is ensured by the Heat of solution of the methylene-bis-acrylamide causes - but then increases as a result of the Heat of reaction to a maximum of 580C again. After stirring at 60 ° C. for a further 6 hours has, the solution of the adduct, which has a viscosity of about 8 to 10 mPas at 600C, at the same temperature under nitrogen in a vacuum to dryness constricted. To prepare a 25% solution in dimethylformamide, one sets the residue, which at 60 ° C is a difficult-to-flow, syrupy mass of yellowish appearance - at room temperature it is barely mobile - so much dimethylformamide that the total weight of the solution is 1608 g. the 25% solution shows a viscosity of 33 to 38 mPas at 250C.

Stabilizer 5 A solution of 176 g of N, N'-dimethoxyethylethylenediamine (1.0 mol) in 330 ml of water are added to 154 g of N, N'-methylenebisacrylamide with stirring at room temperature (1.0 mol) and then heated to 600C within 1 hour. During this time the methylenebisacrylamide goes into solution. Then you continue to heat for so long 600C, until no more increase in viscosity can be determined, which is about 10 hours after Reaching the temperature of 600C the case is. The pale yellowish, 50% strength aqueous solution has a viscosity of 269 mPas at 25 ° C.

Stabilizer 6 and 6a With stirring, 148.5 g of n-butyl-bis- (3-n-butylamino-propyl) -amine (0.49 mol) dissolved in 225.5 g of methanol, added to 77 g of N, N'-methylene-bis-acrylamide (0.5 mol) and then the reaction mixture heated to 600C. After 3 hours, all of the methylene-bis-acrylamide has gone into solution.

The mixture is then heated to 60 ° C. until there is no increase in viscosity is more noticeable, which is the case about 25 hours later. You get one 50% methanolic solution of the polyadduct with a viscosity of 60 mPas at 25 ° C.

Instead of 148.5 g of n-butyl-bis- (3-n-butyl-aminopropyl) -amine 151.5 g (0.51 mol) are added under the same reaction conditions 50% methanolic solution of the polyadduct, which has a viscosity of 117 mPas at 250C. (Stabilizer 6a) Stabilizer 7 57 g of N, N'-di-n-butyl-ethylenediamine (0.25 mol) are added to a dispersion of 38.5 at room temperature with stirring g of N, N'-methylenebisacrylamide (0.25 mol) in 95.5 g of methanol and then heated 28 hours at 600C. After the first 4 hours, the methylenebisacrylamide is in solution went. A 50% strength methanolic solution of the polyadduct is obtained, the one Has a viscosity of 102 mPas at 25 0C.

Stabilizer 8 With stirring, a solution of 21.6 g at 200 ° C. is obtained N, N'-dimethyl-hexamethylenediamine (0.15 mol) in 44.7 g of water for 23.1 g N, N'-methylenebisacrylamide (0.15 moles). Within 3 hours, the methylene-bis-acrylamide rises with dissolution the temperature to 530C. The polyaddition is continued at this temperature. After 17 minutes, the rapidly becoming more viscous solution - the viscosity is then given 2600 mPas at 530C - 25 g of dimethylformamide. The viscosity of the solution drops to 980 mPas at 460C. The polyaddition then continued at 530C is 6 hours after adding the dimethylformamide (final viscosity: 1190 mPas) completed. After adding 12.8 g of dimethylformamide, a 35% strength becomes perfect colorless-looking solution of the polyadduct in dimethylformamide water = 0.85: 1.0 obtained with a viscosity of 2955 mPas at 250C.

Stabilizer 9 and 9a In a 1 liter three-necked flask are 146.5 g (0.95 mol) of N, N'-methylenebisacrylamide. At room temperature one gives under Stir 173 g of methyl bis (3-methylaminopropyl) amine (1.00 mol) dissolved in 319.5 g of dimethylformamide, and heated to 650C for 11 hours. The yellowish tinged, 50% solution has a viscosity of 57 mPas at 250C.

154 g of N, N'-methylenebisacrylamide are added with stirring at room temperature quickly to a solution of 173 g of methyl-bis- (3-methylamino-propyl) -amine in 980 ml Water and heated to 65 ° C for a total of 10 hours. Then at 60 ° C in a vacuum concentrated to dryness. You then add so much dimethylformamide that the total weight the solution is 1308 g. The 25% solution has a viscosity at room temperature of 24 mPas.

(Stabilizer 9a) Stabilizer 10 To 30.8 g of N, N'-methylenebisacrylamide (2.0 mol) are added at room temperature with stirring 23.2 g of N, N'-dimethyltetramethylenediamine (0.2 Mol), dissolved in 54 g of water. The temperature rises rapidly to 580C. The polyaddition is initially continued at this temperature. After about 50 minutes the viscosity is up increased to 4000 mPas. 108 g of dimethylformamide are then added and the mixture is still heated 6 hours at 90 ° C. The viscosity at the end of the polyaddition is 14 mPas / 900C. The yellowish solution thus obtained is 25% in dimethylformamide: water = 2: 1.

Stabilizer 11 40 g of N, N'-methylenebisacrylamide (0.26 mol) are added with stirring to a 20 ° C. solution of 55.2 g of N, N ', N ", N"' - tetramethyltriethylenetetramine (0.273 moles) in 95.2 grams of water. As a result, the solution heats up within 40 minutes the reaction heat to 550C, with a considerable increase in viscosity takes place (to 100 mPas). From then on, the reaction is allowed to continue for another 3 1/2 hours. the 50% aqueous solution finally has a viscosity of 7580 mPas at 25 ° C.

Stabilizers 12 and 12a 50 g N, N1-methylenebisacrylamide (0.325 mol) and 178 g of 64.5% strength aqueous N, N'-dimethyl-ethylenediamine solution (1.3 mol) are heated to 50 ° C. for 8 hours with stirring. Then it is concentrated in a vacuum. The thus obtained liquid residue of 101.4 g is at room temperature within 10 minutes 22.5 g of methyl acrylate (0.26 mol) are added, the temperature rising to 500C rises. The mixture is then heated to the boil for 10 hours.

Thereafter, the methanol formed is in vacuo at a temperature distilled off up to 1000C. The yellow, very viscous residue of 114.5 g is in a Dissolved mixture of 80 g of dimethylformamide and 34.3 g of water. The viscosity of the 5% solution obtained in this way is 75 mPas at 250C.

Analogously to this, a mixed polyaddition condensation product is obtained from the following Starting materials prepared: 50 g of N, N'-methylenebisacrylamide (0.325 mol) 89 g N, N'-dimethylethylenediamine, 64.5% strength (0.65 mol) and 13.6 g of methyl acrylate.

105 g of a yellowish, viscous residue are obtained, the in 105 g of dimethylformamide to a 50% solution with a viscosity of 26 mPas is resolved at 25 0C. (Stabilizer 12a) Stabilizer 13 with stirring 29.0 g of N, N ', N11-trimethyldiethylenetriamine (0.2 mol) are dissolved at room temperature in 48.4 ml of water, to 23.0 g of N-methoxymethyl-acrylic acid amide (0.2 mol). The temperature rises to 440C within 3 minutes as a result of the heat of reaction.

During this time, the color changes several times, from initially colorless over red-brown to finally yellow. The mixture is then heated for a further 10 hours to 50 ° C. The 50% strength aqueous solution of the mixed polyaddition condensation product thus obtained has a viscosity of 46 mPas at 250C.

Stabilizer 14 A mixture of 45.5 g of N, N'-methylene-bis-methacrylamide (Q, 25 mol) 34.1 g of a 64.5% strength aqueous N, N'-dimethylethylenediamine solution and 55.4 g of water are heated to 80 ° C. for 20 hours with stirring. The resulting 50% aqueous solution of the polyadduct has a viscosity of 153 mPas at 250C.

Stabilizer 15 and 15a 91 g of N, N'-methylene-bis-methacrylamide (0.5 Mol) are added at 27 ° C to a solution of 76 g of N, N ', N "-trimethyl diethylenetriamine (0.525 mol) in 167 ml of water. The resulting dispersion is within half a Hour into a solution. This is then heated to 75 ° C. for 10 hours. The light orange one 50% strength aqueous solution then has a viscosity of 53 mPas at 25 ° C.

91 g of N, N'-methylene-bis-methacrylamide (0.5 mol), 76 g of N, N ', N "-trimethyl-diethylenetriamine (0.525 mol), 117 g of dimethylformamide and 50 ml of water are heated to 75 ° C. for 20 hours heated with stirring. A 50% solution in dimethylformamide: water is obtained = 7: 3, which has a viscosity of 18 mPas at 250C. (Stabilizer 15a) Stabilizer 16, 16a and 16b 19.6 g of N, N'-dimethyl-N, N'-ethylenebisacrylamide (0.1 mol) are added at 250 ° C. with stirring, 37.2 g of a 23.7% strength aqueous N, N'-dimethylethylenediamine solution (0.1 mol) to. As a result of the heat of reaction released, the temperature rises within from 4 minutes to 42 ° C. The solution is then heated to 600C until there is no longer any increase in viscosity, which is the case after 5 hours. The yellowish one 50% solution then has a viscosity of 637 mPas at 250C.

The production of a second polyadduct only takes place analogously to this with the difference that not 37.2 g, but only 36.6 g of a 23.1% strength aqueous Solution of N, N'-dimethylethylenediamine (0.0965 mol) can be used. The reacted 50% solution has a viscosity of 1530 mPas / 250C. (Stabilizer 16a) the This polyadduct is produced analogously, but 37.8 g of one are now obtained 24.1% strength aqueous solution of N, N'-dimethylethylenediamine (0.1035 mol) is used. The 50% solution of the end product then has a viscosity of 1040 mPas / 250C.

(Stabilizer 16b) Stabilizer 17, 17a and 17b Within 1 1/2 86 g of methyl acrylate (1.0 mol) are added 88 hours with stirring and cooling g of 3-amino-1-methylaminopropane (1 mol). The further reaction is carried out as follows as indicated below for the manufacture of stabilizer 18. It becomes a residue of 140.8 g obtained, which is a 50% solution with 140.8 g of dimethylformamide a viscosity of 164 mPas at 250C results.

A second product is manufactured in the same way, only with the difference, that instead of 86 g of methyl acrylate (1 mol) used 129.0 g (1.5 mol) will. 164 g of a residue are obtained, which is a 50% strength solution in dimethylformamide with a viscosity of 147 mPas at 250C. (Stabilizer 17a) Another Polyaddition condensation product is formed analogously, but with the difference that an additional 71 g of acrylic acid amide (1.0 mol) are used. One moves in such a way that the solution of 88 g of 3-amino-1-methylaminopropane in 100 ml of methanol 71 g of acrylic acid amide are added and the solution is then added for 7 hours Heated to 70 ° C. It is now cooled to 40 ° C. and is set inside with cooling 86 g of methyl acrylate are added over a period of 1 hour. Further processing then takes place as indicated for stabilizer 18. - A residue of 218 g is obtained, the with the same amount of dimethylformamide a 50% solution with a viscosity of 47 mPas at 25 0C results.

(Stabilizer 17b) Stabilizer 18 While stirring and 43 g of methyl acrylate (0.5 mol) and 58.5 g of N, N'-dimethyl-tetramethylenediamine are used for cooling at 300.degree (0.505 moles). The mixture is then heated to 60 ° C. for 6 hours and to 100 ° C. for 10 hours. It is then distilled with a small column of 4 theoretical plates when the temperature rises to 140 ° C, the split off methanol very slowly. Finally, remove the last volatile components from the oil pump.

A yellowish residue of 85.8 g is obtained, which is in the same Amount of dimethylformamide to a 50% solution with a viscosity of 32 mPas is dissolved at 25 ° C.

Stabilizer 19 43.0 g of methyl acrylate are added dropwise with stirring (0.5 mol) within 1 hour at 40 ° C. in 72.5 g of N, N ', N "-trimethyl diethylenetriamine (0.5 moles) a. Within 4 hours, the temperature is so high that the reaction mixture begins to boil.

The internal temperature is then 147 ° C. Now it is heated for another 5 hours under reflux. During this time, the internal temperature decreases as a result Elimination of methanol to 1260C.

Thereupon the methanol as well as not yet unused starting materials are used at an outside temperature of 1500C initially without vacuum and finally under vacuum distilled off. 91.6 g of a thick, viscous, yellowish residue are obtained, the one with 91.6 g of water to a 50% aqueous solution with a viscosity of Dissolves 159 mPas at 25 ° C.

Stabilizer 20 While stirring, the mixture is added dropwise at 230C within half a time Hour 86 g of N, N'-di-n-butyl-ethylenediamine in 99 g of 1,4-butanediol bisacrylate. The internal temperature rises to 32 ° C. during this process. Thereafter warmed up within 4 hours to 60.degree. C., the viscosity gradually increasing from 6 mPas / 44.degree increases to 38 mPas / 60 ° C.

The mixture is left at 60 ° C. for a further 7 hours and then increased at a viscosity from 280 mPas / 600C to a temperature of 700C, which is then reached until the viscosity has increased maintains, which still takes about 12 hours. The viscosity has afterwards reaches a value of 1460 mPas at 70 ° C. It is diluted with 185 g of dimethylformamide to a 50% solution with a viscosity of 35 mPas / 250C.

Stabilizers 21 and 21a 44 g of N, N'-dimethylethylenedimine are added dropwise with cooling and stirring (0.5 mol) in 99 g of butanediol-1,4-bisacrylate (0.5 mol) at 40 ° C. Then leaves the reaction mixture for 5 hours at 60.degree. The reaction mass is doing continuously more viscous.

Finally, it has a viscosity of 31,800 mPas at 250C 50% solution in dimethylformamide one of 65 mPas / 25 0C.

42 g of N, N'-dimethylethylenediamine are obtained under the same conditions (0.475 mol) reacted with 99 g of 1,4-butanediol bisacrylate (0.5 mol). One receives a Polyadduct with a viscosity of 22,800 mPas at 25 ° C. (Stabilizer 21a) Stabilizer 22 43 g (0.5 mol) of anhydrous piperazine are put under at 40 ° C Cooling and stirring within 1 hour 99 g of 1,4-butanediol bisacrylate (0.5 mol) and then heated to 75 ° C for a further 6 hours. By adding 142 g of dimethylformamide a 50% solution of the polyadduct is produced, which has a viscosity of 143 mPas at 250C-hat.

Stabilizer 23 Within 40 minutes at 250C with stirring 149.7 g of n-butyl-bis- (3-n-butyl-aminopropyl) -amine (0.5 mol) in 99 g of butanediol-1,4-bisacrylate (0.5 mol) was added dropwise and then heated to 600C until the polyaddition is finished. This is the case after 35 hours. The viscosity is 4510 mPas increased at 600C. The polyadduct has a viscosity of 13,300 at 250C mPas.

Stabilizer 24 A mixture of 226 g 1,4-butanediol bismethacrylate (1.0 mol) and 88 g of N, N'-dimethylethylenediamine (1.0 mol) are heated for 53 hours 700C. The polyadduct has a viscosity of 240 mPas at 250C.

Stabilizer 25 A mixture of 99 g of ethylene glycol dimethacrylate (0.5 mol) and 44 g of N, N'-dimethyl-ethylenediamine (0.5 mol) is a total of 84 hours heated to 70 ° C for a long time. The polyaduct has a viscosity of 1003 mPas / 25 ° C.

Stabilizer 26 84 g of anhydrous piperazine (1.0 mole) and 226 g of 1,4-butanediol dimethacrylate (1.0 mol) is heated to 730 ° C. for 48 hours. The viscosity is then 4800 mPas grown at 730C. Man dilutes with 310 g of dimethylformamide to a 50% strength Solution with a viscosity of 14 mPas at 250C.

Stabilizers 27 and 27a 24.9 g of 1,3,5-triacryloyl-hexahydro-s-triazine (0.1 mol) are added to a solution of 10.9 g of diethylamine at 200 ° C. with stirring (0.15 Mol) in 46 ml of water. The internal temperature rises as a result of the heat of reaction released within 10 minutes to 36 ° C 1. The mixture is then heated to 50 ° C. for a further 5 hours. Then 10.2 g of N, N ', N "-trimethyl diethylenetriamine (0.07 Mol) was added and the reaction mixture was left at 50 ° C. for a further 15 hours. the 50% strength aqueous solution has a viscosity of 489 mPas at 250C.

The production of a second polyadduct takes place analogously, only with different amounts of the amine components. 9.5 g of diethylamine are used (0.13 mol) 12.3 g of N, N ', N "-trimethyl diethylenetriamine (0.085 mol).

The 50% strength aqueous solution of the end product has a viscosity at 25 ° C of 2690 mPas. (Stabilizer 27a) Stabilizer 28 and 29 These products are analogous to stabilizer 19, but with the difference that instead of 72.5 g of N, N ', N "-trimethyl diethylenetriamine (0.5 mol) for stabilizer 28 76.2 g (0.525 Mol) in the case of the stabilizer 29, 69.0 g (0.475 mol) are used.

In the case of stabilizer 28, a residue of 99 g is obtained, which is classified as 50 % aqueous solution has a viscosity of 190 mPas at 250C. With stabilizer 29, a residue of 898 g is obtained, which is one with the same amount of water 50% strength aqueous solution with a viscosity of 196 mPas / 25 ° C results.

Stabilizer 30 With cooling, 86 is set within 2 hours g of methyl acrylate at 200C 88 g of N, N'-dimethylethylenediamine. Then warmed up boil within an hour, i.e. up to an internal temperature of 115 ° C. From then on, the mixture is refluxed for a further 6 1/2 hours - the internal temperature falls in the process to 102 ° C.

Then you distill first on the water jet pump and last all volatile components on the oil pump at a maximum outside temperature of 1500C away. A light brownish residue of 19.2 g is obtained. The 50% aqueous Solution of the polyadduct has a viscosity of 32 mPas with 25OC stabilizers in the comparative examples (V 1 to V 5) V 1: methylene-bis-acrylamide V 2: methylene-bis (ß-dimethylamino-propionic acid amide) V 3: Mixture of 1 part of 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -6-chlorobenzotriazole 1 part 1,6-hexanediol-bis- (4-hydroxy-3,5, -di-tert-butylphenyl-propionic acid ester) V 4: Mixture of 1 part of the same benzotriazole as in V 3 1 part of pentaerythritol tetra-bis (4-hydroxy-3,5-di-tert-butyl-phenyl-propionic acid ester) V 5: mixture of 1 part benzotriazole as in V 3 1 part (4-hydroxy-3, 5-di-tert. -butyl-benzyl) -diethylphosphonic acid ester.

Polyurethanes (PUR I-XII), which the stabilizers 1 to 27 as well the comparison substances (V 1 to V 5) were added.

PUR I consists of 2250 g (1.0 mol) of a butanediol-1,4-adipate, 216 g of 1,4-butanediol (2.4 mol) and the equivalent amount of 4,4'-diphenylmethanediisocyanate (850 g). The 30% solution in dimethylformamide / methyl ethyl ketone = 3: 2 has a Viscosity of 12,000 cP at 25 ° C.

PUR II is a 30% solution of a polyester urethane in dimethylformamide / methyl ethyl ketone (1: 1) with a viscosity of 30,000 cP / 25 ° C, it consists of 1800 g (2.0 mol) of a 1,4-butanediol adipate, 174 g of tolylene diisocyanate, 186 g of ethylene glycol (3.0 Mol) and the equivalent amount of 4,4'-diphenylmethane diisocyanate (1000 g).

PUR III is a 25% solution of a polycarbonate polyester urethane in dimethylformamide / MEK = 5: 2 with a viscosity of 10,000 cP at 25 ° C. That Polycarbonate polyester urethane was obtained by melt condensation of 1000 g (0.5 mol) Hexanediol polycarbonate, 1125 g (0.5 mole) of a 1,4-butanediol adipate, 270 g 1,4-butanediol (3.0 mol) and the equivalent amount of 4,4'-diphenylmethane diisocyanate (100 g) produced.

PUR IV is a 25% solution of an aromatic one-component polyurethane in dimethylformamide / methyl ethyl ketone = 4: 1 with a viscosity of 15,000 cP at 25 ° C; it is made up of 2250 g (1.0 mol) of a 1,4-butanediol adipate, 396 g of ethylene glycol, and the equivalent amount of 4,4'-diphenylmethane diisocyanate (1450 g).

PUR V is a 25% solution of an aromatic one-component polyester urethane in dimethylformamide / methyl ethyl ketone = 3: 2, viscosity 1,000 cP / 250C; the polyurethane consists of 1700 g (1.0 mol) of a mixed polyester of hexanediol 1,6 / neopentyl glycol / Adipic acid, 135 g 1,4-butanediol (1.6 moles) and the equivalent lot 4,4'-diphenylmethane diisocyanate (625 g).

PUR VI is a 25% solution of an aromatic one-component polyether urethane in dimethylformamide / methyl ethyl ketone (1: 1), with a viscosity of 10,000 cP / 25 ° C; the polyurethane consists of 2000 g (1.0 mol) of a polypropylene glycol ether, 180 g (2.0 mol) of 1,4-butanediol and the equivalent amount of 4,41-diphenylmethane diisocyanate (750 g).

PUR VII is a 30% solution of an aliphatic one-component polyester urethane in toluene / isopropanol / ethyl glycol = 29: 29: 12 with a viscosity of 22,000 cP / 25 ° C. The polyurethane was made by reacting an NCO prepolymer from 1700 g (1.0 mol) of the polyester described in PUR V and 490 g (2.2 mol) of 1-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethyl-cyclohexane with 205 g (1.2 mol) of 1-amino-3, 3,5-trimethyl-5-aminomethylcyclohexane made in solution.

PUR VIII is a 30% solution of an aliphatic one-component polyether urethane in toluene / isopropanol (1: 1), viscosity 20,000 cP / 250C. The production takes place analogous to PUR VII.

2000 g (1.0 mol) of polypropylene glycol ether are mixed with 490 g (2.0 mol) 1-isocyanato-3,3; 5-trimethyl-5-isocyanatomethylcyclohexane to form an NCO prepolymer implemented. This is in toluene solution with 253 g (1.2 mol) of 4,4'-diaminodicyclohexylmethane converted in isopropanol to polyester urethane urea.

PUR IX is also a 30% solution of an aliphatic one-component polyether urethane in toluene / isopropanol. Viscosity 15,000 cP / 250C. The production takes place in the same way PUR VIII.

Instead of polypropylene glycol, 2000 g (1.0 mol) of tetramethylene glycol polyether are used used.

PUR X is a 30% solution of a polyester urethane in ethyl acetate with 25,000 cP / 250C, the polyester urethane from 500 g of a polyester made from ethylene glycol and adipic acid (molecular weight 2000) and 500 g of a polyester made from diethylene glycol and adipic acid (molecular weight approx. 2000) built up with 78 g of 2,4-tolylene diisocyanate is. This polyurethane solution is 5.0 g per 100 g of solution before processing a 75% solution of a polyisocyanate dissolved in ethyl acetate. (NCO) number 10.5), prepared from 1 mole of trimethylolpropane and three moles of 2,4-tolylene diisocyanate and 5.0 g of a 10% solution in ethylene chloride / ethyl acetate (1: 1) of a reaction product added from 1 mole of N-methyldiethanolamine and 2 moles of phenyl isocyanate.

PUR XI is a 40% dispersion of a polyester urethane in water. 1700 g (1.0 mol) of the polyester used in PUR V are mixed with 303 g (1.8 mol) Hexanediisocyanate converted to an NCO prepolymer; this is in aqueous dispersion with 152 g (0.8 mol) of ethylenediamine-ethylsulfonic acid sodium ale chain extenders built up to polyester urethane urea.

PUR XII is a 40% dispersion of a polyester urethane in water. A mixture of 1.0 mol of an ethyl glycol adipate (OH number 56), 0.25 mol of one Mixed polyester from ethylene glycol / adipic acid / phthalic acid (OH number 56) and 0.06 Mol of neopentyl glycol becomes an NCO prepolymer with 2.0 moles of 4,4'-diphenylmethane diisocyanate implemented. This is with a mixture of 0.6 mol of ethylenediamine-äthylsulfonsaurem Sodium and 0.1 mol of ethylenediamine converted into the polymer as chain extenders.

The lightfastness is determined by white pigmented films made from the polyurethanes I to XII or on polyurethane coatings on textile substrates according to DIN 54 004 determined. The light resistance, i.e. the decrease in tensile strength and the Elongation is also determined on white pigmented films (DIN 53 504). the Polyurethane films were made from solutions by conventional methods. The coating samples were obtained according to the following general procedure: On a coating machine the polyurethane solution is doctored onto a release paper using a roller doctor blade; the application rate is 120 g of solution / m2 in each case. After the first passage through the drying tunnel, which has an air temperature of 100 ° C at the entrance and a those of 140 ° C, are in the second coating plant or after return the web 120 g / m2 of an adhesive coat solution knife-coated in an analogous manner, the textile web, a roughened cotton duvetine product weighing 240 g square meter, laminated and the solvent mixture of the adhesive coating evaporates in the drying tunnel.

When leaving the drying tunnel, the release paper and the coated Fabric web wound up independently of each other.

Examples 1+ to 5+ in Table 4 are comparative tests. Table 1 At- PUR Stabili-% Stabil- Zero value light- light resistance play sator sator, covered- tensile strength- fracture- genuine- after 400 hrs. after 66 hrs. Exposure in the fade-o-meter test is known as stretching PUR- (kp / cm2) (%) (DIN xeno light test Solid (DIN 53504) 54004) tensile strength- fracture- tensile strength- fracture- ability stretching ability stretching (kg / cm2) (%) to (kp / cm2) (%) DIN 53504 1 I 0 0 500 600 3-4 100 300 100 250 I 1 3 500 600 6-7 370 580 370 450 2 II 0 0 500 450 3 - 4 250 350 240 250 II 1 3 500 450 6-7 420 400 420 440 3 III 0 0 450 500 4 235 450 250 370 III 1 3 450 500 7 430 440 350 420 III 1 2 450 500 6-7 300 430 300 400 4 IV 0 0 500 450 4 200 300 250 330 IV 1 3 500 450 7 400 455 370 400 IV 1 2 500 450 6-7 400 470 355 350 5 II 2 3 500 450 6-7 480 440 490 420 6 I 2 3 500 600 6-7 325 630 320 580 7 II 3 3 500 450 6 440 370 440 380 8 iI 4 3 500 450 7 435 430 413 415 Table 2 At- PUR Stabil-% Stabil- Zero value light- play sator sator, covered- tensile strength- fracture- genuine- after 400 hrs. after 66 hrs. No stretching means exposure in the fade-o-meter test PUR- (kp / cm2) (%) (DIN xeno light test Solid (DIN 53504) 54004 tensile strength fracture tensile strength fracture ability stretching ability stretching (kg / cm2) (%) to (kp / cm2) (%) DIN 53504 9 I 5 3 500 600 5 413 690 310 530 10 II 6 3.5 500 450 5-6 360 425 325 400 11 II 7 3.5 500 450 6 443 430 434 420 12 II 8 3.5 500 450 6-7 430 430 405 400 13 II 9 3.5 500 600 5 380 580 200 350 14 II 10 3.5 500 450 6-7 420 440 410 400 15 II 11 3.5 500 450 7 350 520 345 520 16 II 12 3.3 500 450 7 475 465 430 470 17 II 13 3.5 500 450 6 355 540 350 510 18 II 14 3.5 500 450 6-7 480 430 440 530 19 II 15 3.5 500 450 6-7 365 550 300 520 20 I 16 3 500 600 5-6 432 570 375 580 21 II 17 3 500 450 5 480 420 460 480 22 II 18 3.5 500 450 5 413 400 375 420 23 II 19 3.5 500 450 6 424 415 410 430 24 II 20 3.5 500 450 6-7 410 440 390 380 Table 3 At- PUR Stabil-% Stabil- Zero value light play sator sator, covered- tensile strength- fracture- genuine- after 400 hrs. after 66 hrs. No stretching means exposure in the fade-o-meter test PUR (kp / cm2) (%) (DIN xeno light test Solid (DIN 53504) 54004 tensile strength fracture tensile strength fracture ability stretching ability stretching (dp / cm2) (%) (kp / cm2) (%) according to DIN 53504 25 II 21 3.5 500 450 6-7 440 400 340 470 26 II 22 3.5 500 450 6-7 470 460 425 410 27 II 23 3.5 500 450 5-6 435 400 300 410 28 II 24 3.5 500 450 5 420 400 445 420 29 II 25 3.5 500 450 6-7 470 510 425 470 30 II 26 3.5 500 450 6-7 480 440 360 500 31 II 27 3.5 500 450 6 415 420 390 350 32 V 0 0 400 550 4 110 250 100 200 V 4 3 400 550 6-7 315 560 310 570 33 VI 0 0 180 550 5 30 200 30 150 VI 1 3.3 180 550 6-7 150 750 100 730 34 X 0 0 350 700 4-5 90 490 40 180 X 4 1.0 350 700 6 205 770 200 800 35 XII 0 0 250 800 3 - 4 70 320 - - XII 1 2 250 800 6 245 900 - - Table 4 At- PUR Stabil-% Stabil- Zero value light- play sator sator, covered- tensile strength- fracture- genuine- after 400 hrs. after 66 hrs. No stretching during exposure in the fade-o-meter test PUR kp / cm2% (DIN xeno-light test Festsboff (DIN 53504 54004 Tensile strength- Break- Tensile strength- Break- ability to stretch (kp / cm2) (%) (kp / cm2) (%) according to DIN 53504 36 XI 0 0 200 700 7-8 60 100 20 900 XI 1 0.5 200 700 7-8 120 650 140 760 XI 1 2.0 200 700 7-8 120 700 170 760 37 VII 0 0 500 500 7-8 275 650 390 630 VII 1 3 500 500 7-8 500 700 500 500 38 VIII 0 0 400 440 7-8 destroyed destroyed VIII 1 3 400 440 7-8 250 530 380 500 39 IX 0 0 250 700 7-8 destroyed destroyed IX 4 3.5 250 700 7-8 230 700 240 690 1+ I V-1 4 500 600 4 100 290 110 250 I 0 0 500 600 3-4 100 300 100 250 2+ I V-2 4 500 600 4 100 300 120 260 3+ I V-3 2 500 600 5 170 410 130 290 4+ I V-4 2 500 600 5 240 470 170 310 5+ I V-5 2 500 600 5 240 500 180 340 Stabilization of Polyurethane Elastomer Filaments Example 40 Production of Polyurethane XIII 1200 parts of an adipic acid-hexanediol-1,6 / 2, 2-dimethylpropanediol polyester (molecular weight 1615), 288 parts of diphenylmethane-4,4'-diisocyanate and 372 parts of dimethylformamide (DMF) Reacted 110 minutes at 540C until the NCO content is 2.35% (based on solids). 1612.5 parts of the prepolymer solution formed are in a solution of 58.1 parts of ß-semicarbazido-propionic acid hydrazide (H2N.NH.CO.NH. (CH2) 2.CO.NH.NH2) in 116 parts of water and 3356 parts of dimethylformamide within of 10 minutes with thorough stirring and pigmented with 4% TiO2 (based on solids).

Stabilizer additive according to the invention The highly viscous (720 poise) Solution is divided into several parts and a) without the addition of stabilizers b) with 1% by weight of the stabilizer 4 (based on PUR solids) c) with 2% by weight of the stabilizer 4 d) with 3.1% by weight of the stabilizer 4 (100 mVal of tert.

Amino groups) for spinning according to the dry or wet spinning process or prepared for casting films. The stabilizers are in the Polyurethane solution readily soluble and do not result in any malfunctions during dry spinning via a 16-hole nozzle with a diameter of 0.2 mm. The threads are with a stretch of 30% baked on bobbins at 1300C for 1 hour. To the test the threads are 8, 15, 22, 30, 44 and 66 hours for discoloration and polymer degradation irradiated with UV light using an ATLAS-Fade-O-meter and then checked for strength checked (see table 5).

The results show one as the amount of the stabilizer increases strongly increasing stabilizing effect. With an addition of about 100 mVal tert. Amino group / kg of elastomer an excellent level of fastness is already achieved.

If you put a polyurethane of the same composition, but under Incorporation of 100 mVal / kg of N-methyl-bis- (ß-hydroxypropyl) -amine, so with appropriate Fade-0-meter exposure found a polymer degradation at about the same rate as at the polymers takes place without the addition of stabilizers. Discoloration already occurs 22 hours a.

The elastomer solution is spun with or without the addition of a stabilizer after the wet spinning process, stabilizing effects similar to those of the dry spinning process are obtained found. The stabilizer additive is not washed out, but coagulated together with the elastomer substance.

If the solution is poured into films in a thickness of about 0.2 mm, cuts this into strips and then exposed in the Fade-O-meter, so the discoloration goes (and the degradation) on the compact film surface more slowly. While the Films without additives are clearly discolored yellow after 15 hours the films with 2% addition are colorless for up to 88 hours. The 3.1% additive films are the film surface is still colorless even after 110 fade 0-meter exposure hours remains elastic and the strength is still well preserved.

Table 5 Fade-O-meter exposure of dry-spun elastomer threads (chain modification with semicarbazido-propionic acid hydrazide) Stabilizer tear strength (cN / dtex) / elongation at break (%) after exposure while as films 0 15 hours 22 hours 30 hours 44 hours 66 hours without 0.73 / 553 0.30 / 414 0.20 / 351 0.17 / 336 0.10 / 204 0.09 / 148 from 15 hours colorless yellow yellow + 1% 0.72 / 587 0.47 / 500 0.30 / 436 0.31 / 414 0.11 / 244 0.09 / 151 - Stabilizer 4 colorless colorless colorless almost yellowish yellow + 2% 0.66 / 584 0.60 / 561 0.55 / 537 0.45 / 501 0.23 / 372 0.13 / 250 to # 88 hours Stabilizer 4 colorless colorless colorless colorless yellowish yellowish exposure + 3.1% 0.66 / 587 0.55 / 560 0.55 / 563 0.54 / 563 0.50 / 552 0.44 / 520 to # 110 hours Stabilizer 4 colorless colorless colorless colorless colorless colorless exposure colorless EXAMPLE 41 Production of Polyurethane XIV As in Example 40, an NCO prepolymer is produced from 1200 parts of the polyester, 312 parts of diphenylmethane-4,4'-diisocyanate and 378 parts of dimethylformamide by reaction at 530C in the course of 100 minutes (isocyanate content of the prepolymer: 2 , 86% NCO, based on solids).

26.8 parts of ethylenediamine in 3373 parts of dimethylformamide are used in + 100C with 50 parts of dry ice converted into a carbamate suspension and then 1606 parts of the above NCO prepolymer solution are added with stirring. With release of C02 the result is a homogeneous elastomer solution that is pigmented with 4% TiO2 (rutile).

Stabilizer Additive According to the Invention The highly viscous solution is divided and a) without the addition of stabilizer b) with 1% by weight of the stabilizer 4 c) with 2% by weight of the stabilizer 4 d) with 3.1 "of the stabilizer 4 for spinning processed according to the various spinning processes. Spinning and testing will be carried out as in Example 40.

The results (see Table 6) show an increasing stabilizing effect with the amount of stabilizer added, with an amount of about 100 mVal tert. Amine per kg of the stabilized polymer (approx. 3.1% stabilizer 4) is an excellent one Stabilization is achieved.

Compared to this, 100 mVal of N-methyl-bis- (ß-hydroxypropyl) -amine are built or 100 mVal of N-tert-butyl-bis- (ß-hydroxypropyl) -amine into the polymer an effect that is orders of magnitude smaller is observed. A discoloration then already occurs after 8 hours, the polymer degradation is only about 5 fade-0-meter-hours postponed.

Even with a variation in the amount of basic diols incorporated from 0 to 30, 50, 66.6, 100, 150 to 200 mVal tertiary nitrogen (as N-methyl-bis- (ß-hydroxypropyl) -amine) the corresponding polyurethanes are already clear at 8 fade-0-meter hours yellow discolored and with increasing amount of tert. Amin occurs (at 8 hours fade-0-meter exposure time) only a slight reduction in discoloration. The effect is orders of magnitude less than in the method according to the invention.

The excellent stabilizing effect is not only due to the Structure of diamine, for example N, N ', N11-trimethyldi-ethylenediamine, to be traced back, because chain extension of an NCO prepolymer (composition as in example 40) with N, N1, N "-trimethyldiethylenetriamine no better light resistance than can achieve with ethylenediamine. The same applies to the use of N, N ', N "-trimethyl diethylenetriamine (or N, N'-dimethylethylenediamine) as a coextender (5 to 50%) in addition to ethylenediamine.

Table 6 Fade-O-meter exposure of dry-spun elastomer threads (titer approx. 200 dtex) (chain extension with ethylenediamine) Stabilizer tear strength (cN / dtex) / elongation at break (%) after fade-o-meter exposure of comments Addition 0 15 22 30 44 66 hours without 0.72 / 540 0.11 / 210 <0.10 / 167 - - - colorless yellow intense intense discolored yellow 1% 0.71 / 509 0.28 / 381 0.12 / 243 0.11 / 218 0.09 / 157 - Stabilizer 4 colorless yellowish yellowish yellow yellow yellow 2% 0.69 / 509 0.53 / 495 0.48 / 468 0.40 / 447 0.12 / 251 0.09 / 166 Stabilizer 4 colorless colorless almost yellowish yellow colorless colorless 3.1% 0.69 / 536 0.58 / 503 0.57 / 495 0.57 / 494 0.45 / 479 0.10 / 184 Stabilizer 4 colorless colorless colorless colorless almost yellowish colorless yellow 5.0% - - - - - - as a film Stabilizer 4 colorless colorless even after 88 hours. colorless Example 42 Production of Polyurethane XV 1600 parts of a polyester as in Example 40, but with a molecular weight of 1690, 380 parts of diphenylmethane-4,4'-diisocyanate and 495 parts of dimethylformamide are heated at 500 ° C. for 90 minutes until the NCO content of the prepolymer 2.175% (based on solids).

39.5 parts of ß-semicarbazido-propionic acid hydrazide are in 80 parts Dissolved warm water, diluted with 2460 parts of dimethylformamide and with 1140 parts the prepolymer solution stirred. After pigmentation with 4% (rutile) TiO2, a viscous solution obtained (520 poise / 200C).

Stabilizer additive according to the invention proportions of the above solution a) without stabilizer b) mixed with 2% by weight of the stabilizer 4 and after Dry spinning process. The threads, which are dry-spun as usual, are made with typical acid dyes colored: with 2% Supranolechtrot-GG (C.I.-No. 24 790): gives only weak staining in a); most of the dye remains undrawn in the Dye bath; results in practically complete absorption of the dye in b).

with 2% supramine blue FRW (C.I. Acid Blue 220): gives only moderate staining at a); most of the dye remains undrawn in the dyebath; results in b) however complete drawing up on the fiber.

with 12% Telonchromschwarz C (chromium plating dye; C.I.-No.

14645): gives only gray soiling in a) but deep black color with high rub fastness in b).

The two solutions were also poured into films and the films Further investigated: Treatment with sodium chloride solution results in the following findings: 1.) 20 minutes at 700C; 750 ppm Cl + / l: with film from solution a) strong yellow discoloration with film from solution b) significantly reduced discoloration (pale yellowish) 2.) 40 Minutes at 700C; 2250 ppm Cl / 1: in spite of more stringent test conditions, the Advantage obtained: in the case of film from solution a) strong yellow-yellow-brown discoloration in the case of film from solution b) only slightly yellowish discoloration.

The cast films were used for fade 0-meter exposure using Foil cutting machines cut monofilament threads (approx. 330 dtex) and use the Fade-O-meter exposed. The stabilizing effect is excellent. The measurements were made after 88 fade 0 meter hours not continued, although here the threads are still colorless were (see Table 7).

Table 7 Fade-O-meter exposure on cut threads (approx. 330 dtex monofilament) (polyester urethane based on semicarbazidopropionic acid hydrazide) Stabilizer tear strength (cN / dtex) / elongation at break (%) after exposure of 0 15 22 44 66 88 hours. Comments without 0.58 / 656 0.50 / 634 0.40 / 576 0.15 / 422 0.09 / 273 - colorless yellowish yellowish yellow yellowish brown yellowish brown yellow + 3.1% 0.63 / 652 0.59 / 649 0.52 / 617 0.51 / 609 0.50 / 606 0.49 / 593 measurements not Stabilizer 4 colorless colorless colorless colorless colorless colorless continued, films even after 110 hours still colorless Example 43: Production of Polyurethane XVI 1200 parts of the adipic acid polyester from Example 40 (PUR XIII), 24.1 parts of bis (β-hydroxypropyl) methylamine, 357.4 parts of diphenylmethane-4,4'-diisocyanate and 396 parts Dimethylformamide is converted to prepolymer for 95 minutes at 90 ° C. up to an NCO content of 2.76% (based on solids content).

13.7 parts of ß-semicarbazido-propionic acid hydrazide are in 27 parts Dissolved warm water, mixed with 627 parts of dimethylformamide and stirring reacted with 322 parts of the above NCO prepolymer solution. After pigmentation with 4% TiO2 (rutile), the solution (322 poise) is diluted to 20% and mixed with different Amounts of stabilizer provided.

Polyurethane XVII 8.48 parts of ethylenediamine are in 1126 parts of DMF with 25 parts of solid carbon dioxide with precipitation of a very finely divided carbamate dispersion offset. Then 530 parts of the NCO prepolymer of polyurethane XVI stirred into the solution.

The resulting highly viscous solution (513 poise) is pigmented with 4% TiO2 and provided with various amounts of stabilizer.

Stabilization of the polyurethanes XVI and XVII: see Table 8 Table 8 Fade-O-meter exposure (cut threads) a) Polyester urethane chain extension with B-semicarbazido-propionic acid hydrazide Tensile strength (cN / dtex) and elongation at break (%) or discoloration according to Fade-O -meter exposure from 0 8 22 44 66 88 110 hours a) without 0.69 / 669 0.60 / 635 0.31 / 541 0.22 / 020 0.10 / 213 - - Additive colorless almost yellowish yellow yellow yellow- yellow- colorless brown brown b) + 2.99% 0.60 / 631 0.60 / 625 0.56 / 605 0.56 / 593 0.38 / 538 0.31 / 504 0.23 / 448 Stabilisa- colorless colorless colorless colorless almost almost yellowish gate 4 colorless colorless c) + 2.43% 0.66 / 618 0.65 / 626 0.65 / 625 0.58 / 606 0.43 / 526 0.34 / 506 0.23 / 427 Stahilisa- colorless colorless colorless colorless colorless almost almost gate 3 colorless colorless d) + 2.81% 0.62 / 667 0.62 / 666 0.59 / 656 0.40 / 607 0.19 / 417 0.17 / 412 0.10 / 249 Stabilisa- colorless colorless colorless colorless yellowish yellow yellow gate 21 e) + 2.15% 0.67 / 654 0.62 / 619 0.56 / 610 0.44 / 551 0.60 / 468 0.27 / 466 0.18 / 389 Stabilisa- colorless colorless colorless colorless yellowish yellowish yellow gate 28 yellow Continuation from Table 8 f) + 3% Stabilisa- colorless colorless colorless colorless colorless colorless weak gate 15 yellowish g) + 3% Stabilisa- colorless colorless colorless colorless colorless almost weak Sator 10 colorless yellowish h) + 3% Stahilisa- colorless colorless colorless almost almost almost faint gate 8 colorless colorless colorless yellowish i) + 3% Stabilisa- colorless colorless colorless colorless almost almost yellow gate 18 colorless colorless k) + 3% Stabilisa- colorless colorless colorless colorless almost almost yellow gate 22 colorless colorless Table 8 b) polyester urethane chain extension with ethylenediamine tensile strength (cN / dtex) and elongation at break (%) or discoloration after Fade-O-meter exposure of 0 8 22 44 66 hours a) without addition 0.60 / 630 0.27 / 579 0.11 / 446 - - colorless yellowish-yellow yellow-brown brown-yellow yellow b) + 2.99% 0.60 / 630 0.54 / 621 0.48 / 621 0.43 / 606 0.20 / 491 Stabilisa- colorless colorless almost colorless pale yellow-yellow gate 4 lich c) + 2.43% 0.57 / 632 0.52 / 622 0.36 / 572 0.28 / 548 0.12 / 420 Stabilisa- colorless colorless pale yellow-yellow yellow gate 3 lich Comparative experiments: The following substances were used in amounts of 3%: V-6: Polymer made from NIN ', N "-trimethyl-diethylenetriannine and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (in dimethylacetamide solution) V -7: polymer from N, N ', N "-trimethyl-diethylentr-ianine and hexane diisocyanate V-8: polymer from N, N'-dimethyl-N, N'-bis- (B-hydroxyethyl) -ethylenediamine and 1- Isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane V-9: Polymer of N, N'-dimethyl-N, N'-bis (β-hydroxyethyl) ethylenediamine and hexane diisocyanate added to the solutions as above. The films all showed a discoloration tendency which was not reduced (or only by about 1 to 5 fade-o-meter hours) on exposure. The comparison substances V-6 to V-9 have no or very considerably reduced effectiveness in terms of sanitary conditions.

Example 44: Polyurethane XVI II 800 parts of a polytetramethylene ether diol (Molecular weight 1045) with 16.45 parts of N-methyl-bis- (ß-hydroxypropyl -) - amine mixed and with a solution of 286 parts of diphenylmethane-4,4'-diisocyanate and 278 parts of dimethylformamide are heated to 40 to 45 ° C. for 40 minutes until the NCO content of the solution is 2.09% (based on solids).

5.24 parts of ethylenediamine are dissolved in 895 parts of dimethylformamide, converted into the carbamate with 20 parts of solid carbon dioxide and then with 440 Stir parts of the above NCO prepolymer solution. The resulting highly viscous solution is pigmented with 4% TiO2.

Polyurethane XIX 4.37 parts of hydrazine hydrate are in 895 parts of dimethylformamide dissolved, mixed with solid carbon dioxide and with 425 parts of the NCO prepolymer solution stirred by polyurethane XVIII. The resulting viscous polyurethane solution is with 4% TiO2 pigmented.

Addition of stabilizers according to the invention: Both elastomer solutions XVIII and XIX were a) without additive b) with 1% by weight of stabilizer 1 c) with 2 Weight% stabilizer 1 d) with 3 weight% stabilizer 1 e) with 2 weight% Stabilizer 1 + 2% by weight Stabilizer II from DOS 2 012 285 f) with 2% by weight of stabilizer 1 + 1% by weight of stabilizer II from DOS 2 012 285 + 1% by weight QR Tinuvin 127 from Geigy.

Comparative experiments: with 1% by weight of stabilizer II from DOS 2 012 285 + 1% by weight (i) Tinuvin 127 from Geigy dried to form films and the Films exposed as stripes in the fade-o-meter (Tables 9 and 10).

Table 9 Fade-O-meter exposure of film strips (PUR XVIII) 8 22 30 44 66 hours a) yellowish yellowish-yellow yellowish-yellow yellow yellow tears easily tears easily tears very easily tears very easily shows cracks with strong cracks - hardly expandable hardly expandable Elongation in the surface b) colorless colorless colorless pale yellowish yellowish stable stable stable moderately stable moderately stable beginning crack- beginning crack- education education c) """"" no cracking d) """almost colorless almost colorless-yellow- stable no cracking stable no cracking e) """" colorless stable no cracking f) """colorless" Comparison "almost colorless almost colorless yellowish yellowish almost stable moderately stable beginning crack- slight crack- education education Table 10 Fade-O-meter exposure of film strips (PUR XIX) 8 22 30 44 66 hours a) almost colorless yellowish yellowish yellow yellow intense yellow stable almost stable moderately stable tears easily without strength no cracking cracking in strong cracking education surfaces education b) colorless colorless almost colorless almost colorless yellowish stable stable stable almost stable moderately stable no crack- without crack- without crack- light crack- slight crack- education education education education education c) """" almost colorless almost stable slight crack education d) """almost colorless almost colorless stable almost stable without cracking without cracking e) "" colorless colorless almost colorless stable stable stable without cracking without cracking without cracking f) """" colorless stable without cracking Comparison "almost colorless yellowish yellowish yellow almost stable almost stable moderately stable low crack pattern. slight crack pattern. Cracking

Claims (17)

Claims 1) Polyurethane compositions stabilized against discoloration and degradation by light, characterized by a content of stabilizing substances which contain at least three structural units of the general formula in which R1 stands for hydrogen or a methyl group, R2 for a C1-C6-alkyl radical which is optionally substituted by a hydroxy, cyano or carbonamide group and optionally interrupted by an oxygen atom, and X for -0- or where R3 is hydrogen or a C1-C6 alkyl radical optionally substituted by a hydroxy, cyano or carbonamide group, optionally interrupted by an oxygen atom, or together with R2 forms a 5- or 6-membered heterocyclic ring, between two aliphatically bonded carbon atoms . 2. Polyurethanes according to claim 1, the 0.1-10 wt .-% of the stabilizing active substance contain. 3. Polyurethanes according to claim 1, the 0.5-5 wt .-% of the stabilizing active substance contain. 4. Polyurethanes according to claim 1, the 1.5-3.5 wt .-% det stabilizing active substance contain. 5. Stabilized polyurethanes according to claim 1 to 4, characterized in that a substance with the structural unit is used as a stabilizer in the R for M for an optionally substituted alkylene radical in whose chain one or more tert-nitrogen, oxygen atoms and aromatic or hydroaromatic rings can be contained, R3 for a C1-C6-alkyl radical substituted by a hydroxy, cyano or carbonamide group, which is represented by Oxygen can be interrupted or together with R2 forms a 5- or 6-membered ring and v stands for an integer of at least 3. 6. Stabilized polyurethanes according to claim 1) to 4), characterized in that a substance with the structure inhei t as a stabilizer in the R and independently for a grouping and Y stands for an optionally substituted C1-C6-alkyl radical, M has the same meaning as in claim 5 and an integer of at least 2 and R3 and R4 independently of one another are a C1- optionally substituted by a hydroxy, cyano or carbonamide group C6-alkyl radical, which can be interrupted by oxygen, or together represent a 5- or 6-membered ring. 7. Stabilized polyurethanes according to claim 1 to 4, characterized in that a substance having the structural unit of the formula is used as the stabilizer serves in which R, i ', M and w have the same meaning as in claim 6 and Z stands for an optionally substituted C2-C6-alkylene radical. 8. A process for the light stabilization of Polyurethdr, s, characterized in that substances are added to the polyurethanes during or after their preparation, which are at least three times the structural unit in the molecule contain in which X, R1 and R2 have the meaning given above. 9. The method according to claim 8, characterized in that the substances Solutions or dispersions of the polyurethanes are added. 10. The method according to claim 8, characterized in that the substances Polyurethane solids are incorporated during or after their manufacture. 11. A method for light stabilization of polyurethanes according to claim 8 to 10, characterized in that the added amount of stabilizer 0.1 - 10% by weight. 12. A method for light stabilization of polyurethanes according to claim 8 to 10, characterized in that the amount of stabilizer added is 0.5 - 5% by weight. 13. A method for light stabilization of polyurethanes according to claim 8 to 10, characterized in that the added amount of stabilizer 1.5 - is 3.5% by weight. 14. A method for light stabilization of polyurethanes according to claim 8 to 13, characterized in that as stabilizers polyaddition and / or mixed polyaddition condensation products from tape bisecondary aliphatic amines of the general formula in which M, R2 and R3 have the meaning given above and (b | acrylic acid and / or methacrylic acid esters of the general formula where R1 is hydrogen or a methyl group and R6 is an alkyl radical having 1 to 12, preferably 2 to 4, carbon atoms and / or (c) N, N'-alkylenebisacrylamides and / or N, N'-alkylenebismethacrylamides in general formula where Ra, R3, R4 and Y have the meaning given above and / or (d) alkylenebisacrylic and / or alkylenebismethacrylic acid esters of the general formula where R1 and Z have the meaning given above. be used. 15. The method according to claim 14, characterized in that the stabilizers from bis-secondary amines (a) and unsaturated compounds (b) in a molar ratio of (a): (b) between 0.8: 1.6 and 1.6: 0.8. 16. The method according to claim 15), characterized in that the molar ratio (a) :( b) between 0.9: 1.1 and 1.1: 0.9. lies. 17. Polyaddition and / or mixed polyaddition condensation products with a molecular weight of up to 20,000, prepared by reacting (a) bis-secondary aliphatic amines of the general formula and (b) acrylic acid and / or methacrylic acid esters of the general formula and / or (c) N, N'-alkylenebisacrylamides and / or N, N'-alkylenebismethacrylamides of the general formula and / or (d) alkylenebisacrylic and / or alkylenebismethacrylic acid esters of the formula where R1, R2, R4, R6, M, Y and Z have the meaning given above and R3 represents hydrogen or a C1-C6-alkyl radical optionally substituted by a hydroxy, cyano or carbonamide group, optionally interrupted by an oxygen atom, or together with R2 forms a 5-membered heterocyclic ring. Polyaddition and / or mixed polyaddition condensation products according to Claim 17, prepared by reacting (a) bis-secondary aliphatic amines of the general formula in which M has the meaning given above and R2 and R3 together represent a 6-membered heterocyclic ring, and (b) acrylic acid and / or methacrylic acid esters of the general formula where R1 is hydrogen or a methyl group and R6 is an alkyl radical having 1 to 12 carbon atoms and / or c) alkylenebisacrylic and / or alkylenebismethacrylic acid esters of the general formula where R1 and Z have the meaning given above.