CA1164865A - Poly-bis-triazinylamines, a process for their preparation, their use for stabilizing synthetic polymers and the polymers thus stabilized - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Hitherto unknown poly-bis-triazinylamines which have a linear structure, are not crosslinked and have a degree of polymerization of up to approx. 200, of the formula in which at least one of the radicals R1 to R5 must be a polyalkylpiperidyl group or must contain this group, are obtained by controlled reaction of a cyanuric hallde with diamines in several successive proccss stages.
The new compounds can be used as sparingly vola-tile and particularly migration-resistant light stabili-zers for synthetic polymers.

Description

- 2 -The invention relates to new poly-bis-triazinyl-amines, a process for their preparation and their use as light stabilizers having an antioxidative action for synthetic polymers.
The new poly-bis-triazinylamines are descri-bed by the general fQrmula (I) Rl R2 R3 R \
E~--t ~ N - X - N r N ~ 1, - Y - N ~ E2 (I ) RS R . n In this formula n denotes an integer from 1 to 200, pre-ferably 1 to 50 and particularly 1 to 15, Rl and R2 are identical or different and represent hydroger., Cl to C37 alkyl, preferably Cl to C18 alkyl and particu-larly Cl to C10 alkyl which is unsubstituted or substi-tuted by a hydroxyl group, or represent C5 to C12 cycloalkyl which is unsubstituted or substituted by up to four Cl to C4 alkyl groups, preferably unsubstituted C5 to C12 cycloalkyl, or represents C7 to Cl~ aralkyl, preferably C7 to Cg phenylalkyl or a group of the formula (II) CH2R6 H3C ~ R6 HN ~-H3C ~ 6 (II) ~t~2R
' 1 164~6 in which R6 ~enotes hydrogen or Cl to C6 alkyl, prefer-~bly hydrogen or methyl, but especially hydrogen.
R3 and R4 are identical or different and have the meanings indicated for Rl and R2 Preferably, on~ of these radicals is hydrogen, but, in particular, both radicals are hydrogen.
R5 is halogen, phenyl, -oR7 or -NR8R9, particu-larly -NR8R9, R7 in these groups denoting hydrogen, C
to C18 alkyl, preferably Cl to C4 alkyl, C3 to C12 alkenyl, C5 to C12 cycloalkyl, C7 to C18 aralkyl, C6 to C10 aryl or a radical of the formula (II). R radi-cals which are preferred are Cl to C4 alkyl, phenyl or the radical of the formula (II).
R8 and R9 are identical or different and repre-sent hydrogen, Cl to C37 alkyl which, particularly inthe case of C2 and C3 alkyl, can be substituted by Cl to C18 alkoxy and, in the case of C2 to C5 alkyl, can be substituted by Cl to C4 dialkylamino, preferably Cl to C2 dialkylamino, or represent C3 to C12 alkenyl, C5 to C12 cycloalkyl which is unsubstituted or is substituted by up to four Cl to C4 alkyl groups, C7 to C18 aralkyl, preferably C7 to Cg phenylalkyl, phenyl or naphthyl, preferably phenyl, C2 to C30 hydroxyalkyl, preferably C2 to C18 hydroxyalkyl and particularly C2 to C4 hydroxy-alkyl, or the radical of the ~ormula (II) R8 and R9, together with the common nitrogenatom, can also form a pyrrolidine ring or a piperidine, ~ morpholine or hexamethyleneimine ring which is unsubsti-tuted or substituted by up to four Cl to C4 alkyl groups ~ 16486~

X and Y are identical or different and denote C2 to C18 alkylene, preferably C2 to C12 alkylene and particularly C2 to C6 alkylene, or C2 to C12 bis-(propoxy)-alkylene, or C6 to C18, preferably C6 to C12, '5 monocycloalkylene, dicycloalkylene or'tricycloalkylene which is unsubstituted or substituted by up to four methyl groups, but which is preferably unsubstituted, and in which, in the case first mentioned, two C atoms can be replaced by N atoms which can carry propylene groups, or X and Y denote C6 to C18 arylene, preferably phenylene, or C7 to C18 aralkylene, but, in particular, X and Y are dicycloalkylene or tricycloalkylene, orpipera-zinylene radi.cals are present instead of the groupings Rl R2 R~ R4 -N-X-N- or -N-Y-N-, - R3 R4 15El is a halogen atom or a group -N-Y~N-H, ~ 4 R3 -N-~-N-H, -oR7 or -NR8R9,preferably chlorineandE2is hydrogen or an acyl group, preferably hydrogen, R3, R4, R7, R8 and R9 having the meanings indicated above and at .least one of the radicals Rl, R2, R3, R4, R7, R8 and R9 being of necessity a group.of the formula (II).
Rl to R4 can be identical'if X and Y are differ-ent. X and Y can be identical if at least one of the radicals Rl or R2 is different from R3 and R4 The new poly-bis-triazinylamines are obtained by using unsubstituted or partly substituted cyanuric halides as starting ma-terials. The individual interme(liate products can be isolated, but it i.s also possible to 1 16~6 effect the synthesis of the desired end products in a so-called "one-pot process" without isolating the inter-mediate compounds.
The synthesis can be carried out by two different reaction routes, which are outlined in the simplified reaction diagram below.

Hal N Hal ~0~ .
HalR1R2 H-R5 (Vl) / \ HNXNH (UIII) --5 to 40 ~

~ . ~I
Hal ~I~N~Hal Hal rO~ N-X- N ~ N~Hal ~ (VII) Hal ~rl ~IIIa) R1B2 ¦ ~!t r ¦ R3R4 H!JXNH ( III I I ) HNYNH ( IV) 10 - 70 ~ ¦ 10 - 70 4C
, _ _ _ _ _ R1 R2 / R1 R2 R R4 \
HalrN ~ N-X-N ~ N~, Hal ~al~ N~ N-X-N r N ~ ~~Y-;~ H
N~,N I~N ~N ;~N /n Va ri a nt HNYNH ( I V ) \ / H-R ( - 20D ~ \ / 50 - 200 R R2 R R4 \

~5 R R n (I) 1 16~8~5 The diamines (IV) and (VIII) can be employed`in any desired sequence, but the sequence shown in the diagram represents the pre~erred procedure. In the .
.~ormulae of the reaction diagram, Hal, n, Rl, R2, R3, R4, R5, X, Y, El and E2 have the meanings indicated above. In formula (VI), R5 cannot be halogen or phenyl;
In accordance with variant A, a dihalogeno-bis-triazinyldiamine of the formula (III) is reacted with a 0.8 to 1.4, preferably 1.0 to 1.2 and, particularly a 1 to 1 05, molar amount of a diamine of the formula (IV).
Variant B provides for reacting a poly-bis-triazinylamine of the formula (V), which is accessible from the compounds (IIIa) by reacting the latter with a 0.8 to 1.4, preferably 1.0 to 1.2 and, in particular, a 1 to 1,05, molar amount of a diamine of the formula (IV), with 0 8 to 1,4, preferably 1.0 to 1.2 and, in parti-cular, 1 O to 1.05, equivalents of a compound of the formula (VI) Variant C is a multi-stage one-pot process in which a cyanuric halide, preferably cyanuric chloride, is first reactedwit~ a 0.8 tolO3molar,preferably O.9to - 1.1 molar and, in particular, an equimolar, amount of a . compound of the formula (VI) in order to synthesize the intermediate compounds (VII), or is reacted with a 0 4 2~ to 0 7, preferably 0.5 to 0 6 and, in particular, 0,5 to 0.502, molar amount of a diamine of the formula (VIII) in order to prepare the intermediate compounds (IIIa).
The intex~ediate compo~mds thus obtained are then reacted, without being isolated, with a 0.4 to 0.7, preferably 0~5 to 0.6 and, in particular, 0~5 to 0.502~
molar amount either of a diamine of the formula (VIII), if the educt is a compound of the formula (VII), or with 5 a 0.8 to 1.4, preferably 1.0 to 1.2 and, in particular, 1,0 to 1.05, molar amount of a diamine of the formula (IV), if the educt is a compound of the formula (IIIa).
The intermediate compounds (III) or (V) which have been prepared in this manner are subseauently reacted, also without intermediate isolation, under the conditions indicated for the variants A or B, respectively, to give the desired poly-bis-triazinylamine.
The variant A, and the t'multi-stage one-pot reaction" which takes place as an intermediate stage via this mode of implementation, is a preferred embodi-ment The ~eactions are carried out in inert organic solvents, such as, for example, petroleum ether, petrol-.
eum fractions, acetone, ether, dioxane, benzene, toluene, xylene, cumene, mesitylene or mixtures thereof The variants A and B require reaction tempera-tures of 50 to 200, preferably 80 to 100 and, in parti-cular, 100 to 160, C In the process according to ~rariant C, the monosubstitution of the cyanuric halide to give compound (VII) is carried out at -5 to 40, pre-ferably -5 to 20 and, in particular, 0 to 10, C, the monosubstitution of the cyanuric hali.de to ~ive com-pound (IIIa) is carried out at -5 to 20, preferably 0 to 10, C, and the disubstitution of the dihalogenotriazine 1 ~64865 9 _ (VII) to give (III) and the disubstitution of the tetra-llalogenoditriazine (IIIa) to give (V) are carried out at :LO to 70, preferably 30 to 70 and, in particular, 40 to 60, C.
Inorganic bases are added in equivalent quan-tities as hydrogen halide acceptors in the preparation of the new compounds. Examples of suitable bases are sodium hydroxide, potassium hydroxide, sodium car-bonate and potassium carbonate, in solid form or in aqueous solution.
The following are examples of dihalogenotriazine intermediate compounds of the formula (VII): 2,4-di-~chloro - 6-[N-(2,2,6,6-tetramethyl-4-piperidyl)-3-hydroxypropylamino]-1,3,5-triazine, 2,4-dichloro-6-[N-(2,2,6,6-tetramethyl-4-piperidyl)-2-methoxypropylamino]-1,3,5-triazine, 2,4-dichloro-6-[N-(2,2,6,6-tetramethyl-4-piperidyl)-3-etnoxypropylamino]-1,3,5-triazine, 2,4-dichloro-6-[N-(2,2,6,6-tetramethyl-4-piperidyl)-3-octa-decyloxypropylamino]-1,3,5-triazine, 2,4-dichloro-6-[N-(2,2,6,6-tetramethyl-4-piperidyl)-3-dimethylaminopropyl-amino~-1,3,5-triazine, 2,4~dichloro-6-[N-(2,2,6,6-tetra-methyl-4-piperidyl)-3-diethylaminopropylamino]-1,3,5-triazine, 2,4-dichloro-6-[N-(2,2,6,6-tetramethyl-4-piperidyl)-2-dimethylaminoethyl~mino]-1,3,5-triazine, 2,4-dichloro-6-[N-(2,2,6,6-tetramethyl-4-piperidyl)-4-diethylaminobutylamino~-1,3,5-triazine, 2,4-dichloro-6-~N-(2,2,6,6-tetramethyl-4-piperidyl)-4-diethylamino-1-methylbutylamino]~l,3,~-triazine, 2,4-dichloro-6-dioc-ta-decylamino-1,3,5-triazine, 2~4-dichloro-6-bu-tylamino-116~865 1,3,5-triazine, 2,4-dichloro-6-octadecylamino-1,3,5-triazine, ~,4-dichloro-6-dicyclohexylamino-1,3,5--triazine, 2,4-dichloro-5-dibutylamino-1,3,5-triazin~, 2,4-dicl~oro-5-amino-1,3,5-triazine, 2,4-dichloro-6-[N-(2,2,6,6-tetramethyl-4-piperidyl)-amino]-1,3,5-triazine, 2,4-~ichloro-6-[N-(2,2,6,6-tetramethyl-4-piperidyl)-butyl-amino]-1,3,5-triazine, 2,4-dichloro-6-[N-(2,2,6,6-tetramethyl-4-piperidyl)-hexylamino]-1,3,5-triazine, 2,4-dichloro-6-[N-(2,2,6,6-tetramethyl-4-piperidyl)-octadecylamino]-1,3,5-triazine, 2,4-dichloro-6-[N-bis-(2,2,6,6-tetramethyl-4-piperidyl)-amino 3 -1, 3,5-triazine, 2,4-dichloro-6-(1,1,3,3-tetramethyl)-butylamino-1,3,5-triazine, 2,4-dichloro-6-morpholino-1,3,5-triazine and 2,4-dichloro-6-phenoxy-1,3,5-triazine The following are examples of compounds of the formula (VIII) and (IV): ethylenediamine, propylene-diamine, 1,6-diaminohexane, 1,8-diaminooctane, 1,12-diaminododecane, 1,2-diaminopropane, 2,~-diamino-2,5-dimethylhexane, p-phenylene-diamine, 1,8-diamino-p-menthane,l,3-bis-(aminomethyl)-cyclohexane, 4,4~-diamino-dicyclohexylmethane, 3,3'-dimethyl-4,4~-diaminodicyclo-hexylmethane, 4,4'-diaminodiphenylmethane, 2 (3), 5 (6)-bis-(aminomethyl)-norbornane mixed isomers, 3 (4), 8 (9)-bis-(aminomethyl)-tricyclo-[5.2.1 o2 6]-decane mixed iso-mers, bis-(3-aminopropyl)-piperazine, 4,7-dioxadecane-l,10-diamine, 4,g-dioxadodecane-1,12-diamine, 7-methyl-L~,10-dioxatridecane-1,13-diamine, 3-amino-1-methylamino-propane, 3-amino-1-cyclohexylaminopropane, 3-amino-].-(2-ethyl)-hexylaminopropane, N-(cyclohex~ll)-ethylenediamine, 1 16486~

N-(cyclohexyl)-1,6-diamînohexane, N-(2-hydroxypropyl)-ethylenediamine, N-(2,2,6,6-tetramethyl-4-piperidyl)-ethylenediamine, N-(2,2,6,6-tetramethyl-4-piperidyl)-]!,6-diaminohexane, N-(2,2,6,6-tetramethyl-L~-piperidyl) 5 1,3-bis-(aminomethyl)-cyclohexane, N-(2,2,6,6-tetra-methyl-4-piperidyl)-3(4), 8(9)-bis-aminomethyl)-tri-cyclo-~5.2 1 o2 6]-decane mixed isomers, N,N'-bis (2,2,6,6-tetramethyl-4-piperidyl)-ethylenedi.amine, N,N~-bis-(2,2,6,6-tetramethyl-4-piperidyl)-1,6-diaminohexa~e, N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-3(!~), 8(9)-bis-(aminomethyl)-tricyclo[5 2.1 02 6]-decane mixed - isomers, N,N~-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,3-bis-(aminomethyl)-cyclohexane, N,N'-bis-(2,2,6,6-tetra-methyl-4-piperidyl)-4,9-dioxadodecane-1,12-diamine, N,N'-bis-cyclododecyl-1,6-diaminohexane, N,N'-bis-iso-propyl-1,6-diaminohexane, N,N'-bis-cyclohexyl-1,6-diaminohexane, N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-4,4'-diaminodicyclohexylmethane, N-(2,2,6,6-tetramethyl-4-piperidyl)-N'-(cyclododecyl)-1,6-diaminohexane and piperazine.
The ~ollowing are examples o~ compounds of the ~ormula VI: N-(2,2,6,6-tetramethyl~4-piperidyl)-3-methoxypropylamine, N-(2,2,6-6-tetramethyl-4-piperidyl)-

3-ethoxypropylamine, N-(2,2,6,6-tetramethyl-4-piperidyl)--3-octadecyloxypropylamine, N-(2,2,6,6-tetramethyl-4-piperidyl)-3-dimethylaminopropylamine, N-(2,2,6,6-tetra-methyl-4-piperidyl)-2-dimethylaminoethylamine, N-(Z,2,6,6--tetramethyl-4-pi.peridyl)-4-diethylaminobutyl-amine, 2,2,6,6-tetramethyl 4-piperldylaminopropan-3-ol, 1 16~8~5 N-~2,2,6,6-~etramethyl-4-piperidyl)-4-diethylamino-1-methylbutylamine, 2,2,6,6-tetramethyl-4-aminopiperidine, N-(2,2,6,6-tetramethyl-4-piperidyl)-butylamine, N-(2,2,6,6-tetramethyl-4-piperidyl)-octadecylamine, N-5 (2,2,6,6-tetramethyl-4-piperidyl)-cyclododecylamine, N-(2,2,6,6-tetramethyl-4-piperidyl)-hexylamine, di-(2,2,6,6-tetram~thyl-4-piperidyl)-amine, arNmonia, butyl-amine, dicyclohexylamine, cyclododecylamine, hexylamine, dodecylamine J octadecylamine, dioctadecylamine, 2,3-dimethylcyclohexylamine, 2,6-dimethylmorpholine, methyl-cyclohexylamine, pyrrolidine, piperidine, 3,5,5-trimethyl-hexylamine, 2,2-dimethylpropylamine, di-n-octylamine, methanol, phenol and 2,2,6,6-tetramethylpiperidin-4-ol, The following are examples of compounds of the formula ~
1. N,N~-big-~2-chloro-4-~(2,2,6,6-tetramethyl-4-piperidyl)-3-methoxypropylamino~-1,3,5-triazin-6-yl]-N-(2,2,6,6-tetramethyl-4-piperidyl)-1,6-diaminohexane .
2, N,N'-bis-~2-chloro-4-~(2,2,6,6-tetramethyl-4-piperidyl)-3-meth~xypropylamino)-1,3,~-triazin-6-yl]-N-(2,2,6,6-tetramethyl-4-piperidyl)-1,3-bis-(aminomethyl)-cyclo-hexane 3; N~N'-bis-[2-chloro-4-~(2,2,6,6-tetramethyl-4-piperidyl)-3-methoxypropylamino)-1,3,5-triazin-6-yl]-N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-3(4), ~(9)-bis-(arnino-methyl)-tricyclo-[~,2.1,02 6]-decane mixed isomers

4, N,N~ bis-[2-chloro-4-((2,2,6,6-tetramethyl~4-piperidyl)-3-ethoxypropylamino~-1,3,~-triazin-6-yl~-N-(2,2,6,6-tetra--methyl-4-piperidyl)-4,9-dioxadodecane-1,12-diamine 1 16~865 - 13 _ `5. ~,N'~bis-[2-chloro-4-~(2,2,6,6-tetramethyl-4-piperidyl)-butylamino~-1,3,5-triazin-6-yl]-N,NI-bis-(2,2,6,6-tetra-methyl-4-piperidyl)-1,6-diaminohexane 6, N,N'-bis-[2-chloro-4~((2,2,6,6-tetramethyl-4-piperidyl)-butylamino~-1,3,5-triazin-6-yl]-N,N'-bis-cyclododecyl-1,6-diaminohexane 7. N,N'-bis-[2-chloro-4-~(2,2,6,6-tetramethyl-4-piperidyl)-butylamino)-1,3,5-triazin-6-yl~-N-cyclohexyl-1,3-diamino-propane 8. N~N'-bis-[2-chloro-4-dibutylamino-1,3,5-triazin-6-yl]-N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-ethylene-diamine 9, N,N'-bis-[2-chloro-4-morpholino-1,3,5-triazin-6-yl]-N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-ethylene-diamine10, N,NI-bis-[2-chloro-4-octadecylamino-1,3,~-triazin-6-yl]-N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-ethylenediamine ..
11. N,N'-bis- t 2-chloro-4-~(2,~,6,6-tetramethyl-4-piperidyl)-octadecylamino)-1,3,5-triazin-6-yl]-piperazine 12, N,N'-bis-[2-chloro-4-~(2,2,6,6-tetramethyl-4-piperidyl~-3-ethoxypropylamino)-1,3,5-triazin-6-yl]-bis-(3-amino-propyl)-piperazine 13. N,N'-bis-~2-chloro-4-phenoxy-1,3,5-triazin-6-yl~-N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-ethylenedi-amine 14, N,N'-bis-[2-chloro-4-phenyl-1,375-triazin-6-yl]-N,N'-bis-(2 3 2,6,6-tetramethyl-4-piperi~y'.)-4,9-dioxa-dodecane-1,12-diamine, 1 1648~S
~.4 --The reaction of cyanuric halides with primary or secondary monoamines or polyamines and also alcohols or phenols to give definite compounds or polymeric tri-azines has been part of the state of the art for a con-siderable time [J. Am. Chem. Soc. 73 (1951), No. 7,pages 2,981 et seq,; U.S. Patent Specificat~on 2,544,071;
and Swiss Patent Specifications 342,784 and 342,785].
Polytriazine compou~ds of the formula ~N
Z

in which X and Y and Z can be identical or different and denote -0-, -S- or -N-, and one of these groups must carry a polyalkylpiperidyl radical are also known (German Patent.Specification 2,636,144), As already explained in European Patent Application 13,66.~, which also describes polymeric products related to the above patent speci.ficatlon, it has been found that con-siderable difficulties, due essentially to the formation of insoluble by-products which are difficult to remove, must be accepted in the preparation of these products.
A further disadvantage lies in the fact that an appreci-able proportion of low~molecular constituents is present in the end product, which causes a relatively high vola-tility; To sum up, the disadvantages of -~he products described in German Paten-t Specification 2,635,144 can ~ 1648~5 be regarded as due to the fact that the molecular weight distribution is too broad: constituents of too high molecular weight cause the insolubility, even in the polymer, and constituents of too low molecular weight cause an increase in the volatility The disadvantages can only be eliminated by expensive measures of separation and purification. It is a disadvantage of the products of EP-A 13,665 that cross-linked products can be formed to a considerable extent, and these then cause compatability pro~lems with the polymers to be stabilized.
It could not have been foreseen in any way that, amongst the compounds according to the invention, it would also be possible to prepare those in which R8 or R9 has the meaning of a hydroxyalkyl, alkoxypropyl or dialkylaminoalkyl group, since these groups can also . react with acid chlorides, analogously to the NH group, and it would therefore have been expected that bridges would be formed between two different triazine rings, which would have led to undesirable crosslinked products, Such a course of the reaction appeared entirely possible~
i~ not indeed preferred, from publications concerning the known formation of cyanur-c acid esters from alcohols, which can also be formed from alkoxyalkyl groups by cleavage o~ ethers as a result of unavoidable quantities of hydrogen halide, and also publications concerning the synthesis of cyanuric acid dialkylamides from cyanuric chloride and tertiary amines ~Ullm~n volume 9 (1975), page 651; E, Kober and R Ratz, J. Org, Chem 27 (1962), 1 16~865 page 2,509 et seq.~.
The poly-bis-triazinylamines accordin~ to the invention make it possible to solve the problem on which the present invention is based, that is to say the pro-

5 vision of polymeric light stabilizers which have a linear structure and are not crosslinked and which exhib.it an excellent light stabilizing action and are free from the disadvantages of the products of German Patent Specifica-tion 2,636,144, since the new compounds possess the desired prop~rties in a high degree, which could in no way have been expected. This is because it could not have been foreseen that the procedure of first pre-paring dichloro-bis-triazinylamines (III) and reacting the latter in a controlled manner with selected other diamines (IV) would produce polymers which would have met the desired pattern of properties. It would, on the contrary, have been necessar~ to assume that the properties of the new products would be largely similar to those of German Patent Specification 2,636,144.
Surprisingly, however, it is possible by specific selec-tion of the diamines (IV), to control the properties of the new polytriazines according to the invention so that, for example, the molecular weight can be influenced to a very large extent and, if there is a high proportion of groups of the formula (II), also to achieve high molecu-lar weights wi~hin a short reaction time, In addition to their excellent ac~ivity, mention should also be made of the lo~J volatility of the new products, which is in striking comparison with th~ best 1 1648~5 example of the said German Patent Specification 2,636,144, E~ample 6, a fact which is particularly manifest in the case of those products in which the radicals R3 and/or ~4 are hydrogen. The new triazine stabilizers can ~e incorporated without problems in the polymers to be stabilized and are excellently suitable for stabilizing these polymers against oxidative degradation induced by light. In addition to their excellent effectiveness as stabilizers, the new stabilizers are distinguished by 10 their compatability with the polymers to be stabilized, their migration resistance against extraction by aqueous media, which plays an important part in outdoor weather-ing, their heat stability, even at high processing temperatures, and their low volatility, particularly in comparison with Example 6 of German Patent Speci~ication 2,636,144.
As already stated, the new compounds are used as stabilizers for plastics to counteract damage caused to the latter through the action of oxygen, heat and light The following are individual examples of such plastics:
Polymers derived from hydrocarbons with single or double unsaturation, for example polyolefins such as polyethylene, which can optionally be crosslinked, poly-propylene, polybut-l-ene, polyisobutene, polymethylbut-2~ 1 ene, poly~ethylpent-l-ene, polyisoprene, polybutadiene and polystyrene, copolymers of the monomers on ~hich the said homopolymers are based, such as e-thylene-propylene copolymers, propylene-bu-t-l-ene copol~ers, propylene-isobu-tene copolymers and styrene-butadiene copolymers, and also terpolymers of ethylene and propylene with a ~iene, such as, for example, hexadiene, dicyclopenta-~diene or ethylidenenorbornene; mixtures of the above-mentioned homopol~ners, such as, for example, mixtures of polypropylene and polyethylene, polypropylene and polybut-l-ene, polypropylene and polyisobutylene or of a butadiene-acrylonitrile copolyrner with a styrene-butadiene copolymer.
Vinyl polymers containing halogen, such as poly-vinyl chloride 7 polyvinylidene chloride, polyvinylfluoride, polychloroprene and chlorinated rubbers, and copolymers of vinyl chloride and vinylidene chloride with one another and ~ith other olefinically unsaturated monomers.
Polymers derived from a,~-unsaturated acids and derivativés thereof, such as polyacrylates and poly-methacrylates, polyacrylamides and polyacrylonitrile and copolyrners thereof with one another and with other vinyl compounds, such as acrylonitrile/butadiene/styrene, acrylonitrile/styrene and acrylonitrile/styrene/acrylic ester copol~ners Polymers derived from unsaturated alcohols and amines or acyl derivatives or acetals thereof, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl bu-~yral, polyallyl phthalate, polyallylmelamine and copolymers thereof with other vinyl compounds, such as ethylene/
vinyl acetate copolymers.
Homopolymers and copolymers der.ive~ frorn `- 19 --epoxides, such as polyethylene oxide or the polymers which are derived from bis-glycidylethers.
Polyacetals, such as polyoxymethylene and poly-oxyethylene and polyoxymethylenes which contain ethylene oxide as the comonomer.
Polyurethanes and polyureas.
Polycarbonate.
Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11 and poly-amide 12 Polyesters derived from dicarboxylic acids and dialcohols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephtha-late, polybutylene terephthalate or poly-1,4-dimethylol-cyclohexane terephthalate Crosslinked polymers derived from aldehydes on the one hand and from phenols, ureas and melamines on the other hand, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.
Finally, the new compounds can also be employed as stabilizers in the resins and paints field. Ex-amples of these are thermosetting and thermoplastic acrylic resins which are used for automobile finishes ~Encyclopedia of Polymer Science and Technology, Inter-science Publishers, New Yo~k volurne 1 (1964), pages 273-276 and volum~ 13 (1970), pages 530-532; 'IUnderstanding Paint" by ~ R. Fuller, American Paint Journal Co., 1 .164~6~

St. Louis, 1965, pages 124-135], acrylic resin lacquers, that is the customary stoving lacquers [described, for example, in H Kittel's "Lehrbuch der Lacke und Beschicht~gen" ("Textbook of Lacquers and Coatings"), Yolume 1, part 2, pages 735 and 742 (Berlin, 1972) and in H. Wagner and H.F. Sarx "Lackkunsthar7e" ("Synthetic Resins for Lacquers"), pages 229-235] and, very parti-cularly, mixtures based on an acrylic resin(which can be crosslinked by heat)and styrene and also lacquers and coatings based on acrylic/melamine resins and alkyd/
acrylic/melamine resins Lacquers of this type can contain, as further additives, other customary light stabilizers, phenolic antioxidants, pigments, dyestuffs, metal deactivators and the like.
A particularl~J important aspect is the stabili-zation of polyolefins, styrene polymers, polyamides, poly-(meth)acrylates and polyurethanes, for which the compounds are preferentially suitable Examples of -this are polyethylene of high and low density, poly-propylene, ethylene-propylene copolymers, polystyrene and styrene-butadiene-acrylonitrile terpolymers; mix-tures of polyolefins or styrene polymers and polyure-thanes based on polyethers or polyesters The new stabilizers are incorporated into the polymer compositions in accordance with methods which are generally cus-tomary. The incorporation can be effected, for example, by mixing the compounds and optiona]ly ~urther additives into the melt by the methods customary in the art, before or during shaping, or by applying the eompounds, dissolved or dispersed, to the polymer directly or mixing the compounds into a solution, suspension or emulsion of the polymer, where . appropriate with subsequent evaporation of the solvent.
The quantities are 0 01 to 5, preferably 0 05 to 2.5 and, in particular, 0.1 to 1 0, % by weight, relative to the material to be stabilized. The new compounds can also be added to the plastics to be stabilized in the form of a master-batch containing these compounds, for example, i.n a concentration of 1 to 50, preferably 2.5 to 20, % by weight The plastics which have been stabilized by the addition of the substances according to the invention can, if necessary, also contain other known and custom-ary additives, such as, ~or example, antioxidants based on phenols and sulfides, metal deactivators and light stabilizers, phosphite stabilizers, metal compounds, epoxy stabilizérs and polyhydric alcohols (see also German Offenlegungsschrift 2,427,853, pages 18-24) Examples of antioxidants are sterically hindered phenols, such as 2,6-di-tert -butyl-4-methylphenol, 4,4~-butylidene-bis-(2,6-di-tert.-butylphenol), 4,4l~thio-bis-(2-tert.-butyl-5-methylphenol), 2,5-di-tert -butyl-4-hydroxyanisole, 2,2-bis-(3,5-di-tert.-butyl-2-hydroxy-benzyl)-malonic acid dioctadecyl ester, 1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,4,6-trimethyl-benzene, 2,4,6-tri-(3,5-di-tert -butyl-4-hydroxybenzyl)-phenol, phenolic triazine compounds, such as 1,3,5-tris-(3,5-di-tert --butyl~4-hydroxybenzyl) i.socyanurate, 1 1648~S
_ 2~ --esters of ~-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid with, for example, octadecanol, penta-erythritol and tris-hydroxyethyl isocyanurate, esters of 3,3-bis-(3-tert.-butyl-4-hydroxyphenyl)-butanoic acids 5 with, for example, ethylene glycol, thiodipropionic acid esters with fatty alcohols, Ca or Ni salts of 3,5-di-tert;-butyl-4-hydroxybenzylphosphonic acid ethyl ester, dioctadecyl sulfide and dioctadecyl disulfide.
W Absorbers and light stabilizers include 2-10 (2 t -hydroxyphenyl)-benztriazoles, such as, for example, the 5-chloro-39,5 9 -di-tert.-butyl and 5-chloro-3',5'-di-tert,-amyl derivatives, 2-hydroxybenzophenones, such as, for example, the 4-heptoxy or 4-octoxy derivative, salicylates, such as octylphenyl salicylate, nickel com-plexes such as, for example, those of 2,29-thio-bis-4-(1,1,3,3-tetramethylbutyl)-phenol with butylamine or other amines, oxalic acid diamides and sterically hin-dered amines, Phosphites which should be mentioned are ali-phatic, aro~atic or aliphatic-aromatic phosphites, such as, for example, tris-nonylphenyl phosphite, tris-(2,4-di-tert.-butylphenyl) phosphite, tris-(2-tert -butyl-phenyl) phosphite or esters of pentaerythritol p~losphite.
Metal compounds which are known as stabilizers are understood in this context as meaning calcium, barium, strontium, zinc, cadmium, magnesium, aluminum and lead soaps of aliphatic carboxylic acids or hydroxy-carboxylic acids having about 12 to 32 C atoms, s21ts of the said me~als with a.romatic carboxylic acids, such as 1164~65 be.nzoat~s or salicylates and (alkyl)-phenolat~s o.~ the~e metals, and also organotin compo~ds, such as, .t`or ex~
ample, dialkyltin thioglycolates and carbox~lates, - . Kno~n epoxy stabilizers are, for example, epoxi-dized higher fatty acids, such as epoxidized soyabean oil, ~all oil or linseed oil or epoxidized butyl oleate and epoxides of long-chain olefins.
Polyhydric alcohols can, for example, be penta-erythritol, trimethylolpropane, sorbitol or mannitol, that is to say preferably alcohols having 5 or 6 C atoms and 2 to 6 OH groups.
An effective combination of stabilizers for poly-a-olefins, such as, for example, high-pressure, medium-pressure and low-pressure polymers of ~2 to C4 a-olefins, in particular polyethylene and polypropylene or copolymers of such a-olefins, is composed, for ex-ample, relati.ve to 100 parts by ~7eight of polymer, of . ..
0.01 to 5 parts by weight of one o~ the compounds to be used in accordance with the invention, 0,05 to 5 parts by weight of a phenolic stabilizer, if appropriate 0.01 to 5 parts by weight of a sulfur-containing co-stabilizer and, if appropriate, 0.01 to 3 parts by weight of a basic or neutral metal soap, such as, for example, calciurn stearate or zinc stearate, or the corresponding oxides and, if appropriate, 0,01 to 5 parts by ~eight of a known W stabilizer belonging to the group comprising alkoxyhydroxybenzophenones, 4-hydroxyphenylbenzotri.azoles, benzylidenem210nic acid mononitrile-ester or the so-called quenchers, such as, for example, nickel chelates, 1 1fi48~5 Examples of substances which can be regarded as other customary additives are plasticizers, slip agents, emulsifiers, fillers, such as, for example, chalk, talc or asbestos, pigments, optical brighteners 7 flameproof-ing agents and antistatic agents, The plastics which have been stabilized in accordance with the invention can be used in a wide variety of shapes, for example as sheets, fibers, tapes or profiles or as binders for lacquers, adhesives or cements.
The examples below serve to illustràte the invention further. In this connection, Examples 1 to 13 illustrate the preparation of compounds of the formula (III), which are then reacted in accordance with Examples 14 to 47 with a diamine of the formula (IV) to give the poly-bis-triazinylamines according to the inven~
tion, Neither the intermediate products nor the oligomers have a sharp melting point, but a melting range, Example 1 N,N1-bis-[2-Chloro-4-((2,2,6,6-tetramethyl-4-piperidyl)-3-methoxypropylamino)-1,3,5-triazin-6-yl]-N-(2,2,6,6-tetra--methyl-4-piperidyl)-1,6-diaminohexane 260 g of toluene and 120 g of acetone are initially placed in a 1 1 stirred apparatus. 36,8 g (0,2 mole) of cyanuric chloride are added and the solution is cooled to 0C, 45 6 g (0,02 mole) of N-(2,2,6s6-tetramethyl-4-piperidyl)-~-metho~ypropylamine (= a compound of the formula (VI)) are then added drop~ise a-t 0 to 10C, ~ 8~5 - ~5 -~ollowed ~y 32 g of 25% strength aqueous sodium hydr-oxide solution addeà in the course of 3 hours at 5 to 10C After adding 25.5 g (O.l mole) of N-(2,2,6~6-tetramethyl-4-piperidyl)-l,6-diaminohexane (=the compound of the formula (VIII)), the mixture is warmed to 50C
and 32 g of 25% strength aqueous sodium hydroxide solu-tion are added dropwise in the course of 2 hours at this temperature After adding 80 ml of acetone and 60 ml of water, the organic phase is separated off and concen-trated to dryness in vacuo at a heating bath tempera-ture of approx. 70C and the residue is dried in a high vacuum at 70C. This leaves 9l.5 g = 98% of theory, of a colorless solid of melting point approx. 100C (a ~iscous melt) ~ les 2 to 13 _, .
Further compounds (III) are prepared in accord-ance with the instructions of Example l from cyanuric chloride and the components listed in Table l. The numbers recorded in column 4 of the table refer to the list of the compounds on pages 12 and 13 1 :~&~8~5 -- ~6 __ q~ ., o o o o ~
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~ . ___ ___ _ ._ _ ___ _ 2~ -Example ~4 Poly-bis-tl~iazinylamine from compound l and hexam~thylene-diamine , 18 0 g (O.Ol9 mole) of the `compound obtained in Example l, together with 2.3 g (0.02 mole) of hexa-methylenediamine and l.6 g (0.04 mole) of NaOH powder, are stirred in lOO ml of xylene in a 250 ml stirred apparatus for 9 hours under reflux (132C). The mix-ture is then filtered, the filtrate is concentrated on a rotary evaporator in vacuo and the residue is dried at 150C in a high vacuum for 4 hours This leaves a nearly colorless resin of melting point 115C, in a quantitative yield. Molecular weight 3,300 Examples 15 to 47 The procedure followed is analogous to that of Example 14, using further compounds of the formula (III).
The experimental data are listed in Table 2. Column 2 refers to the compound number recorded in Table 1, column 4, which refers to the list on pages 12 and 13 ___ ~ o s~
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r~ I P~ ~ ~ O H ~J ~ J 1~ ~) C--,D ~ O ~ J ~:J' J;l' ~ ~ ;~' ;1 ta E~ _ 1 16~865 Example 48 12.05 g ~1/20 mole) of N-(2,2,6,6-tetramethyl-4-piperidyl)-3-dimethylaminopropylamine are initially t;aken in 40 r~ of xylene in a 250 r~ stirred apparatus.
9.2 g (1/20 mole) of cyanuric chloride, dissolved in 60 ml of xylene, are then added dropwise at an internal temperature of -5 to +5C. The mixture is warmed to 10C, 2.0 g (1/20 mole) of NaOH powder are added and the mixture is stirred for 3 hours at 10C. 5.0 g (1/40 mole) of N-(2,2,6,6-tetramethyl-4-piperidyl)-ethylenediamine are then added, after which the mixture is warmed to 50C and, after 2.0 g (1/20 mole) of NaOH
powder have been added, is stirred at this temperature for 5 hours. After 1.5 g (1/40 mole) of ethylene-diamine and 2.0 g (1/20 mole) of NaOH powder have been added, the mixture is stirred under reflux for a further 8 hours and is then filtered and the filtrate is concen-tra~ed to dryness in vacuo The residue is dried in a high vacuum at 150C. This leaves a pale yellow solid resin in a virtually quantitative yield. M.p.

Example 49 9 2 g (1/20 mole) of cyanuric chloride are initi-ally taken in 40 ml of xylene in a 250 rnl stirred appa--ratus. 12.0 g (1/20 rnole) of N-(2,2,6,6-tetramethyl-4-piperidyl)-aminohexane, dissolved in 60 ml o~ ~ylene, are then added dropwise at O to 10C After 2 0 g (1/20 mole) of NaOH powder have ~een added, the mi~ture is stirred for 3 hours at 10~ and is then processed further as indicated in Example 40) to give a colorless resin~ M,p. 215C.
Examples 50 to 52 The procedure followed is as in ExamplQ 49, using the substances listed below:

.
Ex- Starting materials Result-ample Monoamine (VI) Diamine (VIII) Diamine (IV) ng No M.p (~
. .
50 piperidine analogous to analogous to 230 4.2~ = 1/20 Example 35 Example 18 51 dioctadecyl- analogous to analogous to 85 amine Example 17 Example 24 22.3 = 1/10 52 diethanol- analogous to analogous to 155 amine Example 22 Example 27 5.25 = 1/20 Examp]e 53 The compound 14 is obtained, analogously to Example 1, from 45.2 g (0.2 mole) of 2-phenyl-4,6-dichloro-1,3,5-triazine and 48.2 g (0.1 mole) of the diamine obtained in Example 4, Yield 67 g = 78%, - m.p. 60C.
Example 54 This example demonstrates the volatility of the new triazine stabilizers compared with a product of the nearest state of the art.
The vola-tility figures were determined in an apparatus for thermogravimetric analysis, For the determination, equal quantities ~';00 mg) of the compounds according to the invention and of -t~e comparison substance were heated to 300C in a nitrogen atmosphere at a heating 1 ~64865 rate of 2 K¦mi~ute and the loss of substance was measured in mg/cm2 of sample surface, The results are shown in the table below.

. . .
Stabilizer Loss of weight in mg/cm2 on reaching ...,C
according tc 220 260 300 10 minutes at 300C
Example .31 2.37 6. oo 7.58 14 .16 2,05 4,42 5;21 18 .31 0.95 2.84 3,-36 26 ,16 1. 58 3.48 4.42 Comparison~ ~. 47 3.48 10.59 17.38 ~)substance according to Example 6 of ~erman Offenleg~ngs-schrift 2,636,144 Example 55 This example is intended to demonstrate the light stabilizing action of the new compounds in poly-~-olefins.
100 parts by weight of polypropylene having a melt index i5 (230C ) of approx. 6 g/10 minutes (deter-mined as specified in ASTM D 1238-62 T) and a density of O,90 were mixed with O.l part by weight of pentaerythri-tyl tetrakis-3-(3,~-di-tert.-butyl-4-hydroxyphenyl) propionate, 0,2 part by weight of calcium stearate and O.l part by weight of the stabilizer according to the invention to be.tested.
In order to achi.eve as uniform as poss~ble a distributiorl on the polymer par-ticles, the stabilizers were dissolved in a solvent and the so~ut;ion~as added 1 1~486~

dropwise to the polypropylene powder, whilst stirring~
the bulk o~ the solvent being re-vaporized by simulta-neous irradiation with an IR lamp, After approx. 20 minutes, the calcium stearate was added and mixing was continued for a further 10 minutes. Residues of solvent were removed by drying at ~0C/120 minutes in a drying cabinet.
The polypropylene was injection molded at 240C
on a type SP 50 Windsor injection molding machine to give sheets measuring 60 x 60 x 1 mm. Test speci-mens were punched out from these sheets as specified in DIN 53,4~5, type 3, reduced on a scale of 1:3. The test specimens required as comparison samples were pre-pared analogously, but omitting the stabilizer to be tested or adding ths comparison stabilizers, The stability to light was determined by sub-jecting the samples to irradiation with alterna-ting light in a Xenotest 1200 apparatus made by Original -Hanau Quarzlampen GmbH. The intensity of radiation was modulated by W filters (special filter glass, d -1.7 mm), The fastness to light was tested as speci-fied in DIN ~3,387 (17 minutes drying period, 3 minutes sprinkling, black-body temperature 4~C and a relative atmospheric humidity o~ 70 to '7~/ during the drying period). The elongation at break was measured on a tensile testing machine made by Instron at a draw-o~f rate of 5 cm/minute after a specified period of exposure, in hours.

_ , . . .
Stabilizer Period of e~xposure Measured elongation according toin hours at break as % of Example initial value 14 1,400 >50 1,400 ~ ~ 50 26 .1,400 > 50 polypropylene 260 .
comparison 1) 320 .
comparison 1,400 ..

1) with no light stabilizer 2) compound according to Example 6 of German Offenlegungs-schrift 2,636,144 Example ~6 Using a laboratory high-speed mixer, a homogeneous mixture is prepared from polypropylene powder ( ~ Hostalen PPU VP 1770 F of Hoechst AG) having a melt index MFI 190/5 = 1.9 g/10 minutes, see DIN 53,53.~, and the constituents of the formulation indicated below, and is converted into granules. The material thus stabi-lized is then melted in a laboratory extruder under thecustomary processing conditions and is processed via a spinning pump having an 8-orifice spinneret to give mono-filaments, which are then after-stretched in a ratio of 1:3, textured to give yarn of 40 dtex and processed to give tes-t fabrics 100 parts by weigh~t of polypropylene, 0,2 part by weight of calcium stearatel 0,1 part by weight o~ 3,3-bis-(3-tert,-butyl-4-.

1~648~5 hydroxyphenyl)-butanoic acid ethylene glycol ester, 0.1 par~ by weight of dioctadecyl disulfide and 0.3 part by weight of the stabilizer to be tested The fabric samples are stretched oYer a perforated piece of cardboard in such a way that a free aperture of diameter approx. 15.5 mm remains. The test specimens are exposed in this forrn in the Xenotest X 1200 as des-cribed in the preceding Example. At specific intervals of time, the fabrics are loaded centrally with a weight of diameter 6 rmm, exerting a pressure of 0.1 N/mm2. The breakthrough of the weight is taken as the -tirne of fail-ure.

Stabilizer according Period of exposure to Example in hours ~,100 4) 14 3 100 4) 26 3,100 4) polypropylene ~ 280 20 comparison 1) 400 comparison 2) 1,400 comparison 3) 3,000 1) with no stabiliser 2) compound according to Example 1 of German Offenlegungs-B~ 2~ schrift 2,719,131 (cornmercial product Tinuvin 622) 3) compound according to Example 6 of German Offenlegungs-schrif-t 2,635,144 1 16~8~5 4) weight had not yet broken through Example 57 The stabilized granules prepared as inthe preced-ing example are processed on a laboratory film blowing machine (screw diameter 25 mm, length 20 D), temperature schedule 200, 240, 250 and 255C) to give blown fiims of a thickness of approx, 70 ~m, These films are sub-jected to artificial weathering in the Xenotest X 1200 as described, The carbonyl number is determined, as a characteristic of damage, by a method based on DIN
53,383, part 2, (This is defined for PP as the ratio of the extinction values at 1,71.5 cm 1 and 1,524 cm 1, The disintegration of the test specimens into powder begins at a C0 number > 2,) Stabilizer according C=0 number after ,,, hours to Example 500 1,000 2,000 2,500 .
< 0,1 ~ 0,1 0.3 0.4 14 ~ 0,1 < 0,1 0,3 0,5 26 C 0,1 ~ 0,1 0,3 0,5 20 polypropylene ~ 2 _ _ comparison 1) > 2 _ _ comparison _ > 2 _ comparison 3) 0,1 0,1 0,4 0,9 1)~ 2) and 3) correspond to the compari.son samples of the previous exa~ple

Claims (6)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A poly-bis-triazinylamine of the general formula (I) (I) in which n is an integer from 1 to 200, R1 and R2 are identical or different and denote hydrogen, C1 to C37 alkyl, cycloalkyl which is unsubstituted or substituted by up to four C1 to C4 alkyl groups, C7 to C14 aralkyl or a group of the formula (II) (II) in which R6 represents hydrogen or C1 to C6 alkyl, R3-and R4 are identical or different and have the meanings indicated under R1 and R2, R5 is halogen, phenyl, -OR7 or -NR8R9, R7 representing hydrogen, C1 to C18 alkyl, C3 to C12 alkenyl, C5 to C12 cycloalkyl, C7 to C18 aralkyl, C6 to C10 aryl or a radical of the formula (II), and R8 and R9 being identical or different and denoting hydrogen, C1 to C37 alkyl which is unsubstituted or sub-stituted by a hydroxyl group, a C1 to C18 alkoxy group or a C1 to C4 dialkylamino group , C3 to C12 alkenyl, C5 to C12 cycloalkyl, C7 to C18 aralkyl, phenyl, naphthyl or a radical of the formula (II), or R8 and R9, together with the common nitrogen atom, forming a pyrrolidine ring or a piperidine, morpholine or hexamethyleneimine ring which is unsubstituted or substituted by up to four C1 to C4 alkyl groups, X and Y are identical or different and represent C2 to C18 alkylene or C2 to C12 bis-(pro-poxy)-alkylene or C6 to C18 monocycloalkylene, dicyclo-alkylene or tricycloalkylene which are unsubstituted or substituted by up to four methyl groups and in which, in the case of the group first mentioned, two C atoms can be replaced by N atoms which can carry propylene groups, or X and Y represent C6 to C18 arylene or C7 to C18 aralkyl-ene, or piperazinylene radicals are present instead of the groupings or , E1 is a halogen atom or a group , , -O-R7 or -NR8R9 and E2 is hydrogen or an acyl group, R3, R4, R7, R8 and R9 having the meanings indicated above and at least one of the radicals R1, R2, R3, R4, R7, R8 and R9 being of neces-sity a group of the formula (II).

2. A process for the preparation of poly-bis-triazinylamines as claimed in claim 1, which comprises reacting, in an inert organic solvent, either A. a dihalogeno-bis-triazinyldiamine of the formula (III) (III) at 50 to 200°C with a 0.8 to 1.4 molar amount of a diamine of the formula (IV) (IV) Hal, R1, R2, R3, R4, R5, X and Y in these formulae having the meanings indicated in claim 1, in the pre-sence of an equivalent amount - relative to the compound (IV) - of an inorganic base which acts as a hydrogen halide acceptor, or B a poly-bis-triazinylamine of the general formula (V) (V) at 50 to 200°C with a 0.8 to 1.4 equivalent amount of a compound of the formula (VI) H-R5 (VI) Hal, R1, R2, R3, R4, R5, X and Y in these formulae having the meanings indicated in claim 1, but R5 not being Hal or phenyl, in the presence of an equivalent amount -relative to the compound (VI) - of an inorganic base, or C. a cyanuric halide and a 0.8 to 1.3 molar amount of a compound of the formula (VI) in which, however, R5 is not Hal or phenyl, initially at -5 to 40°C and in the presence of an equivalent amount of a hydrogen halide acceptor, to give a dihalogenotriazine of the formula (VII) (VII) then, without intermediate isolation of the latter, deriving from it, at 10 to 70°C and in the presence of an equivalent amount of a hydrogen halide acceptor, by reaction with a 0.4 to 0.7 molar amount of a diamine of the formula (VIII) (VIII) a dihalogeno-bis-triazinyldiamine of the formula (III) and reacting the compounds (III) thus obtained, in situ in accordance with process A, to give the desired end products, Hal, R1, R2, R3, R4, R5, X and Y in the formu-lae having the meanings indicated in claim 1.

3. A composition,stabilized against decomposition by UV
light, comprising a synthetic polymer and 0.01 to 5 parts by weight, relative to the polymer, of a stabilizer as claimed in claim 1.

4. A composition as claimed in claim 3 in which the polymer is a polyolefin.

5. A composition as claimed in claim 3 in which the polymer is a polyacrylate or polymethacrylate.

6. A composition as claimed in claim 3 in which the polymer is a homopolymer or copolymer of styrene.