CH592129A5 - Stabilising organic materials, esp. polymers - against light, oxygen and heat, with piperidine derivs. - Google Patents

Abstract

A stabilised organic material contains a piperidine deriv. of formula (I) or its salt (m = 0 or 1, n = 1 or 2 and R1 and R2 are each opt. branched 1-12C alkyl or together complete a 5-12C cycloalkyl, R3 is H, opt. branched 1-12C alkyl, 7-12C aralkyl or 5-6C cycloalkyl. A is O or NR4, where R4 is opt. branched 1-12C alkyl (opt. substd. by halo, CN or OH, or interrupted by one or more O or S), 7-12C aralkyl, 3-12C alkenyl or 5-12C cycloalkyl. R5 is H, mono- or di-valent 1-20C hydrocarbyl (opt. substd. by halo, CN or OH or interrupted by >=1 O or S) or is a gp. of formula (II): where p = 0 or 2, Y is H, 1-20C alkyl 3-12C alkenyl or alkynyl, 7-13C aralkyl or CH2CM(OH)R8, where R8 is H, phenyl or 1-4C alkyl. When A is O, then X is CO, CONH CS, CSNH, when it is NHR4 then X is CO, CONH, - C(NH)NH -q (q = 1 or 2), CS, CSNH, COO, SO2, or if n = 1, and R5 = (II). and p = 2, also SO2 NH, with the provisos that when A is O, R5 is not H, and when A = NR4, m = 1, n = 2, and X = CO or CS then R5 can be absent. (I) stabilise polymers against degradation by light (visible or UV), oxidation and heat, generally at 0.01-5, pref. 0.1-2 wt %. Specified substrates are high- or low-density polyethylene, polypropylene and polystyrene. A typical cpd. is 2-(2', 2', 6', 6'-tetramethylpiperidinyl-4')ethylamine.

Description

  

  
 



   The invention relates to a stabilized organic material containing new piperidine derivatives, in particular new 2- (piperidinyl-49-ethyl derivatives, which are particularly useful as light stabilizers for polymers.



   These piperidine derivatives are new compounds of the formulas
EMI1.1
 and their salts where m is 0 or 1, n is 1 or 2, R1 and R2 are the same or different and each are straight-chain or branched alkyl groups with 1 to 12 carbon atoms or where R and R2 together with the ring carbon atom to which they are bonded , form a cycloalkyl group with 5 to 12 carbon atoms, R3 denotes hydrogen, a straight-chain or branched alkyl group with 1 to 12 carbon atoms, an aralkyl group with 7 to 12 carbon atoms or a cycloalkyl group with 5 or 6 carbon atoms,
EMI1.2
 wherein
R4 is hydrogen, a straight-chain or branched alkyl group with 1 to 12 carbon atoms, which is either unsubstituted or substituted by halogen, cyano or hydroxyl,

   or is interrupted by one or more oxygen or sulfur atoms, an aralkyl group with 7 to 12 carbon atoms, an alkenyl group with 3 to 12 carbon atoms or a cycloalkyl group with 5 to 12 carbon atoms, R5 denotes hydrogen, a monovalent or divalent hydrocarbon radical with 1 to 20 carbon atoms and is either unsubstituted or substituted by halogen, cyano or hydroxyl or is interrupted by one or more oxygen or sulfur atoms, or in which R5 is a group of the formula II
EMI1.3
 denotes in which p denotes 0, 1 or 2, R1 and R2 have the meanings given above and
Y is hydrogen, an alkyl group with 1 to 20 carbon atoms, an alkenyl or alkynyl group with 3 to 12 carbon atoms,

   an aralkyl group with 7 to 12 carbon atoms or the group CH2CH (OH) R8, in which R8 denotes hydrogen, phenyl or an alkyl group with 1 to 4 carbon atoms, and when A denotes, denotes and
EMI1.4
 if A> N-R4 means,
EMI1.5
 wherein q is 1 or 2, is or
EMI1.6
 if n is 1 and R5 has the formula II given above, in which p is 2, X is also an -SO2-NH-,
EMI1.7


<tb> -CNH- <SEP> or <SEP> -CNH group
<tb> <SEP> II
<tb> <SEP> O <SEP> S
<tb> means, with the proviso, that when A means-0-, R5 has a different meaning than hydrogen, and when A> NR4, m 1, n 2
EMI1.8
 mean that R5 can be absent.



   When n is 1, the substituent R5 can be hydrogen (except when A is-0-), a monovalent, straight-chain or branched aliphatic group with 1 to 20 carbon atoms, which is saturated or unsaturated and either unsubstituted or substituted by halogen, cyano- or hydroxyl groups or is interrupted by one or more oxygen or sulfur atoms, an alicyclic group with 5 to 20 carbon atoms, an optionally substituted aralkyl group with 7 to 12 carbon atoms or an optionally substituted aryl group with 6 to 15 carbon atoms or the group
EMI1.9
 mean in which R1, R2, Y and p have their meanings given above.



   Specific examples of substituent groups R5 include hydrogen (except when A is), methyl, methylthiomethyl, ethyl, 2-hydroxyethyl, 2-cyanoethyl, n-propyl, isopropyl, n-butyl, 4-chloro n-butyl-, sec-butyl-, t-butyl-, n-pentyl-, neopentyl-, 2-ethylpropyl-, 2-methylbutyl-, n-hexyl-, n-octyl-, t-octyl-, n- Dodecanyl, n octadecanyl, 2-methoxyethyl, 2-n-dodecylthioethyl, allyl, a-methallyl, dec-9-enyl, heptadec-8-enyl, crotyl, cinnamyl, propargyl, 2,4-hexadienyl, benzyl, 2-chlorobenzyl, a methylbenzyl, 4-methoxybenzyl, ap-dimethylbenzyl, diphenylmethyl, cyclopentyl, cyclohexyl, cyclooctyl, 4-methylcyclohexyl, cyclododecenyl, 9 -Fluorenyl-, adamantyl-, phenyl-, 4-methylphenyl-, 4-6-octylphenyl-, a-naphthyl-, 4-biphenyl-, 2-fluorenyl-,

   2-chlorophenyl and 4-methoxyphenyl groups.



   When n is 2, the substituent R5 can be a divalent straight-chain or branched aliphatic (saturated or unsaturated) group having 2 to 20 carbon atoms, a divalent alicyclic group having 5 to 12 carbon atoms, a divalent aralkyl group having 8 to 12 carbon atoms or a divalent aryl group having 6 to 15 carbon atoms, or when m is 1 and
EMI2.1

EMI2.2
 mean, the substituent R5 can be absent.



   Specific examples of substituent groups for R5 include 1,2-ethylene, 1,4-n-butylene, 1,3-n-butylene, 1,6-n-hexylene, 1,7-n-heptylene, 1 , 10-n-decylene, 2,2-dimethyl1,3-propylene, trimethyl-1,4-butylene, 1,2-vinylene, 3-thia-n-pentane, 3-oxa-n-pentane , 1,4-but-2-enylene, 1,4-but-2ynylene, 2,5-hex-3-enylene, 1,2-cyclohexylene, 1,4-cyclohexylene, hexahydro-p- xylylene, p-xylylene, m-xylylene, 1,2-phenylene, 1,4-phenylene, 2,2'-biphenylene, 4,4'-biphenylene and 4,4'-biphenylenemethane groups.



   Examples of substituents Y in compounds of the formula I include hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-hexyl, n-octyl, n-dodecyl -, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxy-2-phenylethyl, allyl, α-methyllyl, 10-undecenyl, oleyl, benzyl, α-methylbenzyl, p-methylbenzyl -, ap-dimethylbenzyl and a-naphthylmethyl groups.



   Particularly preferred substituents Y are hydrogen, straight-chain or branched alkyl groups having 1 to 4 carbon atoms and the most preferred substituent Y is hydrogen or a methyl group.



   Examples of substituents R1 and R2 are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-hexyl, n-dodecyl, or R1 and R2 together with the carbon atom to which they are attached can form a group as shown below, for example:
EMI2.3

Particularly preferred substituents Rf and R2 are straight or branched chain alkyl groups having 1 to 4 carbon atoms, and the most preferred substituents R and R2 are methyl groups.



   Examples of groups R3 include hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-hexyl, n-octyl, n-dodecyl, benzyl, α-methylbenzyl, ap-dimethylbenzyl, cyclohexyl and cyclopentyl groups. Particularly preferred alkyl groups are those containing 1 to 8 carbon atoms and the most preferred substituent R3 is hydrogen.



   The substituent R4 can be hydrogen, methyl, ethyl, 2-hydroxyethyl, 2-cyanoethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-hexyl, n-octyl, n-dodecyl, benzyl, ex -Methylbenzyl, ap-dimethylbenzyl, cyclohexyl, cyclopentyl, allyl or a-methallyl, but-3-enyl, 10-undecenyl or propargyl.



  Particularly preferred substituents R4 are hydrogen and alkyl groups having 1 to 8 carbon atoms and the most preferred substituent is hydrogen.



  Preferred groups X are
EMI2.4
 and when n 1, A -N-R4- and R5 are a group of formula II as previously defined, wherein p is 2, then is the preferred group
EMI2.5

Examples of salts of compounds of Formula I include salts of an inorganic acid such as the phosphates, carbonates, sulfates, chlorides and the like. as well as salts of organic acids such as the acetates, stearates, maleates, citrates, tartrates, oxalates, benzoates and substituted carbamic acids.



   Specific examples of compounds of Formula I are given in the following list.



  a) Where A => N-R4 2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') - ethylamine N-methyl-2- (2 ', 2', 6 ', 6'- tetramethylpiperidinyl-4 ') - ethylamine N-isopropyl-2- (2', 2 ', 6', 6'-tetramethylpiperidinyl-4 ') - ethylamine N-benzyl-2- (2', 2 ', 6', 6 '- tetramethylpiperidinyl-4') - ethylamine Nn-octyl-2- (2 ', 2', 6 ', 6' tetramethylpiperidinyl-4 ') - ethylamine N-cyclohexyl-2- (2', 2 ', 6', 6'-tetramethylpiperidinyl-4 ') - ethylamine N-acetyl-2- (2', 2 ', 6', 6'-tetramethylpipieridinyl-4 ') - ethylamine Nn-butyryl-2- (2', 2 ', 6 ', 6'- tetramethylpiperidinyl-4') - ethylamine Nn-octanoyl-2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') - ethylamine Nn-dodecanoyl-2- (2 ', 2' , 6 ', 6' - tetramethylpiperidinyl-4 ') ethylamine Nn-octadecanoyl-2- (2

   ', 2', 6 ', 6' - tetramethylpiperidinyl-4 ') ethylamine N-Cyclohexanoyl-2- (2', 2 ', 6', 6'-tetramethylpiperidinyl-4 ') ethylamine N-phenylacetyl-2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethylamine N-Benzoyl-2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') -ethylamine N - [(2 ", 2 ", 6", 6 "- tetramethylpiperidinyl-4") - acetyl] -2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') - ethylamine N, N'-di- [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') -thyl] - sebacamide N, N'-di- [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4' ) - ethyl] malonamide N, N'-di- [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') - ethyl] maleoylamide N, N'-di- [2- (2 ' , 2 ', 6', 6'-tetramethylpiperidinyl-4 ') - ethyl] oxalylamide N, N'-di- [2- (2', 2 ', 6', 6'-tetramethylpiperidinyl-4 ') -

   ethyl] thioxalylamide N, N'-di- [2 '- (2 ", 2", 6 ", 6" -tetramethylpiperidinyl-4 ") - ethyl] cyclohexyl-1,4-dicarboxoylamide N, N'-di- [2 '- (2 ", 2", 6 ", 6" -tetramethylpiperidinyl-4 ") -ethyl] phenyl-1,4-dicarboxoylamide N-allyl-N' - [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') - ethyl] urea N-methyl-N '- [2- (2', 2 ', 6', 6'-tetramethylpiperidinyl-4 ') ethyl] urea N- (n -Hexyl) -N'- [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethyl] -urea N-cyclohexyl-N'- [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethyl] urea N-benzyl-N'- [2- (2 2 6 6'-tetarmethylpiperidinyl-4 ') ethyl] urea N-phenyl-N' - [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethyl] urea N - (?

  ; -Naphthyl) -N '- [2- (2', 2 ', 6', 6'-tetramethylpiperidinyl-4 ') -ethyl] -urea N, N'-di- [2- (2', 2 ' , 6 ', 6'-tetramethylpiperidinyl-4') -ethyl] urea 1,6-di- [2 '- (2 ", 2", 6 ", 6" -tetramethylpiperidinyl-4') -ethylureido] -hexane N , N-dicyanoethyl- [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethylamine] N-isobutyryl-2- (2 2 ', 6 6'-tetramethylpiperidinyl-4') ethylamine p, p'-di- [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') -ethylureido] - diphenylmethane [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl -4 ') - ethyl] guanidine [2- (2', 2 ', 6', 6'-tetramethylpiperidinyl-4 ') - ethyl] -biguanidine N-thioacetyl-2- (2'.2', 6 = 6'-tetramethylpiperidinyl-4g-ethylamine Nn-thiohexanoyl-2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethylamine Nn-thiododecanoyl-2- (2 ', 2', 6 ', 6 '-

   tetramethylpiperidinyl-4 ') ethylamine N-phenylthioacetyl-2- (2', 2 ', 6', 6'-tetramethylpiperidinyl-4 ') ethylamine N-thiobenzoyl-2- (2', 2 ', 6', 6'- tetramethylpiperidinyl-4 ') ethylamine N-ethyl-N'- [2- (2', 2 ', 6', 6'-tetramethylpiperidinyl-4) - ethyl] thiourea N-allyl-N'- [2- (2 ' , 2 ', 6', 6'-tetramethylpiperidinyl-4 ') - ethyl] thiourea N-Cyclohexyl-N' - [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethyl] - thiourea Nt-octyl-N '- [2- (2', 2 ', 6', 6'-tetramethylpiperidinyl-4 ') ethyl] -thiourea N- (ss-naphthyl) - N' - [2- (2 ' , 2 ', 6', 6'-tetramethylpiperidinyl) ethyl] thiourea ethyl {N- [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') -ethyl]} carbamoate Nn-butyl - {N- [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') -ethyl]) carbamoate N- [2- (2 ', 2', 6 ', 6'- Tetramethylpiperidinyl-4 ') -

   ethyl] p-toluenesulfonamide sulfonylamino-bis [2- (2 2 ', 6', 6'-tetramethylpiperidinyl-4 ') ethane] 2- (1', 2 ', 2', 6 ', 6'-pentamethylpiperidinyl -4 ') - ethylamine 2- (1'-n-propyl- 2', 2 ', 6', 6'-tetramethylpiperidinyl-4 ') - ethylamine 2- (1'-benzyl- 2', 2 ', 6 ', 6'-tetramethylpiperidinyl-4') - ethylamine N-acetyl-2- (1 ', 2', 2 ', 6', 6- pentamethylpiperidinyl-4 ') ethylamine Nn-butyryl-2- (1', 2 ', 2', 6 ', 6'-pentamethylpiperidinyl-4) - ethylamine Nn-octanoyl-2- (1', 2 ', 2', 6 ', 6'-pentamethylpiperidinyl-4') ethylamine 2- [1 ' - (2 "-Hydroxyethyl) - 2 ', 2', 6 ', 6'-tetramethylpiperidinyl4] -ethylamine 2- [1' - (2" -Phenyl-2 "-hydroxyethyl) -2 ', 2', 6 ' , 6'-tetramethylpiperidinyl-4 ') -

   ethylamine Nn-dodecanoyl-2- (1 ', 2', 2 ', 6', 6'-pentamethylpiperidinyl-4 ') ethylamine N-cyclohexoyl-2 (1', 2 ', 2', 6 ', 6'- pentamethylpiperidinyl-4 ') ethylamine N-phenylacetyl-2- (1', 2 ', 2', 6 ', 6'-pentamethylpiperidinyl-4') ethylamine N-benzyl-2- (1 ', 2', 2 ', 6 ', 6'-pentamethylpiperidinyl-4') -ethylamine N, N'-di- [2- (1: 2: 2:

  : 6 ', 6'-pentamethylpiperidinyl-41-sebacamide N-allyl-N' - [2- (1 ', 2', 6 ', 6'-pentamethylpiperidinyl-4') -ethyl] urea N-methyl-N ' - (2- (1 ', 2', 6 ', 6'-pentamehylpiperidinyl-4') ethyl] - urea N-Cyclohexyl-N'- (2- (1 ', 2', 2 ', 6', 6 '- pentamethylpiperidinyl4') - ethyl] urea N-phenyl-N '- [2- (1', 2 ', 2', 6 ', 6'-pentamethylpiperidinyl-4') ethyl] urea N, N'- Di- [2- (1 ', 2 "2', 6 ', 6'-pentamethylpiperidinyl-4') -ethyl] urea 1,6-di- [2- (1 ', 2', 2 ', 6' , 6'-pentamethylpiperidinyl-4 ') - ethyl ureido] -hexane N-thioacetyl-2- (1', 2 2 ', 6', 6'-pentamethylpiperidinyl) -4 ') - ethylamine N-phenylthioacetyl-2- ( 1 ', 2', 2 ', 6', 6'-pentamethylpiperidinyl 4 ') -ethylamine N-methyl-N'- [2- (1', 2 ', 2', 6 ', 6'-

   pentamethylpiperidinyl-4 ') ethyl] -thiourea N-Cyclohexyl-N' - [2- (1 ', 2', 2 ', 6', 6'-pentamethylpiperidinyl4 ') -ethyl] -thiourea N- (ss-naphthyl) -N '- [2- (1', 2 ', 2', 6 ', 6'-pentamethylpiperidinyl4') -ethyl] -thiourea Ethyl- {N- [2- (1 ', 2', 2 ', 6 ', 6'-pentamethylpiperidinyl-4') ethyl]) carbamoate N- [2- (1 '- (1', 2 ', 2', 6 ', 6'-pentamethylpiperidinyl-4) ethyl] ptoluenesulfonamide N -Acetyl-2- (1'-allyl-2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4) ethylamine N-benzoyl-2- (1'-n-propyl-2,2,6,6- tetramethylpiperidinyl-4) ethylamine N-methyl-N- [2- (1'-dodecyl-2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') -ethyl] urea Nn-octanoyl-2- (2 ', 2'-diisopropyl-6', 6'-dimethylpiperidinyl4 ') - ethylamine N-phenyl-N' - [2- (2,2-diethyl-6,6'-dimethylpiperidinyl-4 ') ethyl] urea N - (2 "-Hydroxyethyl) - [2- (1 ', 2', 2 ', 6', 6'-pentamethylpiperidin yl-4 ') j-

   ethylamine N, N-di- (2 "-hydroxyethyl) - [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4')] - ethylamine N, N-di- (2" -hydroxyethyl) - [2- (1 ', 2', 2 ', 6', 6'-tetramethylpiperidinyl-4 ')] - ethylamine N, N'-di- [2- (2', 2 ', 6', 6 ' - tetramethylpiperidinyl-4 ') - ethyl] thiodipropionamide.



  b) If A = -O- [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') -ethyl] -n-dodecanoate n-octyl- [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') -ethyl] -ether N-phenyl- [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') -ethyl] urethane N-methyl- [ 2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4) - ethyl] urethane N-Cyclohexyl- [2- (2', 2 ', 6', 6'-tetramethylpiperidinyl-4 ') [2 - (2 ', 2', 6 ', 6'-Tetramethylpiperidinyl-4') -ethyl] - (2 ", 2", 6 ", 6" -tetramethylpiperidinyl-4 ") - acetate.



   Compounds of the formula I in which m are O, A> N-R4 and R5 are hydrogen, can be prepared by a compound of the formula
EMI4.1
 wherein R, R2, R3 and Y have the definitions given above, with the proviso that Y is a saturated group, in the presence of an amine R4NH2, hydrogenated, wherein R4 has the meaning given above, provided that R4 is a saturated group.



   The hydrogenation of the compound of Formula III can conveniently be carried out using molecular hydrogen or using chemical agents such as lithium aluminum hydride. If molecular oxygen is used, the hydrogenation can be carried out in a known manner using a hydrogenation catalyst such as palladium, platinum, rhodium or nickel, preferably on a support such as silicon dioxide, calcium carbonate or carbon. The reaction is advantageously carried out at elevated temperature and elevated pressure in a suitable solvent such as ethanol or cyclohexane.



   The compounds of formula 1 (where A => NR4) can also be prepared by adding a compound of formula
EMI4.2
 wherein R1, R2, R3 and Y have the meanings given above, with the corresponding aldehyde and formic acid, by carrying out a Leuckart reaction.



   In a further modification, compounds of the formula IV can be reacted with the corresponding aldehyde and the Schiff base thus obtained can then be hydrogenated over a catalyst such as nickel or palladium. This reaction cannot be used to prepare compounds of Formula I in which the R4 and Y substituents are unsaturated since such substituents would be hydrogenated during the process.



   In a further modification, the compounds of the formula IV can be reacted with an alkyl, alkenyl, cycloalkyl or aralkyl halide.



   The starting materials of the formula III can be prepared by reaction in an inert solvent of a phosphonate of the formula [(R6O) 2p (O) CH (R3) CN] - B + V where R3 has the meaning given above, R6 is an alkyl group having 1 to 4 carbon atoms and B + is the cation of an organic or inorganic base with the piperidine derivative of the formula
EMI4.3
 be prepared, wherein R1, R2 and Y have the meanings given above, with the proviso that Y does not mean an unsaturated group.



   Suitable examples of inert solvents are benzene, dioxane and cyclohexane and base cations B + which can be used are alkali metal cations.



   The compounds of formula V are well known.



   The substituent Y, if it has a meaning other than hydrogen, can be converted into the corresponding compounds of the formulas I, III or VI, in which Y is H, by known processes such as by reaction with an alkyl, aralkyl, alkenyl or alkynyl halide or by Leuckart or Wallach reaction or by reacting with
EMI4.4
 are introduced, in which R8 has the meaning given above.



   To prepare a compound of the formula I in which m is O, A> N-R4 or one or both of the groups R4 and R5 is a -cH2cH (oH) Rs group, one can also proceed in such a way that a compound of the formula IV, as previously defined, with a compound of the formula
EMI4.5
 converts, in which R8 has the meaning given above.

 

   To prepare a compound of the formula I in which m is 1, one can also proceed in such a way that a compound of the formula
EMI4.6
 wherein R1, R2, R3, A and Y have the meanings given above, with a compound VIII which is capable of introducing a group -XRs to the nitrogen or oxygen atom of the side chain.



   In a further process, a compound of the formula I in which A is> N-R4 and one or both groups R4 and R5 are a cyanoethyl group is prepared by reacting a compound of the formula VII with acrylonitrile.



   The reactants VIII capable of introducing the -XRs group will of course depend on the nature of the X group. However, suitable reactants can be summarized under the following headings.



  I. A means> N-R4 or -0 (i) X means -CO or (a) Suitable reactants are those of the formula R, (COZ), or Rs (CSZ) n in which R5 and n have the definitions given above and Z is halogen; for example, when n is 1, suitable reactants are butyryl chloride, acetyl chloride, benzoyl chloride, crotonyl chloride; when n is 2, suitable reagents are sebacoyl chloride, fumaryl chloride, succinyl chloride, adipyl chloride; alternatively, when R5 is absent, a suitable reagent is, for example, oxalyl chloride.



   The reaction is preferably carried out in an inert solvent such as benzene or cyclohexane.



   (b) Other suitable reactants are those of the formula R5 (C02R7) n or R5 (CSOR7) n in which R5 and n have the meanings given above and R7 is an alkyl group having 1 to 4 carbon atoms. A suitable reactant in this group is, for example, ethyl benzoate, ethyl (2,2,6,6-tetramethylpiperidinyl-4) acetate and methyl octanoate.



   The reaction can be carried out at a temperature in the range from 0 to 200.degree. C., preferably it is carried out at a temperature in the range from 140 to 1800.degree. The reaction can be carried out in the absence or presence of a catalyst and an inert solvent such as xylene. However, if a catalyst is used, an alkali metal amide, p toluenesulfonic acid, tetrabutyl titanate or an alkali metal alcoholate can be used, for example.



  (ii) (a) X is -CONH- or -CSNH
Examples of reactants are those of the formula Rs (NCO) n or R5 (NCS) n in which R5 and n have the meanings given above, for example when n is 1, methyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, 1-naphthyl isothiocyanate, and when n is 2 , Hexane-1,6-diisocyanate, 4,4'-diisocyanatodiphenylmethane.



   The reaction can expediently be carried out in a suitable solvent such as petroleum ether, cyclohexane or benzene and with or a catalyst such as diazo-bis-cyclooctane or piperidine.



     II. X means only> N-R4
EMI5.1


<tb> <SEP> -C-NH- <SEP> -C-NH
<tb> <SEP> II <SEP> II
<tb> (i) <SEP> (a) <SEP> X <SEP> means <SEP> 0 <SEP>, <SEP> S <SEP> or
<tb> SO2NH, if R5 has the formula II, in which p2 is
Compounds of the formula I in which R5 has the formula
EMI5.2
 has, wherein R1, R2 and Y have the meanings given above and
EMI5.3
 means can be prepared by reacting the compound of the formula VII with phosgene (or urea) or thiophosgene (or thiourea or carbon disulfide together with an alkali metal hydroxide).



   (c) If X is -SO2-NH-, compounds of the formula I can be prepared by reacting compounds of the formula IV with sulfuryl chloride.



  (ii) (X means
EMI5.4
 in which q has the meaning given above (a) Compounds in which q is 1 can be prepared, for example, by reacting compounds of the formula IV with a cyanamide or substituted cyanamide of the formula RsNHCN, in which R5 has the meaning given above.



   (b) The compounds in which q is 2 can be prepared, for example, by reacting the compounds of the formula IV with a dicyandiamide or substituted dicvandiamide of the formula
EMI5.5
 wherein R5 has the meaning given above.



  (iii) X means -SO2-
These compounds can be prepared by reacting a compound of the formula IV with a compound of the formula R5 (SO2Z) n, in which Rs and n have the meanings given above and Z is halogen, for example p-toluenesulfonyl chloride.



  III. A denotes -0- and m is absent (i) A compound of the formula VII in which A denotes 0- is reacted with an alkali metal, the alkali metal salt being obtained, and then reacted with a compound of the formula RsZ in which Z is a Halogen atom means (ii) Alternatively, a compound of the formula Ix
EMI5.6
 where Z is a halogen atom, are reacted with compounds of the formula RsOM, where M is an alkali metal.



   Compounds of the formula IX can be prepared by known processes from compounds of the formula VII in which A-O- and R3 are H.



   The reactions under heading III can be carried out in a solvent which is inert towards the reactants, for example in toluene or cyclohexane, preferably at the reflux temperature of the solvent.



   The salts of compounds of the formula I are also new compounds. The salts can be prepared by reacting an acid with a compound of Formula I in an inert solvent, preferably at ambient temperature, although higher reaction temperatures can be used if desired.



   After their preparation, as described above, the compounds of the formula I or the salts thereof can be isolated and purified by known processes, such as by fractional crystallization from a suitable solvent.



   When incorporated into polymeric substrates, the compounds of the formula I and their salts protect the substrates against decomposition caused by visible and / or ultraviolet light, against oxidative decomposition or against thermal effects.



   It has been found that compounds of the formula I give polyolefins an exceptionally high stability to decomposition, which is usually caused by the action of ultraviolet radiation or the action of heat. The improved stability is also achieved without the color properties of the treated polyolefins being affected. The stabilizers according to the invention enable effective light and / or heat stabilization, in particular for low and high density polyethylene and polypropylene and polystyrene as well as for polymers made from 1-butene, 1-pentene, 3-methylbutene-1, 1-hexene, 4-methylpentene -1, 4-methylhexene-1 and 4,4-dimethylpentene-1 and also for copolymers and terpolymers of olefins, in particular of ethylene or propylene.



   Other organic materials which are decomposed by the action of light and whose properties are improved by the incorporation of compounds of the formula I include natural and synthetic polymeric materials, for example natural and synthetic rubbers, the latter being for example homo-, co- and terpolymers of acrylonitrile, butadiene, and styrene.



   Specific synthetic polymers include polyvinyl chloride and vinyl chloride copolymers, polyvinyl acetate as well as the condensation polymers derived from ethers, esters (derived from carboxylic acids, sulfonic acids, or carbonic acids), amides, or urethane compounds; Polyvinyl acetals; Polyacrylates such as the polymers and copolymers of methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate; Polyamides; Urea-formaldehyde and melamine-formaldehyde resins; Cellulose plastics such as cellulose acetate, cellulose butyrate and cellulose nitrate. Certain of these polymers can, for example, be the basis for surface coating agents such as paints and varnishes and contain an oil or resin base such as an alkyd or
Polyamide resin.



   The amount of compound of formula I that is incorporated into the organic material in order to obtain maximum protection against decomposition by light varies according to the properties of the organic material to be treated and according to the strength of the light irradiation and the duration of the Irradiation. For most purposes, however, it is sufficient to add an amount of the compound of the formula I in the range from 0.01 to 5% by weight, more preferably from 0.1 to 2% by weight, based on the weight of the untreated organic material use.



   The compounds of the formula I can be incorporated into the polymeric material by any of the known methods used in the processing of additives with a polymer. For example, the compounds of the formula I and the polymer can be mixed in an internal mixer. Alternatively, the compound of formula I can be added to the powdered polymer as a solution or slurry in a suitable solvent or dispersant, for example an inert organic solvent such as methanol, ethanol or acetone, and all of the mixed material can be intimately mixed in a mixer and the solvent can then be removed.

  As a further alternative, the compound of formula I can be added to the polymer during its preparation, for example at the latex stage of polymer preparation, thereby obtaining a pre-stabilized polymer material.



   The composition according to the invention can optionally contain further additives, in particular those used in polymer formulations, such as antioxidants of the phenol or amine type, UV absorbers and light stabilizers, phosphite stabilizers, peroxide decomposers, polyamide stabilizers, basic co-stabilizers, polyvinyl chloride -Stabilizers, nucleating or nucleating agents, plasticizers, lubricants, emulsifying agents, antistatic agents, fire retardants or flame retardants, pigments, carbon black, asbestos, glass fibers, kaolin and talc.



   The invention thus also relates to binary, tertiary and multicomponent compositions which contain a stabilizer of the formula I together with one or more functional additives for polymers.



   Examples of suitable antioxidants are those of the sterically hindered phenols.



   Further examples of antioxidants are those of the aminoaryl series.



   In binary mixtures with one or more antioxidants or in tertiary mixtures with antioxidants and UV absorbers, the compounds of the formula I produce a very effective stabilizer composition for polyolefin formulations.



   The following examples illustrate the invention without restricting it. The parts and percentages are expressed by weight unless otherwise specified.



   Example 1 (a) A mixture of 450 parts by weight of diethylphosphonoacetonitrile, 380 parts by weight of 2,2,6, 6-tetramethylpiperidin-4-one and 135 parts by weight of sodium methylate in 2,500 parts by volume of ethyl alcohol was refluxed for 6 hours with stirring warmed up. The solvent was then removed by distillation under reduced pressure, the residue was treated with water (1500 parts by volume) and the resulting oil was extracted with ether (6 x 200 parts by volume). The combined ether extracts were dried over magnesium sulfate and the ether was removed by distillation under reduced pressure.

 

   Distillation of the oil that remained gave 302 parts by weight of (2,2,6,6-tetramethylpiperidinylidene-4) acetonitrile, boiling point 130 to 132 ° C./12 mm Hg.



   (b) This material was hydrogenated in 1500 parts by volume of methyl alcohol which was saturated with ammonia at a pressure of 60 atmospheres hydrogen and 60 ° C. for 12 hours using a Raney nickel catalyst. After removal of the catalyst and solvent, 250 parts by volume (80% theoretical yield) of pure 2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethylamine, boiling point 110 to 112 "were obtained by distillation. C / 12 mm Hg.



     Elemental Analysis: C1 1H24N2 Calculated: C 71.70% H 13.12% N 15.20% Found: 71.49 12.81 15.32
Example 2 (a) 60 parts by weight of (2,2,6,6-tetramethylpiperidinylidene-4) acetonitrile (prepared as described in Example 1), 31.4 parts by volume of formic acid (98%) and 28.2 parts by volume of 36 % aqueous formaldehyde was heated with stirring at 100 ° C. for 4 hours.



   46% aqueous sodium hydroxide solution was added to the cooled solution until it had a basic reaction. The resulting oil was extracted with 4.50 parts by volume of ether.



  The combined ether extracts were dried over magnesium sulfate and the ether was removed by distillation under reduced pressure.



   The remaining oil was purified by distillation, 56 parts by weight (86% theoretical yield) 1,2,2,6,6 pentamethylpiperidinylidene-4) acetonitrile being obtained, bp.



     152 "C / 20 mm Hg.



   (b) This material was hydrogenated in 250 parts by volume of methyl alcohol, which was saturated with ammonia, at a pressure of 100 at and at 100 "C over the course of 24 hours using Raney nickel as a catalyst. After removal of the solvent and of the catalyst, the remaining oil was purified by distillation, 45 parts by weight (78% of the theoretical yield) of 2- (1 ', 2, 2', 6 ', 6'-pentamethylpiperidinyl-4') ethylamine being obtained, boiling point 82 up to 84 "C / 1.0 mm Hg, elemental analysis: C12H26N2 Calculated:

  C 72.66% H 13.21% N 14.12% Found: 72.58 13.00 13.97
Example 3
A mixture of 3.1 parts by weight of methyl isocyanate, 9.2 parts by weight of 2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethylamine and 100 parts by volume of petroleum ether (boiling range 60 to 80 "C) was refluxed with a trace of diazo-biscyclooctane for 24 hours.



   The petroleum ether was removed by distillation under reduced pressure to give an oil which solidified on standing. This was dissolved in 50 parts by volume of carbon tetrachloride and reprecipitated by adding 200 parts by volume of petroleum ether (boiling range 60 to 80 ° C.). The colorless solid was collected by filtration and dried at 50 ° C., 10.3 parts by weight (86% of the theoretical yield) pure N-methyl-N'- 2- (2 \ 2 ', 6 \ 6'-tetramethylpiperidinyl-4') -ethyl] urea obtained, Afp. 730 C.



  Elemental Analysis: C13H27N3O Calculated: C 64.69% H 11.27% N 17.41% Found: 64.67 11.26 17.57
Example 4
A mixture of 6.9 parts by weight of cyclohexyl isocyanate, 9.2 parts by weight of 2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4) ethylamine, 100 parts by volume of benzene and a trace Diazo-biscyclooctane was heated to reflux for 24 hours. The benzene was then removed by distillation under reduced pressure and the remaining oil was treated with water (400 parts by volume) to give a colorless solid. This was collected by filtration, dried and purified by recrystallization from ethyl acetate (150 parts by volume), N-cyclohexyl-N'- 2- (2 \ 2 ', 6', 6'-tetramethylpiperidinyl-4 ') ethyl ] urea, m.p. 1100 C.



  Elemental analysis: C1BH35N30 Calculated: C 69.86% H 11.40% N 13.58%
Found: 69.90 11.32 13.59
Example 5
A mixture of 6.6 parts by weight of phenyl isocyanate, 9.2
Parts by weight of 2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') - ethyl amine and 100 parts by volume of benzene was refluxed during
Heated for 18 hours. The benzene was then stripped off by distillation under reduced pressure to give a colorless solid which was recrystallized from 100 parts by volume of ethyl acetate to give N-phenyl-N'- [2- (2 ', 2 6 6' - tetramethylpiperidinyl-4 ') - ethyl] urea obtained, m.p. 151 to 152 "C.



  Elemental analysis: C18H29N3O
Calculated: C 71.25% H 9.63% N 13.85%
Found: 71.40 9.7 13.56
Example 6
A mixture of 3.6 parts by weight of hexamethylene diisocyanate, 11 parts by weight of 2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl4') ethylamine and 100 parts by volume of petroleum ether (boiling range 60 to 80 ° C ) was heated to reflux for 24 hours in the presence of a trace of diazo-bis-cyclooctane.



  The resulting solid was collected by filtration and purified by continuous extraction with ethyl acetate, after drying 10.5 parts by weight (82% theoretical yield) of 1,6-di- [2 '- (2 ", 2" , 6 ", 6" - tetramethylpiperidinyl-4 ") - ethylureido] -hexane, Afp. 1350 C.



  Elemental analysis: C30H60N602 Calculated: C 67.11% H 11.27% N 15.66% Found: 67.04 11.08 15.77
Example 7
A mixture of 6.25 parts by weight of di (4-isocyanatophenyl) methane, 9.2 parts by weight of 2- (2 2: 6 6'-tetramethylpiperidinyl-4 ') ethylamine and 200 parts by volume of benzene was on Heated to reflux for 24 hours. The resulting colorless solid was collected by filtration and purified by continuous extraction with ethyl acetate, p, p'-di- [2- (2 2 ', 6 6'-tetramethylpiperidinyl-4') ethyl ureido] diphenylmethane being obtained, m.p. . 208 to 209 C.

 

  Elemental Analysis: Ca7H, 8N6O2 Calculated: C 71.80% H 9.45% H 13.58% Found: 71.75 9.37 13.73
Example 8
43 parts by volume of a 122% w / v solution of phosgene in toluene were added dropwise with stirring at 10 to 20 ° C. over the course of 15 minutes to a solution of 36.8 parts by weight of 2- (2 ', 2 ', 6', 6'-tetramethylpiperidinyl-4 ') ethylamine in 200 parts by volume of toluene.



   The resulting suspension was stirred at room temperature for 4 hours. Then it was refluxed for an additional hour.



   A colorless solid was separated off by filtration, this was dissolved in water (100 parts by volume) and then sodium hydroxide was added to the solution up to a pH value of 14. A colorless oil separated out, this was washed with diethyl ether (4 x 50 parts by volume). The ether was dried over magnesium sulfate and removed by distillation under reduced pressure to give N, N'-di- [2 (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4? -Ethyl] urea, Afp 750 C.



  Elemental Analysis: C23H46N4O Calculated: C 70.00% H 11.75% N 14.20% Found: 69.95 11.93 14.40
Example 9
A solution of 9.2 parts by weight of 2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') -ethylamine in 20 parts by volume of benzene was added dropwise to a solution with stirring over the course of 15 minutes 3.9 parts by weight of acetyl chloride in 80 parts by volume of benzene.



   The resulting suspension was refluxed for 2 hours, then cooled and the solid was filtered off.



  The solid was dissolved in 50 parts by volume of water, and sodium hydroxide was added until a basic reaction of pH = 14.



  The precipitated oil was extracted with diethyl ether (5 × 30 parts by volume). The combined ether extracts were dried over magnesium sulfate and the ether was distilled off.



   Distillation of the remaining oil gave N-acetyl-2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') -ethylamine, b.p. 156 to 1600 ° C. / 0.6 mm Hg.



  Elemental Analysis: C13H26N2O Calculated: C 68.98% H 11.58% N 12.38% Found: 68.69 11.31 12.24 Example 10
A solution of 9.2 parts by weight of 2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethylamine in 20 parts by volume of benzene was added dropwise to a solution of 4.5 parts by weight of n -Butyryl chloride in 80 parts by volume of benzene was added over the course of 15 minutes with stirring. The suspension was refluxed for 2 hours and then worked up as described in Example 9.



   This gave N-butyryl-2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethylamine, boiling point 1600 C / 0.7 mm Hg.



  Elemental Analysis: CtsH3oN2o Calculated: C 70.82% H 11.89% N 11.01% Found: 70.56 11.64 11.04
Example 11
A solution of 9.2 parts by weight of 2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethylamine in 20 parts by volume of benzene was stirred into a solution of 8.1 parts by weight n Octanoyl chloride given in 80 parts by volume of benzene. It was then worked up as described in Example 9.



   In this way, N-octanoyl-2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethylamine, boiling point 188 to 192 ° C./0.8 mm Hg.



  Elemental Analysis: CtgH38N2O Calculated: C 73.49% H 12.33% N 9.02% Found: 73.17 12.16 8.68
Example 12
A solution of 18.4 parts by weight of 2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethylamine in 50 parts by volume of benzene was stirred into a solution of 21.8 parts by weight n-Dodecanoyl chloride in 200 parts by volume of benzene for 30 minutes. The procedure was then as described in Example 9, N-dodecanoyl-2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethylamine being obtained, boiling point 208 to 212 ° C./0.6 mm Hg.



  Elemental Analysis: C23H46N2O Calculated: C 75.35% H 12.65% N 7.64% Found: 73.37 12.65 7.46
Example 13
A solution of 9.2 parts by weight of 2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethylamine in 20 parts by volume of benzene was stirred into a solution of 7 in the course of 30 minutes , 0 parts by weight of benzoyl chloride in 80 parts by volume of benzene. The resulting suspension was refluxed for 2 hours, cooled and the solid was collected by filtration. The solid was dissolved in 100 parts by volume of water and the pH of the solution was then adjusted to 14 by adding sodium hydroxide. The precipitated oil was extracted with diethyl ether (6 × 30 parts by volume) and the combined extracts were dried over magnesium sulfate.

  After removal of the ether by distillation, a colorless solid was obtained which was recrystallized from 100 parts by volume of petroleum ether (boiling range 60 to 80 ° C.), pure N-benzoyl-2- (2 ', 2', 6 ', 6 'tetramethylpiperidinyl-4') ethylamine obtained, m.p. 101 to 102 "C.



  Elemental Analysis: C18H28N2O Calculated: C 74.96% H 9.78% N 9.71% Found: 74.68 9.62 9.44
Example 14
A mixture of 11.4 parts by weight of ethyl (2,2,6,6-tetramethylpiperidinyl-4) acetate, 9.2 parts by weight of 2- (2 ', 2', 6 ', 6' tetramethylpiperidinyl-4) ') - Ethylamine and 2.7 parts by weight of sodium methylate were heated at 1600 C for 1 hour while stirring. During this time, the ethyl alcohol was able to distill off from the reaction mixture. The mixture was finally heated at 1600 C / 12 mm Hg for 15 minutes, then cooled and dissolved in 100 parts by volume of diethyl ether.

  The ether extract was washed with water (4 × 20 parts by volume), dried over magnesium sulfate and the ether was finally removed by distillation, the N -] (2 ", 2", 6 ", 6" - tetramethylpiperidinyl-4 " ) - acetyl] -2 (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') - ethylamine was obtained as a pale green, highly viscous oil.



  Elemental Analysis: C22H43N3O Calculated: C 72.28% H 11.85% N 11.59% Found: 72.48 11.73 11.34
Example 15
A solution of 9.9 parts by weight of 2- (1 ', 2', 2 ', 6', 6'-pentamethylpiperidinyl-4 ') ethylamine in 20 parts by weight of benzene was stirred into a solution of 3.9 Add parts by weight of acetyl chloride in 80 parts by weight of benzene. The resulting suspension was then treated as described in Example 9, 8.3 parts by weight (68% theoretical yield) of N acetyl-2- (1 ', 2', 2 ', 6', 6'-pentamethylpiperidinyl -4 ') - ethylamine, boiling point 158 to 1600 C / 0.6 mm Hg.



  Elemental Analysis: C14H28N2O Calculated: C 69.95% H 11.74% N 11.65% Found: 70.19 11.96 11.83
Example 16
A solution of 9.9 parts by weight of 2- (1 ', 2', 2 ', 6', 6'-pentamethylpiperidinyl-4 ') ethylamine in 20 parts by volume of benzene was converted into a solution of 4.5 parts by weight. Parts of n-butyryl chloride in 80 parts by volume of benzene. The procedure described in Example 9 was then followed.



   In this way, N-butyryl-2- (1 ', 2', 2 ', 6', 6'-pentamethylpiperidinyl-4) ethylamine, boiling point 166 to 168 ° C./0.2 mm Hg.



  Elemental Analysis: C16H32N20 Calculated: C 71.59% H 12.02% N 10.44% Found: 71.84 11.92 10.35
Example 17
A solution of 9.9 parts by weight of 2- (1 2 ', 2 6 6'-pentamethylpiperidinyl-4') ethylamine in 20 parts by volume of benzene was stirred into a solution of 7 parts by weight in the course of 30 minutes Benzoyl chloride given in 80 parts by weight of benzene. The suspension was then refluxed for 2 hours, the benzene was then decanted from the flask and the remaining gum was dissolved in 200 parts by volume of water. The pH of this solution was adjusted to 14 by adding sodium hydroxide and the colorless solid that separated was collected by filtration, dried and purified by recrystallization from 50 parts by volume of cyclohexane, 10 parts by weight (67% of theory).

  Yield) N-benzoyl-2- (1, 2 ', 2', 6 \ 6'-pentamethylpiperidinyl-4 ') -ethylamine obtained, Afp. 1070 C.



  Elemental Analysis: C1gH30N2O Calculated: C 75.45% H 10.00% N 9.26% Found: 75.72 10.05 9.50
Example 18
A solution of 6.6 parts by weight of phenyl isocyanate, 9.9 parts by weight of 2- (1 ', 2', 2 ', 6', 6'-pentamethylpiperidinyl-4 ') ethylamine and petroleum ether (boiling range 80 to 100 " C), which contained a trace of diazo-bis-cyclooctane, was refluxed for 2 hours. The solid precipitate formed was separated off by filtration and recrystallized from 150 parts by volume of ethyl acetate, N-phenyl-NI [2- (1 = 2 = 2: 6 = 6 'pentamethylpiperidinyl-4') ethyl] urea obtained, m.p. 143 to 144 "C.



  Elemental Analysis: C19HS1N90 Calculated: C 71.88% H 9.84% N 13.24% Found: 72.23 9.91 13.22
Examples 19 to 28
38 parts of polypropylene were homogenized with 0.076 parts of n-octadecyl-ss- (4¯hydroxy-3 ', 5¯t-butylphenyl) propionate in a kneader at a temperature of 200 "C in the course of 3 minutes. 0.19 Portions of the product from Example 1 were then added and then homogenization was continued for an additional 7 minutes.



   The homogenized mixture was then removed from the kneader and pressed to a thickness of 2 to 3 mm in a press at a temperature of 200.degree. 9 parts of the polypropylene mixture were then placed in a press, the press plates or tables being protected with a 0.1 mm thick aluminum foil. The samples were surrounded by four strips of steel bands, 0.3 mm thick, in the shape of a square, which acted as spacers between the aluminum foils. The press was closed and no pressure was applied for 2 minutes. The pressure was then increased to a maximum of 12 t over the course of 2 minutes; this pressure was maintained for a further 2 minutes, the temperature being 260.degree. The pressure was removed and the material (0.3 mm thick) was immediately cooled under running water.



   2.2 parts of this material were cut into the shape of a square and returned to the press. The conditions were the same as in the previous pressure treatment, with the exception that a 0.1 mm thick steel spacer was used to provide the space between the aluminum foils. The press was closed and no pressure was applied for 2 minutes. The pressure was increased to 8 t for a further 2 minutes, the temperature in the press being 260 "C. This pressure was maintained for 2 minutes and then the pressure was removed. The sandwich structure made of the 0.1 mm thick polypropylene film and the aluminum foils were then removed and immediately thereafter heated in an oven with closed air at 1500 C for 1 hour.

  The sandwich structure was then quenched in cold running water and the aluminum foils peeled from the inner polypropylene sheet and the spacers removed.



   An area 44 x 1100 mm was separated from the 0.1 mm tempered polypropylene film and placed in a fade meter
Device comprising a circular bank with 28 alternating
Containing sunlight and black light lamps exposed to light. The sunlight lamps were 2 feet (0.6 m) long, 20 watt fluorescent lamps that ran through a
Peak emission of 3000 units are characterized. The
Black light lamps were 0.6 m (2 feet) long, 20 W ultraviolet lamps, which are characterized by a peak emission of 3500 units. The sample was rotated concentrically within the lamp bank so that the irradiation therefrom was uniformly distributed over the test sample.

 

   The exposed sample was examined periodically and the
The time (T) at which the sample reached 50% of its original elongation to break was noted.



   The time (Tc) for a comparative sample (which did not contain the product of Example 1) to elongate, which it took to decrease to 50% of the original elongation, was then determined.



   The effect of the compound of formula I as a light stabilizer could then be calculated using the
Factor T / Tc determined.



   The results that are obtained are as follows
Table listed, where the results of experiments are also listed when other compounds of the formula I were used.



  Table e.g. Product Factor T / Tc No.



   Time to 50% of the originally



   Elongation to break
Time to 50% of the original Elongation to break d. Comparative sample
19 N-Benzoyl-2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') -ethylamine 3,5 20 N-Phenyl-N'- [2- (2 ', 2', 6 ' , 6'-tetramethylpiperidinyl-4 9-ethyl] -urea 7.3 21 N-Cyclohexyl-N'- [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') -ethyl] -urea 6.3 22 N-octanoyl-2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') -ethylamine 8.3 23 N-acetyl-2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4 ') ethylamine> 6.0, ie 6.2 24 N-butyryl-2- (2', 2 ', 6', 6'-tetramethylpiperidinyl-4 ') ethylamine> 5.7 , ie

   6.0 25 N - [(2 ", 2", 6 'tetramethylpiperidinyl-4 ") -acetyl] -2- (2', 2 ', 6', 6'- 6.4 tetramethylpiperidinyl-4 ') -ethylamine 26 2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') - ethylamine> 9.3, ie 9.5 27 N-methyl-N'- [2- (2 ', 2', 6 ', 6'- tetramethylpiperidinyl-4') - ethyl] urea> S, 8 28 N-phenyl- [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') - ethyl] - urea 6.0
Example 29
A solution of 9.9 parts by weight of 2- (1 ', 2 "2', 6 ', 6'-pentamethylpiperidinyl-4') ethylamine in 20 parts by volume of dry benzene was stirred into a solution of 8.1 Parts by weight of n-octanoyl chloride in 80 parts by volume of dry benzene were added over the course of 20 minutes.

  The resulting suspension was stirred at room temperature for 15 minutes, then refluxed for a further 2 hours. The suspension was then cooled and the solid was filtered off and worked up as described in Example 9. This gave pure N-octanoyl [2- (1 2 ', 2', 6 6'-pentamethylpiepridinyl-4) ethylamine], boiling point 196 to 198 C / 0.6 mm Hg.



  Elemental Analysis: C20H40N2O Calculated: C 74.02% H 12.42% N 8.63% Found: 73.96 12.42 8.39
Example 30
A solution of 19.8 parts by weight of 2- (1 ', 2 2', 6 ', 6'-pentamethylpiperidinyl-4') ethylamine in 50 parts by weight of dry benzene was stirred into a solution of 21.8 parts by weight .Parts of n-dodecanoyl chloride in 200 parts by volume of dry benzene added over the course of 20 minutes. The suspension was stirred at room temperature for 15 minutes, then heated under reflux for 4 hours and finally worked up as described in Example 9. This gave 21.0 parts by weight (55% theoretical yield) of Nn-dodecanoyl- [2- (1 ', 2, 2', 6 ', 6'-pentamethylpiperidinyl-4 9-ethylamine], bp / 0.6 mm Hg.



     Elemental Analysis: C24H48N2O Calculated: C 75.73% H 12.71% N 7.36% Found: 75.83 12.56 7.38
Example 31
A solution of 9.6 parts by weight of sebacoyl chloride in 25 parts by volume of dry benzene was stirred into a solution of 19.2 parts by weight of 2 (1 ', 2', 2 ', 6', 6 ' Pentamethylpiperidinyl-4 ') ethylamine in 75 parts by volume of dry benzene was added. The resulting suspension was heated to reflux for 24 hours then cooled and the solid was collected by filtration.



  The solid was dissolved in 100 parts by volume of water and then 46% strength aqueous sodium hydroxide was added until the solution was strongly alkaline. An oil was obtained which was extracted into ether (6 × 50 parts by volume). The combined ether extracts were dried over magnesium sulfate and the ether was removed by distillation under reduced pressure, a colorless solid being obtained. This was purified by recrystallization from ethyl acetate, giving di- [2- (1 ', 2', 2 ', 6', 6'-pentamethylpiperidinyl-4 ') ethyl] sebacamide, melting point 122 to 123 C.



  Elemental Analysis: C34H66N4o2 Calculated: C 72.55% H 11.82% N 9.95% Found: 72.86 11.77 9.78
Example 32
A solution of 6.2 parts by weight of succinyl chloride in 25 parts by volume of dry benzene was added dropwise over 15 minutes with stirring to a solution of 19.8 parts by weight of 2- (1 ', 2', 2 "6 ', 6 '- Pentamethylpiperidinyl-4') - ethylamine was added in 75 parts by volume of dry benzene.



   The suspension was heated to reflux for 2 hours, then cooled, the solid was filtered off and worked up in the same way as described in Example 31, the N, N'-di- [2- (1 ', 2', 2 ', 6 ', 6'-pentamethylpiperidinyl-4') ethyl] succinamide, m.p. 171 to 172 "C.



  Elemental Analysis: C28H54N402 Calculated: C 70.25% H 11.37% N 11.70% Found: 69.97 11.31 11.65
Example 33
A solution of 9.9 parts by weight of 2- (1 ', 2', 2 ', 6', 6'-pentamethylpiperidinyl-4 ') ethylamine and 6.9 parts by weight of cyclohexyl isocyanate in 100 parts by volume of dry benzene, which contained a trace of diazo-bicyclooctane was refluxed for 24 hours. The benzene was removed by distillation under reduced pressure and the solid residue was recrystallized from ethyl acetate, giving 9.3 parts by weight (57% of theory) of N-cyclohexyl-N'- [2- (1 ', 2', 2 ', 6', 6'-pentamethylpiperidinyl-4 ') -ethyl] urea obtained, m.p. 154 to 155 C.



  Elemental Analysis: C19H37N3O Calculated: C 70.54% H 11.53% N 12.99% Found: 70.79 11.67 12.70
Example 34
A solution of 11.8 parts by weight of 2- (1 ', 2', 2 ', 6', 6'-penta methylpiperidinyl-4 ') ethylamine and 3.6 parts by weight of 1,6-diisocyanatohexane in 50 Parts by volume of petroleum ether (boiling range 60 to 80 "C) containing a trace of diaza-bicyclooctane was used on
Heated to reflux for 2 hours.



   The suspension was cooled and the resulting
Solid was separated by filtration. Recrystallization from ethyl acetate gave 8.2 parts by weight (58% of theory) pure
1,6-di- [2- (1 ", 2 '2", 6 ", 6" - pentamethylpiperidinyl-4 "- ethyl ureido] - hexane, m.p. 198 to 199 C.



   Elemental analysis: C32H64N6O2
Calculated: C 68.10% H 11.35% N 14.90%
Found: 67.82 11.19 14.80
Example 35
A solution of 9.9 parts by weight of 2- (1 2 ', 2', 6 ', 6'-penta methylpiperidinyl-4') ethylamine and 3.1 parts by weight of methyl isocyanate in 100 parts by volume of petroleum ether (boiling range 60 to 80 "C) was refluxed for 24 hours. The petroleum ether was then removed by distillation under reduced pressure and the residue was recrystallized from ethyl acetate, whereby pure N-methyl-N'- [2- (1 ', 2 = 2 ', 6', 6'-penta methylpiperidinyl-4 ') -ethyl] -urea obtained, m.p. 87 to 88 "C.



   Elemental analysis: Ci4H29N3O Calculated: C 65.84% H 11.44% N 16.45%
Found: 65.94 11.40 16.21
Example 36
A solution of 8.6 parts by weight of thiodipropionyl chloride in 50 parts by volume of benzene was added dropwise with stirring in the
It took 20 minutes to form a solution of 2- (2 ', 2 6', 6'-tetramethylpiperidinyl-4 ') ethylamine in 200 parts by volume
Given benzene. The resulting suspension was on
The mixture was heated to reflux for a further 2 hours, the solid was separated off by filtration, dissolved in 500 parts by volume of water and then 40% strength sodium hydroxide solution was added until a pH of 14 was established. The precipitated oil was extracted with chloroform (6 x 50 parts by volume), the combined extracts were dried and the chloroform was removed by distillation under reduced pressure.

  The residue was purified by distillation, N, N 'di- 2- (2', 2 ', 6 6'-tetramethylpiperidinyl-4') -ethyl] -thiodipropionamide, bp. 280 "C / 0, 6 mm Hg.



  Elemental Analysis: C28Hs4N402S Calculated: C 65.84% H 10.66% N 10.97% Found: 66.09 10.51 10.85
Example 37
A solution of 9.9 parts by weight of 2- (1, 2 ', 2', 6 ', 6'-pentamethylpiperidinyl-4') ethylamine in 50 parts by volume of cyclohexane was added dropwise to a solution of 7.7 parts by weight Phenylacetyl chloride in 100 parts by volume of cyclohexane was added in the course of 30 minutes. The resulting suspension was heated to reflux for 2 hours and worked up as described in Example 9, N-12- (1 ', 2, 2', 6 ', 6'-pentamethylpiperidinyl-4') -ethyl] -phenylacetamide, bp .



  185 to 188 C / 0.3 mm Hg.



  Elemental Analysis: C20H32N2O Calculated: C 75.90% H 10.19% N 8.85% Found: 75.78 10.07 8.79
Example 38
A solution of 9.9 parts by weight of 2- (1: 2 2 6 ', 6'-pentamethylpiperidinyl-4') ethylamine in 50 parts by volume of cyclohexane was added dropwise to a solution of 5.3 parts by weight of isobutyryl chloride in 100 Parts by volume of cyclohexane are added. The suspension was heated to reflux for 2 hours and worked up as described in Example 9, giving the N- [2 (1 2 ', 2 6', 6'-pentamethylpiperidinyl-4 ') ethyl] isobutyramide, bp 150 up to 155 C / 0.2 mm.



  Elemental Analysis: C16H32N2O Calculated: C 71.59% N 12.02% N 10.44% Found: 71.77 11.72 10.22
Example 39
A solution of 6.1 parts by weight of fumaric chloride in 50 parts by volume of cyclohexane was added dropwise to a solution of 15.8 parts by weight of 2- (1 ', 2', 2 ', 6', 6'-pentamethylpiperidinyl-4 ') - Given ethylamine in 100 parts by volume of cyclohexane in the course of 30 minutes at room temperature. The resulting solid was collected by filtration and dissolved in 500 parts by volume of water. 40% strength sodium hydroxide solution was added to the solution until it had an alkaline reaction. The precipitate was collected by filtration and purified by recrystallization from ethyl acetate to give the N, N'-di [2- (1 2 2 6 ', 6'-pentamethylpiperidinyl-4') ethyl] fumaramide, m.p. up to 253 C.



  Elemental Analysis: Q8H52N4O2 Calculated: C 70.54% H 10.99% N 11.75% Found: 70.72 10.89 11.46
Example 40
A solution of 9.9 parts by weight of 2- (1 ', 2', 2 ', 6', 6'-pentamethylpiperidinyl-4 ') ethylamine and 6.7 parts by weight of n-hexyl isocyanate in 100 parts by volume of petroleum ether ( Boiling range 60 to 80 ° C) was refluxed for 24 hours. The solvent was removed by evaporation under reduced pressure and the remaining oil was distilled, whereby 8.0 parts by weight (50% of theory) N- (n-hexyl ) -N'- [2 (1 ', 2', 2 ', 6', 6'-pentamethylpiperidinyl-4 ') -ethyl] -urea, b.p. 198-204 C / 0.2 mm Hg.

 

  Elemental Analysis: Ct9H39NsO Calculated: C 70.10% H 12.08% N 12.91% Found: 70.60 12.08 12.81
Example 41
A solution of 9.9 parts by weight of 2- (1 2 ', 2: 6', 6'-pentamethylpiperidinyl-4 ') ethylamine and 14.8 parts by weight of n-octadecyl isocyanate in 150 parts by volume of cyclohexane was 48 hours heated to reflux. The solvent was removed by distillation and the remaining solid was recrystallized from methyl alcohol, 13.2 parts by weight (51% of theory) of N- (n-octadecyl) -N'- [2 (1 ', 2', 2 ', 6', 6'-pentamethylpiperidinyl-4 ') -ethyl] urea obtained, m.p. 67 to 69 "C.



  Elemental Analysis: C31H63N3O Calculated: 75.39% H 12.86% N 8.51% Found: 75.61 12.48 8.25
Example 42 Ethylene oxide gas was passed through a stirred solution of 19.8 parts by weight of 2- (1 ', 2', 2 ', 6', 6'-pentamethylpiperidinyl-4) ethylamine in 100 parts by volume of water at 10 to 15 " until 4.4 parts by weight were absorbed. The resulting solution was distilled, whereby N- (2 "-hydroxyethyl) - [2 (1 ', 2', 2 ', 6', 6 '- pentamethylpiperidinyl-4 9] - ethylamine, bp 168 to 172 "C / 1.5 mm Hg.



  Elemental Analysis: C14H30N2O Calculated: C 69.37% H 12.47% N 11.56% Found: 69.36 12.36 11.39
Example 43 Ethylene oxide gas was passed through a stirred solution of 18.4 parts by weight of 2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4,) - ethylamine in 100 parts by volume of water at 15 to 20 to a total of 15 parts by weight was absorbed. The resulting solution was distilled, 15 parts by weight (55% of theory) of N, N-di (2 "-hydroxyethyl) - [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4 ')] - ethylamine, b.p. 160 to 162 "C / 0.2 mm Hg.



  Elemental Analysis: C15H32N2O2 Calculated: C 66.13% H 11.84% N 10.28% Found: 65.90 11.62 9.99
Example 44 Ethylene oxide gas was passed through a solution of 19.8 parts by weight of 2- (1 ', 2', 2 ', 6', 6'-pentamethylpiperidinyl-4 ') ethylamine in 100 parts by volume of water at 25 ° C until 9.0 parts by weight had been absorbed. The solution was distilled using N, N-di- (2 "-hydroxyethyl) - [2- (1 ', 2', 2 ', 6', 6'- Pentamethyl piperidinyl-4 ') j-ethylamine received, bp 158 to 162 "C.



  Elemental Analysis: Ca6H34N202 Calculated: C 67.09% H 11.96% N 9.78% Found: 67.32 11.83 9.85
Example 45
14.4 parts by weight of ethyl chloroformate were added to a stirred mixture of 22.0 parts by weight of 2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethylamine, 5.0 parts by weight of potassium carbonate, 30 parts by volume of water and 10 parts by volume of cyclohexane are added at 15 to 20 ° C. in the course of 20 minutes. The suspension was stirred at room temperature for 1 hour and then extracted with ether (6 × 25 parts by volume). The ether extracts were combined, dried over magnesium sulfate and evaporated under reduced pressure. The remaining oil was purified by distillation, ethyl (2,2,6,6-tetramethylpiperidinyl-4) carbamate, bp.



     115 C / 0.5 mm Hg.



  Elemental Analysis: Ct4H28N202 Calculated: C 65.59% H 11.01% N 10.93% Found: 65.29 10.76 10.74
Example 46
19.8 parts by weight of 2- (1 ', 2', 2 ', 6', 6 '- pentamethylpiperidinyl4') - ethylamine were added dropwise over 10 minutes to a stirred mixture of 4.8 parts by weight of carbon disulfide and 13 Given parts by volume of water. The resulting suspension was stirred for a further 2 hours at room temperature. 4.5 parts by weight of 50% sodium hydroxide solution was then added and the suspension was heated to reflux for 3 hours.



   After cooling, the solid was collected by filtration and extracted with boiling ethyl alcohol (500 parts by volume). The ethyl alcohol extract was evaporated under reduced pressure and the remaining oil was treated with water, whereby the N, N'-bis- [2- (1 ', 2', 2 ', 6', 6'-pentamethylpiperidinyl-4 ') - ethyl] thiourea obtained as a monohydrate, melting point 118 to 1200 C.



  Elemental Analysis: C25H52N4OS Calculated: C 65.75% H 11.45% N 12.27% Found: 65.88 10.98 12.0
Example 47
A solution of 35.6 parts by weight of (2,2,6,6-tetramethylpiperidinylidene-4) acetonitrile (see Example 1) and 17.1 parts by weight of benzyl bromide in 100 parts by volume of toluene was refluxed for 48 hours . The resulting precipitate was removed by filtration and the solution was evaporated under reduced pressure. The oil that remained was purified by distillation (boiling point 160 to 164 "C / 0.7 mm Hg), dissolved in 60 parts by volume of methyl alcohol saturated with ammonia and hydrogenated at room temperature and a pressure of 20 atm. Hydrogen over a Raney nickel catalyst .



   After removal of the catalyst by filtration and removal of the solvent by evaporation under reduced pressure, the remaining oil was distilled to give 2- (1'-benzyl-2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethylamine obtained, Kr. 1650 C / 0.2 mm Hg.



  Elemental Analysis: C18H30N2 Calculated: C 78.78% H 11.02% N 10.21% Found: 78.53 10.82 9.76
Example 48
A solution of 17.8 parts by weight of (2,2,6,6-tetramethylpiperidinylidene-4) acetonitrile (see Example 1) and 50 parts by volume of styrene oxide in 50 parts by volume of n-hexanol was refluxed for 48 hours , then distilled to obtain a fraction with a boiling point of 210 to 215 C / 0.6 mm Hg. This fraction was hydrogenated at 100 ° C./100 atm. Hydrogen over Raney nickel in 100 parts by volume of saturated methyl alcohol / ammonia solution.



   The product was isolated as described in Example 47, giving [1- (2'-hydroxy-2'-phenylethyl) -2,2,6,6-tetramethylpiperidinyl-4] ethylamine, Kr 1850 C / 0.3 mm.



  Elemental Analysis: C19H, 2N2O Calculated: C 74.95% H 10.59% N 8.74% Found: 74.59 10.41 8.39
Example 49
A solution of 11.3 parts by weight of N-acetyl [2- (2 ', 2', 6 ', 6'tetramethylpiperidinyl-4')] ethylamine (see Example 9) and 3 parts by weight of allyl bromide in 100 Parts by volume of toluene were refluxed for 16 hours. The resulting solid was removed by filtration and the toluene was evaporated under reduced pressure. The remaining oil was distilled to give N-acetyl [2- (1 '-allyl-2', 2 ', 6', 6 'tetramethylpiperidinyl-4')] ethylamine, bp 161-162 "C / 0.4 mm Hg.



  Elemental Analysis: C16H30N2O Calculated: C 72.13% H 11.35% N 10.51% Found: 72.10 11.15 10.53
Example 50
9.2 parts by weight of 2- (2 2 6 6'-tetramethylpiperidinyl-49-ethylamine were added dropwise to a solution of 9.5 parts by weight of p-toluenesulfonyl chloride in 100 parts by volume of benzene. The suspension was refluxed for 2 hours heated, cooled and the solid was collected by filtration. Recrystallization from water gave 12.0 parts by weight (64% of theory) N- [2 '- (2', 2 ', 6', 6'-tetramethylpiperidinyl4 ') - ethyl] toluene-4-sulfonamide hydrochloride, melting point 258 to 265 ° C. (decomposition).



  Elemental Analysis: C18H31ClN2O2S Calculated: C 57.60% H 8.27% N 7.47% S 8.54% Found: 57.99 8.23 7.63 8.47
Example 51
4.0 parts by weight of sodium hydride (60% in oil) and 15.5 parts by weight of 2,2,6,6-tetramethylpiperidin-4-one in 125 parts by volume of cyclohexane (dry) were stirred together at room temperature. 23.3 parts by weight of (<r-n-butyl) diethylphosphonoacetonitrile in 25 parts by volume of cyclohexane were added to this mixture in the course of 30 minutes. The suspension was stirred at room temperature for 1 hour, then refluxed for 2 hours, and then 100 parts by volume of water were added to the cooled suspension. The cyclohexane was separated off, dried over magnesium sulphate and evaporated under reduced pressure.

  The oil that remained was distilled, 9.7 parts by weight (40% of the theoretical yield) of butyl- (2,2,6,6-tetramethylpiperidinyl-4) acetonitrile, boiling point 150 to 154 "C / 12 mm Hg identified by PMR spectroscopy.



   This product was then hydrogenated at 100 ° C. / 100 atm. Hydrogen over a Raney nickel catalyst in 100 parts by volume of saturated methyl alcohol / ammonia solution. The product was isolated as described in Example 47, giving 2- (n-butyl) -2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethylamine, bp 104 C / 0 , 3 mm Hg.



  Elemental Analysis: C15H32N2 Calculated: C 74.93% H 13.42% N 11.65% Found: 74.37 13.00 12.45
Example 52
A solution of 9.25 parts by weight of 2- (2 ', 2, 6', 6'-tetramethylpiperidinyl-4 ') ethyl alcohol and 6.6 parts by weight of phenyl isocyanate in 100 parts by volume of petroleum ether (boiling range 60 to 80 ° C ) was heated to reflux for 24 hours, the solvent was removed by evaporation under reduced pressure and the residue was recrystallized from petroleum ether (boiling range 60 to 80 ° C.), 8.3 parts by weight (55% of theory) N-phenyl - [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') -ethyl] urethane obtained, m.p. 91 to 92 "C.



  Elemental Analysis: C18H28N202 Calculated: C 70.54% H 11.53% N 12.99% Found: 70.79 11.67 12.70
Example 53
A solution of 7.4 parts by weight of 2- (2 ', 2 6', 6'-tetramethylpiperidinyl-4 ') ethyl alcohol and 2.3 parts by weight of methyl isocyanate in 100 parts by volume of cyclohexane was refluxed for 24 hours. The solvent was removed by evaporation under reduced pressure and the remaining oil was distilled, whereby 4.9 parts by weight (51% of theory) N-methyl- [2- (2 ', 2', 6 ', 6'- tetramethylpiperidinyl-4 ') ethyl] urethane obtained, boiling point 124 to 128 C / 0.5 mm Hg.



  Elemental Analysis: C13H26N202 Calculated: C 64.43% H 10.81% N 11.56% Found: 64.66 10.70 11.32
Example 54
A solution of 9.3 parts by weight of 2- (2 2 6 = 6 'tetramethylpiperidinyl-4') ethyl alcohol and 6.2 parts by weight of cyclohexyl isocyanate was refluxed for 24 hours. The product was isolated as described in Example 53, 9.8 parts by weight (63% of theory) of N-cyclohexyl [2 (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethyl ] urethane, bp 186 to 1900 C / 2.0 mm Hg.



  Elemental Analysis: Cl8H34N202 Calculated: C 69.63% H 11.04% N 9.02% Found: 69.73 11.39 8.86
Example 55
A solution of 9.3 parts by weight of 2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethyl alcohol and 3.3 parts by weight of hexamethyl diisocyanate in 100 parts by volume of cyclohexane was refluxed for 24 hours heated and worked up as described in Example 53, using N, N'-di- [2 '- (2 ", 2", 6 ", 6" - tetramethylpiperidinyl-4 ") - ethyloxycarbonyl] - hexane-1,6- diamine, b.p. 270 C / 0.5 mm Hg.



  Elemental Analysis: C30H58N404 Calculated: C 66.87% H 10.85% N 10.40% Found: 67.05 10.68 10.65
Example 56
A solution of 7.4 parts by weight of 2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethyl alcohol, 8.0 parts by weight of dodecanecarboxylic acid and 0.5 parts by weight of tetra (b -butyl) -titanate in 150 parts by volume of xylene was refluxed for 6 hours. The water from the distillation was collected in a Dean and Stark apparatus. The xylene solution was then cooled and washed with sodium carbonate solution and dried over magnesium sulfate. The xylene was evaporated under reduced pressure at 100 "C and the remaining oil was purified by distillation, whereby [2- (2: 2 = 6 = 6 'tetramethylpiperidinyl-4') ethyl] dodecanoate was obtained, bp 2000 C / 0.5 mm Hg.

 

  Elemental Analysis: C33H45NO2 Calculated: C 75.15% H 12.23% N 3.81% Found: 75.07 12.06 3.61
Example 57
1.6 parts by weight of sodium hydride (60% in oil) were added to a solution of 7.4 parts by weight of 2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethyl alcohol in 100 vol. Parts of toluene given. The resulting suspension was heated to reflux for 24 hours. 7.7 parts by weight of n-bromooctane were then added and then refluxed for a further 24 hours.



   The solid precipitate was removed by filtration and the toluene was evaporated under reduced pressure to leave a residue of the oil, which was purified by distillation to give 5.6 parts by weight (50% of theory) (n-octyl) - [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4) -ethyl] - ether obtained, b.p. 200 C / 0.5 mm Hg.



  Elemental analysis: C19H39NO
Calculated: C 76.70% H 13.21% N 4.71%
Found: 76.78 13.23 4.58
Example 58
A mixture of 11.4 parts by weight of ethyl (2,2,6,6-tetramethylpiperidinyl-4) acetate, 9.3 parts by weight of 2- (2 2 6 6'-tetramethylpiperidinyl-4 ') ethyl alcohol and 0.5 parts by weight of lithium amide was heated at 1800 C for 1 hour, during which time the ethyl alcohol could distill off from the reac tion container. The suspension was then cooled and poured into water. The resulting oil was extracted with ether (3 x 50 parts by volume). The combined ether extracts were dried over magnesium sulphate and the ether was evaporated under reduced pressure.

  Distillation of the remaining oil gave 8.3 parts by weight [2 (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') - ethyl] - (2 ", 2", 6 ", 6" - tetramethylpiperidinyl- 4 ") acetate, bp 180 to 181" C / 0.9 mm
Ed.



   Elemental Analysis: C22H42N202 Calculated: C 72.08% H 11.55% N 7.64% Found: 71.51 11.45 7.52
Example 59
A solution of 9.9 parts by weight of 2- (1 ', 2', 2 ', 6', 6'-pentamethylpiperidinyl-4 ') - ethylamine in 75 parts by volume of cyclohexane was added dropwise to a solution of 5.2 .Parts of cortonyl chloride in 75 parts by volume of cyclohexane. The suspension was then refluxed for 1 hour and worked up as described in Example 9, N cortyl- [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') j-ethylamine, bp. 160 to 163 C / 0.25 mm Hg, m.p. 79 to 81 "C.



  Elemental Analysis: C16H30N2O Calculated: C 72.13% H 11.35% N 10.51% Found: 72.63 11.30 10.82
Examples 60 to 62
The procedure of Examples 19 to 28 was repeated except that high-density polyethylene was used as the substrate, kneading was carried out at 1800 C for 10 minutes, and the homogenized material was pressurized into films having a thickness of 0.110 mm using a temperature deformed at 210 C for 6 minutes.



   The pressure formed films to be tested were then placed in a Xenotest 150 apparatus and the time required for the carbonyl content of the sample to increase to 0.1% by weight was determined and noted.



   The results obtained are shown in Table II below: Example: Light stabilizer Time until d. Carbonyl content 0.1% was comparison 0.5% N-octadecyl-3- [3,5-di-t-butyl-4-hydroxyphenyl] propionate 700 60 0.5% N-octadecyl-3- [3,5 -di-t-butyl-4-hydroxyphenyl] propionate +> 2000
0.25% N-phenyl-N'- [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethyl] urea 61 0.05% N-octadecyl-3- [3, 5-di-t-butyl-4-hydroxyphenyl] propionate +> 2000 0.25% N- (n-octanoyl) -2- (2 ', 2', 6 ', 6'-tetramethylpiperidine-4) ethylamine 62 0.05% N-octadecyl 3- [3,5-di-t-butyl-4-hydroxyphenyl] propionate + 1300 0.25% 2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl -4 ') - ethylamine
Examples 63 to 65
100 parts of crystalline polystyrene pellets were dry with 0.25 parts

   of the light stabilizer to be tested, and the dry mixture was homogenized by extrusion. The stabilized pellets thus obtained were molded into plates 1.5 mm thick by injection molding.



  These plates were irradiated for 3000 hours in a Xenotest 150 exposure unit and the yellowing of the plates was measured by determining the yellow factor according to the following equation: #T (420) - #T (680)
Yellow factor = x 100
T (560) where the A T values mean the loss of transmission of the sample at wavelengths of 420 mm and 680 mm after exposure in the xenotest unit and T (560> the transmission value of an unexposed sample at a wavelength of 560 mm.



   The results obtained in this way, as well as the results obtained in a comparative experiment and in the case of other compositions according to the invention, are listed in Table III below.



  Table III Example of light stabilizer yellow factor after 2000 h - none 20.2 63 N-phenyl-N'- [2- (2 "2" 6 "6'-tetramethylpiperidinyl-4 ') - ethyl] urea 9.1 64 N- (n-octanoyl) -2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') -ethylamine 7.9 65 2- (2 ', 2 "6" 6'-tetramethylpiperidinyl-4') - ethylamine 8.9
Examples 66 to 68
25 parts by weight of a film-forming polyester-based polyurethane are dissolved in 75 parts by weight of a 1: 1 mixture (volume) of dimethylformamide and acetone. 1% by weight of light stabilizer is added to the solution.



   The clear and homogeneous solution is poured onto a glass plate to form a film with a thickness of 400 to 500 ij and then dried as follows: at 500 C for 4 minutes at 140 C for 6 minutes
The final thickness of the film is 80 to 100.



   The dried film samples are removed from the glass plate, glued to white cardboard and exposed in a Xenotest 450 exposure unit, half of the exposed sample being covered in order to facilitate the subsequent visual determination of yellowing caused by exposure. The sample was checked and visually assessed at intervals of 100 hours.



   The results obtained are shown in the following Table IV, which also gives the results of a comparative experiment (in which no light stabilizer was added) and which also shows the results of others
Experiments are listed in which inventive
Stabilizers were used.



  Table IV Example of light stabilizer Time to pronounced yellowing unprocessed pigmented - none 200 200 66 N-phenyl-N'- [2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4,) - 1000 800 ethyl] -urea 67 N- (n-octanoyl) -2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') - 800 800 ethylamine 68 2- (2 ', 2', 6 ', 6' - Tetramethylpiperidinyl-4 ') -ethylamine 600 600
Example 69
A solution of 4.0 parts by weight of 2- (1 ', 2', 2 ', 6', 6 'Pentamethylpiperidinyl-4') - ethylamine and 3.7 parts by weight of 1 naphthyl isothiocyanate in 50 parts by volume of cyclohexane was 24 Heated at reflux for hours.

  The cyclohexane was removed by distillation and the residue was recrystallized from petroleum ether (boiling range 60 to 80 "C), whereby (1 ', 2', 2 ', 6', 6'-pentamethylpiperidinyl-49-ethyl] -N'- (1'naphthyl) thiourea obtained, m.p. 107-109.



  Elemental Analysis: C23H33N3S Calculated: C 72.10% H 8.63% N 10.96% Found: 71.82 8.77 14.47
Example 70
24.9 parts by weight of n-dodecyl bromide and 36.5 parts by weight (2,2,6,6-tetramethylpiperidinylidene-4) acetonitrile were heated together at 140 ° C. for 6 days. The solid precipitate was removed by filtration and the liquid was distilled to give 10.5 parts by weight of [1- (n-dodecyl) -2,2,6,6-tetramethylpiperidinylidene-4] acetonitrile, b.p. 200 bis 205 "C / 0.6 mm. This compound was hydrogenated and worked up as described in Example 47, the 2- [1 '- (n-dodecyl) - 2', 2 ', 6 = 6'-tetramethylpiperidinyl-4 ') - ethylamine received, bp 190 to 195 C / 0.2 mm Hg.

 

  Elemental Analysis: C23H48N2 Calculated C 78.34% H 13.72% N 7.94% Found: 79.45 13.89 7.57
Example 71
A mixture of 40 parts by volume of acrylonitrile and 9.2 parts by weight of 2- (2 ', 2', 6 ', 6'-tetramethylpiperidinyl-4') ethylamine was refluxed for 18 hours. The solution was then distilled, 8 parts by weight (67% of theory) N- (2 "-Cyanoethyl) -2- [(2 ', 2', 6 ', 6'-tetramethyl piperidinyl-4') - ethylamine], bp 128 to 1300 C.



  Elemental Analysis: Cl4H27N3 Calculated: C 70.83% H 11.46% N 17.70% Found: 70.80 11.37 17.50.

 

Claims (1)

PATENT CLAIM Stabilized organic material containing a compound of the formula I as a stabilizing component EMI16.1 or a salt thereof, in which m is 0 or 1 and n is 1 or 2, R, and R2 are identical or different and each represent a straight-chain or branched alkyl group with 1 to 12 carbon atoms or R1 and R2 together with the ring carbon atoms to which they are bonded form a cycloalkyl group with 5 to 12 carbon atoms, R> hydrogen, a straight-chain or branched alkyl group with 1 to 12 carbon atoms, an aralkyl group with 7 to 12 carbon atoms or a cycloalkyl group with 5 or 6 carbon atoms, EMI16.2 <tb> <SEP> R4 <tb> <SEP> I <tb> A-0- <SEP> or-N- <SEP> means <tb> in which R4 hydrogen, a straight-chain or branched alkyl group with 1 to 12 carbon atoms, which is either unsubstituted or substituted by halogen, cyano or hydroxy, or which is interrupted by one or more oxygen or sulfur atoms, an aralkyl group with 7 to 12 carbon atoms, an alkenyl group with 3 to 12 carbon atoms or a cycloalkyl group with 5 to 12 carbon atoms, R5 is hydrogen, a mono- or divalent hydrocarbon group with 1 to 20 carbon atoms, which is either unsubstituted or substituted by halogen, cyano- or hydroxyl, or which is interrupted by one or more oxygen or Sulfur atoms, or in which Rs is a group of the formula EMI16.3 means, wherein p means 0, 1 or 2, R1 and R2 have their previously given meanings, and Y is hydrogen, an alkyl group with 1 to 20 carbon atoms, an alkenyl or alkynyl group with 3 to 12 carbon atoms, an aralkyl group with 7 to 13 carbon atoms or a group CH2CH (OH) R8, in which R8 denotes hydrogen, phenyl or an alkyl group with 1 to Represents 4 carbon atoms, and when A represents -0- represents, EMI16.4 and, if A> N-R4 means, EMI16.5 EMI16.6 or, if n is 1 and Rs has the meaning given for formula II, in which p is 2, is a -SO2NH- group, with the proviso that, if A is-0-, R5 is not hydrogen, and A> NR4, m 1, n 2 and EMI16.7 EMI16.8 <tb> -C- <SEP> mean <tb> <SEP> s <tb> R5 can be absent. SUBCLAIMS 1. Material according to claim, containing a compound of the formula I, wherein n 1 and R5 are hydrogen, a monovalent straight-chain or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms, which is either saturated or unsaturated and either unsubstituted or substituted by halogen, cyano or Hydroxyl groups or which is interrupted by one or more oxygen or sulfur atoms, an unsubstituted alicyclic hydrocarbon group with 5 to 20 carbon atoms, an aralkyl group with 7 to 12 carbon atoms, an aryl group with 6 to 15 carbon atoms or the group EMI16.9 means in which R 1, R 2, Y and p have the meanings given in the patent claim. 2. Material according to claim, containing a compound of the formula I in which n is 2 and Rs is a divalent straight-chain or branched aliphatic hydrocarbon group with 2 to 20 carbon atoms, an unsubstituted divalent alicyclic hydrocarbon group with 5 to 12 carbon atoms, a divalent aralkyl group with 8 to 12 Is carbon atoms or a divalent aryl group having 6 to 15 carbon atoms, it being possible for R5 to be absent when m is 1, X is C- or -C- and A> N-R4. 3. Material according to claim, containing a compound of the formula I, wherein Y is hydrogen or a methyl group. 4. Material according to claim, containing a compound of the formula I in which Rt and R2 each represent a methyl group. 5. Material according to claim, containing a compound of the formula I in which R3 is hydrogen. 6. Material according to claim, containing a compound of the formula I in which R4 is hydrogen or an alkyl substituent having 1 to 8 carbon atoms. 7. Material according to claim, containing a compound of the formula I wherein X is the group. EMI17.1 8. Material according to claim, containing a compound of formula I, wherein EMI17.2 and, when n is 1, A> NR4 and R5 is a group of the formula II as defined in the claim, in which p is 2. 9. Material according to claim, containing a compound of the formula I in the form of a phosphate, carbonate, sulfate, chloride, acetate, stearate, maleate, citrate, tartrate, oxalate, benzoate, or a salt with a substituted carbamic acid. 10. Material according to claim, characterized in that it contains a polymer, in particular a polyolefin, as the organic material. 11. Material according to patent claim, characterized in that it contains a low- or high-density polyethylene, polypropylene or polystyrene. 12. Material according to claim, characterized in that it contains a binary, tertiary or multi-component composition in which a compound of the formula I, as defined in the claim, is contained as a stabilizer together with one or more functional additives for polymers.