DE2146692A1 - Acylhydrazones of 2,2,6,6-tetramethylpiperidin-4-one - Google Patents

Description

Acylhydrazones of L, 2,6,6-tetramethylpiperidin-4-one

The present invention relates to a new class of acylhydrazone derivatives of 2,2,6,6-tetramethylipieridin-4 - one, the represent valuable stabilizers for organic materials.

The present invention relates more particularly to compounds of the general types Formula I.

CIL

C -

I IN

_v _

/ CH, CII, *

CIL

CIL

C = N.NH C H

(D

and their acid salts, in which E is hydrogen, a straight-chain or branched alkyl radical having 1 to 20, preferably 1 to 17 and most preferably Λ to 12 carbon atoms, the Al-

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ORIGINAL INSPECTED

2H6692

alkyl chain through one or more, preferably 1, sulfur atom can be interrupted, a cycloalkyl radical having 5 to 12, preferably 6 carbon atoms, a cycloalkylalkyl radical with up to 12, preferably 7 to 11 carbon atoms, a phenyl radical, a naphthyl radical, an aralkyl radical with 7 to 14, preferably 7 Ms 11 carbon atoms or an alkaryl radical, preferably an alkylphenyl radical with 7 to 14, preferably up to 10 carbon atoms, or in which R is a group of the formula II

- · CH 0 CII ₀ C ^ *

ι, ti / ² ^

- (Y) -CNlLN = C NlI

ClI C ^

² / cn,

ClL ^?

represents wherein Y is divalent, straight-chain or branched Alkylene radical having 1 to 20, preferably 1 to 10, most preferably 4 to 10 carbon atoms, the alkylene chain can be interrupted by one or more, preferably one, sulfur atom, or an arylene radical with 6 to 12, preferably 6 is carbon atoms, and a is 0 or preferably 1, or R is a group of the formula III

CII,

- NlLN = C NlI

CH ₂ -

means.

Examples of the present invention to use salts of piperidine derivatives of general formula I are salts with anorgani rule acids, such as phosphates, carbonates, sulfates and _chlorides%

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the like as well as salts with organic acids such as citrates, acetates, stearates, maleates, oxalates and benzoates.

Examples of monovalent groups E are methyl, ethyl, n-propyl, isopropyl, η-butyl, tert-butyl, n-amyl, 2-ethylpropyl, n-hexyl, n-heptyl , n-octyl, n-undecyl, n-dodecyl, n-heptadecyl, n-octadecyl, eicosyl, ß-hercaptoethyl, mercaptomethyl, ß-methylthioethyl, ß-octylthioethyl, α- and ß-Dodecylthioethyl, cyclopentyl, cyclohexyl, methylcyclohexyl, 4-tert-butylcyclohexyl, cyclododecyl, adamantyl, 1- and 2-perhydronaphthyl, cyclopentylmethyl, cyclohexylmethyl, ß-cyclohexylethyl 2- (perhydronaphthyl) -methyl-, ß- [i- and 2-perhydronaphthyl] -ethyl-, benzyl-, ß-phenylethyl-, 1- and 2-naphthylmethyl-, ß- [1- and 2-naphthyl] - ethyl-, diphenylmethyl-, o-, m- and p-tolyl-, o _T) ffi- and p-ethylphenyl-, o-, m- and p-isopropylphenyl-, o-, m- and p-tert.- Butylphenyl-, 4-methj-1-Ί-naphthyl-, 4-ethyl-1-naphthyl-, 4-1 sopropyl-1-naphthyl- and 4-tert. -Butyl-1 -naphthyl groups.

Examples of groups T are methylene, 1,2-ethylene, 1,4-n-butylene, 1,8-n-octylene, 1,10-n-decylene, 1,2-eico sylene, 1,2-, 1,3- and 1,4-phenylene, 1,4- and 1,5-naphthylene, 4,4'-diphenylene groups and the group of the formula

Preferred groups for the substituent / are hydrogen, methyl, Isopropyl, 3-methylbutyl, n-hexyl, 2-ethylpentyl, n-undecyl-, n-heptadecyl-, phenyl-, p-tolyl-, p-tert-butylphenyl-, Benzyl, diphenylmethyl, a-haphthyl, a-raphthylmethyl, Cyclohexyl groups and one of the groups of the following formulas:

- ^CI! 3

j- C- * TI.K = C. HH

6 CH, -C

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- (CH ₂ ) g-C -NH.N = C

Λ / cn

CH ₂ -. C _x

NH

CH

(CH ₀ ) -C NH.N = C

ch ₂

NH

CH _n

C-NILN = C O

CH ₂ -C

NH

^CH 3

CH ₀ CII ₀ SCH ₀ CH ₀ - C-NILN = C

²²²² p

* f \ * f __ f% r

NH

CIL · - C

CIL

For reasons of compatibility, however, are used for stabilization of polyolefins compounds of the formula I are particularly preferred,

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• 2U6692 ' - 5 -

which have a high ratio of organophilic radical to secondary amine function.

Examples of preferred compounds of the general formula I are:

Di- (2,2,6, e-tetramethylpiperidinyl - ^ -) -adipoyl-di-hydrazone, Di- (2,2,6,6-tetramethylpiperidinyl) -4) -sebacoyl-di-hydrazone, Di- (2,2,6, ö-tetramethylpiperidinyl-O -thiodipropionyl-di-hydrazone, 2,2,6, G-tetramethylpiperidinyl - ^ - isocaproyl-hydrazone, 2,2,6,6-tetramethylpiperidinyl-4-heptanoylhydrazone, 2,2,6,6- (detramethylpiperidinyl-4-lauroylhydrazone, 2,2,6,6-Tetramethylpiperidinyl-4-ste aroylhydrazone, 2,2,6,6-tetramethylpiperidinyl-4-isobutyroylhydrazone, 2,2,6, ö-tetramethylpiperidinyl ^ -benzoylhydrazone, 2,2,6,6-tetramethylpiperidinyl-4-p-toluoylhydrazone, 2,2,6,6-tetramethylpiperidinyl-4-a-naphthoylhydrazone, 2,2,6,6-tetramethylpiperidinyl-4-phenylacetylhydrazone, 2,2,6,6-Tetramethylpiperidinyl - ^ - a-naphthylacetyl-hydrazone, .2,2,6,6-Tetramethylpiperidinyl-4-α, (x-diphenylacetylhydrazone, 2,2,6,6-tetramethylpiperidinyl-4-cyclohexane-carboxyl-hydrazone, Di- (2,2,6,6-tetramethylpiperidinyl-4) -isophthaloyl-dihydrazone, di- (2,2,6,6-tetramethylpiperidinyl-4) -dodecane-1: 10-dioyl-dihydrazone,

2,2,6,6-tetramethylpiperidinyl-4-p-tert-butylbenzoyl hydrazone and 2,2,6,6-tetramethylpiperidinyl-4-2'-äthylhexanoyl hydrazone as well as the corresponding ze Säuresal.

The present invention also relates to a process for preparing the compounds of the general formula I, which is characterized in that an acid monohydrazide of the general formula IV

RC-HH NH _{2 (IV)}

or an acid dihydrazide of the general formula V

H ₀ N-HN-C- (Y) -C-NH-NH ₀ (V)

0 0

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2U6692

wherein R and Y have the meanings given above, with triacetonamine of the formula VI

CH

\ / ^CH 3

C CH ₀

HN C = O (VI)

CH ₃

implements.

The reaction is conveniently carried out by heating the reactants in a solvent which is inert for the reactants, e.g. in an aliphatic alcohol, an ether or an aromatic hydrocarbon, especially in methanol or ethanol, dietary ether or toluene. Advantageously the reaction is carried out at the reflux temperature of the mixture using essentially equimolar ratios of reactants carried out. After the reaction has ended, the solid product can be isolated and, if desired, in a customary manner getting cleaned.

The present invention further relates to compositions which an organic material and a small proportion of a compound of general formula I contain.

It has been found that the compounds of general formula I impart exceptional stability to polyolefins with respect to the decomposition which normally occurs as a result of ultraviolet rays. This light stability is also achieved without impairing the color properties of the treated polyolefin. The stabilizers according to the invention give in particular low and high density polyethylene and polypropylene and polystyrene as well as polymers of 1-butene, 1-pentene, 3-methyl -1-butene, 1-hexene, 4-methylpentene-1, 4-methylhexene-1 and 4,4-dimethylpentene-1 as well as mixed and ter-polymers of olefin

209813/1824

nen, especially of ethylene or propylene, an effective stabilization against the effects of light and / or heat. The compounds of general formula I are for stabilization Polystyrene is particularly suitable against actinic radiation.

Other organic materials subject to decomposition by light and their properties due to the incorporation of a Compounds of general formula I include natural and synthetic polymeric materials, e.g., natural and synthetic rubbers, the latter e.g. homo-, mixed- and per-polymers of acrylonitrile, butadiene and styrene lock in.

Examples of synthetic polymers are polyvinyl chloride and vinyl chloride copolymers, as well as polyvinyl acetate Condensation polymers, which differ from ether, ester (such as carboxylic acid ester, sulfonic acid ester or carbonic acid ester) Derive amide or urethane groups. These polymers can e.g. represent the basis of a surface coating material, such as a basis for a paint or a varnish, which are based on an oil or a resin, e.g. an alkyd resin or a polyamide resin.

The amount of the compound of the general formula I, which is in the organic material is incorporated in order to achieve maximum protection against decomposition by light varies depending on the properties of the organic material to be treated, depending on the severity of the Light radiation and the duration of the irradiation. However, for most purposes it is sufficient to make a lot of the compound of the to use general formula I, which are in the range from 0.01 to 5% by weight, preferably in the range from 0.1 to 2% by weight on the weight of the untreated organic material.

In addition, the compositions according to the invention can contain further additives, in particular those used in polyolefin formulations used, such as antioxidants, other light

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Stabilizers, metal complexing agents, metal deactivators, pigments, anti! Lubricants and antistatic agents, fillers, Dyes and glass or other fibers.

The compounds of general formula I can with the help of any one known method for compounding additives be incorporated into the polymeric material with a polymer. For example, the compounds ^ id of the general formula I and the polymer can be compounded in an internal mixer. Alternatively, the compound of general formula I can be in the form a solution or a slurry in a suitable solvent or dispersants, for example in an inert organic solvent such as methanol, ethanol or acetone, to the powdered polymer are given, whereupon the whole thing is intimately mixed in a mixer and the solvent removed. As a further alternative, the compound of general formula I can be used during the preparation of the polymer, e.g. in the latex stage of polymer production, are added to the polymer, so that a pre-stabilized polymer material receives.

Examples of suitable antioxidants are the sterically hindered phenols, such as 2,6-di-tert-butyl-p-cresol, 4,4 -'-bis- (2,6-di-tert-butylphenol), 4,4'-bis - (2,6-di-isopropylphenol), 2,4,6-triisopropylphenol and 2,2'-thio-bis- (4-methyl-6-tert-butylphenol); Tetrakis-C-methylene-SO ', 5'-dibutyl-4 ( ^1- hydroxy-phenyl) propionate] methane; Esters of thiodipropionic acid, for example dilauryl thiodipropionate; Alkyl, aryl or alkaryl phosphites such as triphenyl phosphite, trinonyl phosphite and diphenyl decyl phosphite and combinations of these antioxidants.

Further light stabilizers include the class of substituted benzotriazoles, such as 2- (2'-hydroxy-5'-methyl) -phenylbenztriazole, 2- (2'-hydroxy-5 ', 5 ¹ -di-tert-butyl) ^ -chlorophenyl -benstriasol; the stabilizers of the hydroxybenzophenone type; the sterically hindered phenols, such as 2 ¹ ^ '- di-tert.-butylphenyl-J ^ -cli-tert.-butyl ^ -hydroxybenzoate and those in German patents and (German patent applications no.

2098 13/1824

P 21 18 298.9, P 21 28 757.0) described stabilizers, while suitable metal complexing agents, metal deactivators, Salicylidene-propylenediamine, 5,5'-methylene-bis-benzotriazole and salts of salicylaminoguanidine.

The other additives are, like the compounds of general formula I, advantageously in an amount in the range from 0.01 "to 5 wt .-%, based on the weight of the untreated organic Materials used.

Together with an antioxidant suitable for inhibiting the oxidative decomposition of polyolefins, e.g. an antioxidant from Kind of a sterically hindered phenol, the compounds of the general formula I result in extremely effective, generally applicable Stabilizer systems for polyolefins, especially for polystyrene.

The following examples are intended to explain the present invention further without, however, restricting it. All parts and percentages are based on weight unless otherwise specified.

example 1

A mixture of 17.4 parts of adipic acid dihydrazide and 31 parts of triacetone amine in 150 parts of methanol was refluxed for 12 hours. After the methanol had been separated off by distillation under reduced pressure, a white solid was obtained which was recrystallized from ethanol to give 42 parts of di- (2,2,6,6-tetramethylpiperidinyl-4) adipoyldihydrazone in the form of a white solid. This product had a melting point of 212 ° C. and the following analysis values: Analysis: C ₂₄ H ₄₄ N ₆ O ₂

calc .: C 64.22 H 9.99 N 18.74% found: 64.03 9.90 18.85

Example 2

The procedure given in Example 1 was repeated with the difference that instead of adipic acid dihydrazide, 23 parts

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Sebacic acid dihydrazide were used.

. In this way, 25 parts of di- (2,2,6,6-tetramethylpiperidinyl-4) -sebacoyl-dihydrazone with a melting point of 195 ° to 197 ° C. and the following analytical values were obtained: Analysis: ^C 28 ^H 52 ¹¹ 6 ⁰ 2

calc .: .C 66.62 H 10.39 N 16.66% found: 66.87 10.56 16.51%

Example 3

The procedure described in Example 1 was used, except that instead of 20.6 parts of adipic dihydrazide were used Thiodipro- W pionsäuredihydrazid.

In this way, 20.3 parts of di (2,2,6,6-tetramethylpiperidinyl-4) thiopropionyl dihydrazone were obtained with a melting range of 192 to 195 ° C and the following analysis values: Analysis:

ber .: C. 59 , 98 H 9, 23 N 17, 50 S. 6th , 66 found: 57 , 35 9, 29 17, 34 6th , 86

Example 4

A mixture of 7.4 parts of acetic acid hydrazide and 15.5 parts of triacetone amine in 80 parts of methanol was refluxed for 12 hours. After removal of the methanol by distillation under reduced pressure, a white solid was obtained, which was recrystallized from ethyl acetate to give 16.5 parts of 2,2,6,6-tetramethylpiperidinyl-4-acetylhydrazone in the form of a white solid with a Melting point of 149 to 150 ⁰ C and the following analysis values obtained:
Analysis: G ^ H ^ IUO

calc .: C 62.56 H 9.95 N 19.91% found: 62.99 10.34 19.95%

Example5
A mixture of 21.6 parts of heptanoic acid hydrazide and 23.25 parts

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• 2H6692 '·

len triacetonamine in 150 parts of methanol was refluxed for 24 hours. After removal of the methanol by distillation under reduced pressure, a white solid was obtained which was recrystallized from absolute ethyl alcohol, whereupon 21 parts of 2,2,6,6-tetramethyl-4-heptanoylhydrasone with a melting point of 69 to 71 were added ⁰ C and the following analysis values:
Analysis: Ο ^ Η, ^ Ν ^ Ο

her .: 0 "68.50 H 11.05 N 14.95% found: 68.40 10.83 14.66%

Example 6

A mixture of 27.0 parts of lauric acid hydrazide and 18.3 parts Triacetone amine in 300 parts of methanol was refluxed for 12 hours. After the methanol has been separated off by distillation a white waxy solid was obtained under reduced pressure. This solid was dissolved in ether, to remove trace amounts of the lauric acid hydrazide filtered, whereupon the ether by distillation under reduced The pressure was removed and 2,2,6,6-tetramethylpiperidinyl-4-lauroylhydrazone was obtained with the following analytical values:

Analysis: ^C 21 ^H 41 N ₂ O
3 H 11 ■ - , 75 N 11 , 95 ber .: C 71, 74 11 , 80 11 , 76 found: 72, 18th

Example 7

A mixture of 2.98 parts of stearing acid hydrazide and 2.33 parts Triacetonamine was refluxed in 100 parts of toluene for 36 hours, with the water formed during the reaction was removed using a Dean-Stark device. After the toluene has been separated off by distillation under reduced pressure A white solid was obtained under pressure, which was recrystallized from methanol, whereupon 1.10 parts of 2,2,6,6-tetramethylpiperidinyl-4-stearoylhydrazone were obtained with a melting point of 72 to 73 ° 0 and the following analytical values:

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Analysis: 2 C. 74 3 3 H 12, 20th N 9 , 64 ber .: 74 , 50 12, 18th 9 , 58 found: , 46

Example 8

A mixture of 11.0 parts of dodecane-1:10 dicarboxylic acid dihydrazide and 12.24 parts of triacetonamine in 600 parts of methanol was refluxed for 12 hours. Upon cooling, a small amount of a white solid crystallized out which was collected by filtration and found to be the starting unreacted hydrazide. The methanol was then removed by distillation under reduced pressure to give a white solid which was recrystallized from ethyl acetate to give 5.70 parts of di- (2,2,6,6-tetramethylpiperidinyl-4) -dodecane-1 : 10-dioyl-di-hydrazone with a melting point of 166 to 167 ° C and the following analysis values received:
Analysis: C ₃₀ H ₅₆ N ₆ O ₂

calc .: C 67.62 H 10.59 N 15.78% found: 67.66 10.69 15.52

Example 9

A mixture of 20.4 parts of isobutyric acid hydrazide and 81.0 parts of triacetone amine in 150 parts of methanol was refluxed for 24 hours. On cooling the solution, a white solid crystallized out, which was collected by filtration and recrystallized from methanol, giving 25.2 parts of 2,2,6,6-tetramethylpiperidinyl-4-isobutyroylhydrazone in the form of white needles with a melting point from 164 to 165 ° C and received the following analysis values:
Analysis: G ^ Η ,,, - Ν, Ο

calc .: C 65.20 H 10.45 N 17.55% found: 65.42 10.64 17.37

Example 10

A mixture of 13.6 parts of benzoic hydrazide and 15.5 parts Triacetonamine in 100 parts of methanol was 20 hours on

2 09813/1824

Heated to reflux. After separation of the methanol by distillation under reduced pressure to give a white Peststoff consisting of petroleum ether (boiling point 100 to 120 ⁰ C) was recrystallized, after which 2,2,6,6-tetramethylpiperidinyl-4-benzoyl-hydrazone having a melting point from 194 to 195 ° C "and received the following analysis values:
Analysis: C ^ ₆ H ₂ JtM)

calc .: C 70.33 H 8.42 N 15.40% found: 70.59 '8.72 15.59%

Example 11

A mixture of 24.9 parts of p-toluic acid hydrazide and 31.0 parts of triacetone amine in 500 parts of ethanol was refluxed for 24 hours. After removal of the ethanol by distillation under reduced pressure, a white solid was obtained which was recrystallized from petroleum ether (boiling point 100 to ^ 20 ⁰ C), whereupon 20.6 parts of 2,2,6,6-tetramethylpiperidinyl-4 -p-toluyl hydrazone with a melting point of 18? to 188 ° C (decomposition) and the following analytical values: Analysis: C ^ n

calc .: C 71.05 H 8.77 N 14.62% found: 70.92 8.56 14.82%

Example 12

A mixture of 9.70 parts of isophthalic acid hydrazide and 31.0 parts of triacetone amine in 100 parts of methanol was refluxed for 24 hours. After cooling, a white solid crystallized from the solution, which was collected by filtration and recrystallized from methanol, whereupon 10.0 parts of di- (2,2,6,6-1etramethylpiperidinyl-4) -isophthaloyl-dihydrazone were added a melting point of 240 to 241 ° C (decomposition) and the following analytical values: Analysis: C ₂ 6 ^H 40 ^N 6 ° 2

calc .: C 66.80 H 8.50 N 17.90% found : 66.52 8.69 17.70%

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Example Ί3

A mixture of 18.80 parts of α-naphthoic acid hydrazide and 23.0 parts of triacetonamine in 300 parts of methanol was refluxed for 24 hours. Removal of the methanol by distillation under reduced pressure gave a white solid which was washed three times with ether and finally recrystallized from ethyl alcohol so that 16.70 parts of 2,2,6,6-tetramethylpiperidinyl-4-a-naphthoyl were obtained -hydrazone received in the form of a white solid with a melting point of 210 to 211 ⁰ C and the following analysis values: Analysis:

calc .: C 74.27 H 7.79 N 12.99 found: 74.67 8.04 12.98

Example 14

A mixture of 22.40 parts of phenylacetic acid hydrazide and 31.0 parts of triacetone amine in 500 parts of ethanol was refluxed for 24 hours. Removal of the ethanol by distillation under reduced pressure gave a white solid which was recrystallized from acetone to give 32.80 parts of 2,2,6,6-tetramethylpiperidinyl-4-phenylacetylhydrazone, melting point 158 to 159 ° C and the following analysis values:
Analysis: C ₁₇ H ₂₁ -N ₃ O

* calc .: C 71.05 H 8.77 N 14.62 %

found: 71.23 8.83 14.80%

Example 15

A mixture of 10.0 parts of a-naphthylacetic acid hydrazide and 11.62 parts of triacetonamine in 150 parts of methanol were refluxed for 24 hours. After removing the methanol through Distillation under reduced pressure gave a white solid, which was recrystallized from acetone to give 11.20 parts of 2,2,6,6-tetramethylpiperidinyl-4-α-naphthylaeetylhydrazone with a melting point of 196 to 197 ° C and the following analytical values:

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Analysis: C. 21 ^H 27 ^N 3 ° H 8th, 06 N 12, 46 "ber .: C. 74.72 7, 99 12, 39 found: 74.51

Example 16

A mixture of 4.53 parts of α, α-diphenylacetic acid hydrazide and 4.65 parts of triacetone amine in 75 parts of methanol was refluxed for 24 hours. After cooling the solution, it separated a white solid which was collected by filtration and recrystallized from methanol, whereupon 1.50 parts of 2,2,6,6-tetramethylpiperidinyl ^ -o ^ cx-diphenylacetylhydrazone with a melting point of 216 "to 217 ° C and the following analysis values received:

Analysis: Q ^^ - ^^^

her .: C 76.00 H 8.04 N 11.56%

found: 75.60 8.06 11.78%

Example 17

A mixture of 9.90 parts of cyclohexanecarboxylic acid hydrazide and 10.85 parts of triacetone amine in 150 parts of methanol was added for 24 hours heated to reflux. After removing the methanol by distillation under reduced pressure, a white one was obtained Solid which was recrystallized from benzene, whereupon 13.20 parts of 2,2,6,6-tetramethylpiperidinyl-4-cyclohexane-carboxylic acid hydrazone in the form of a white solid with a melting point of 194 "to 195 ° C and the following analytical values: Analysis: C-gHpgN ^ O

her .: C 69.10 H 10.05 N 15.10% found: 69.35 10.45 15.19%

Example 18

A mixture of 6.80 parts of formic hydrazide and 23.0 parts Triacetonamin.in 150 parts of methanol was on for 12 hours Heated to reflux. After the methanol was separated off by distillation under reduced pressure, a solid which was recrystallized from ethanol, so that 2,2,6,6-tetramethylpiperidinyl-4-formylhydrazone in the form of a white solid

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having a melting point of 148 to 15O ⁰ C and the following analytical values:
Analysis: C ^ qH ^ N ^ O

calc .: C 60.88 H 9.71 N 21.30% found: 61.17 9.99 21.34%

Example 19

A mixture of 23.0 parts of isocaproic acid, 100 parts of methanol and 1.0 part of concentrated sulfuric acid was refluxed for 18 hours. The solution was cooled and 11.0 parts of hydrazine hydrate were added and the solution was refluxed for an additional 24 hours. The solution was then cooled and a small amount of a white crystalline solid was filtered off. 28.17 parts of triacetonamine were added to the filtrate and the solution was refluxed for a further 24 hours. After removal of the methanol by distillation under reduced pressure, a solid was obtained, which was recrystallized from ethyl acetate, whereupon 17.80 parts of 2,2,6,6-tetramethylpiperidinyl-4-isocaproylhydrazone were obtained as a white solid having a melting point from 128.5 to 129.5 ° C and received the following analysis values:
Analysis: CL ₁ -HpQN ^ O

calc .: C 67.40 H 10.93 N 15.71% found: 67.80 11.08 15.94%

Examples 20 and 21

100 parts of crystalline polystyrene beads (pellets) were made dry with 0.25 parts of the protective agents given in the table mixed, whereupon the dry mixture was homogenized by extrusion. The stabilized granules obtained were deformed into platelets with a thickness of 2 mm. The obtained plates were placed in an exposure device for 1000 hours ("Xenotest 150") exposed, whereupon the resulting yellowing of the plates by determining the yellowing factor (yellowness factor) was measured according to the following formula:

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Yellowing factor:

. 100

worm

Tabel

(560)

Δ Τ the transmission losses "at wavelengths 420 or 680 mn after 1000 hours of exposure in the Xenotest device, and "

the transmission value of a non-t-exposed

(560)
Mean sample at a wavelength of 560 nm.

Yellowing factor for crystalline polystyrene plates after 1000 hours of exposure in a Xenotest device

Ice cream
No. Yellowing factor additive _ 16.8 comparison - 5.6 Compound of Example 9 of the
British patent specification 1 196 224 - 5.1 Connection of "example no.37"
the. OS 1,929,928 - 3.4 Connection of example no. 3
the British patent 1 202 298 20th 0.6 (Example 2) according to the invention 21st 1.0 (Example 5) according to the invention

Similar results were obtained with the products of Examples 7, 8 and 10.

Examples 22 to 24

A 0.15 w / v percent solution of the product of Example 1 in acetone was prepared and then 50 parts by volume of this solution were added to 40 parts by weight of powdered polypropylene which was essentially free of stabilizers. An additional 60 volumes of acetone were then added to form a slurry which was mixed by hand to homogenize. Finally, the solvent was removed in a dirch evaporation maintained at 80 ⁰ C oven.

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14 parts by weight of the dried powder were placed in a mold. Weighed in with the dimensions 15.24 15.24 χ 0.038 mm (6 χ 6 χ 0.015 inch.). The mold and polished plate were then heated under constant pressure in the press for 5 minutes. A pressure of 3.1 tons / cm (20 tons per square inch) was maintained in the press for one minute, then cooling continued and the pressure increased so that by the time the temperature reached 150 ^° C it was assumed a value of 12.4 tons / cm (80 tons per square inch). Cooling was then continued until the temperature of the mold reached 50 ⁰ G, at which point the mold was removed from the press.

^ The formed sheet thus obtained was in an exposure device, which comprised 28 daylight and ultraviolet lamps mounted alternately in a circle, exposed. The sunlight lamps were 61 cm (2 feet) long fluorescent lamps with an output of 20 watts and had a peak emission of 3000 angstrom units, while the ultraviolet light lamps are 61 cm (2 feet) long ultraviolet light lamps with an output of 40 Represent watts that represent a peak emission of 3500 inflow units exhibited. The samples were rotated concentrically around the lamp groups so that the radiation from these lamps was uniform spread over the formed sheet.

The exposed sample was periodically checked, and ψ bent by 180 °, vobei the time at which the material was due to embrittlement interrupted, arrested.

Strip of the molded sheet with dimensions of 15.24 χ 2.54 cm (6.0 inch χ.1,0) oven aging study were subjected to a forced air oven that was maintained at 150 ⁰ C. The time which was required until the test strip broke by bending the sample by 180 ^° C. was determined.

Similar tests were carried out on polypropylene samples which did not contain any stabilizer or products of Examples 1, 2 and 3. The results obtained are summarized in the following table.

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Ex. Additional time until time until

Brittleness (hrs.) Embrittlement (hrs.) Oven aging light aging test test

none 2 82

22 di- (2,2,6,6-tetramethylpiperidinyl-4) -adipoyl-dihydrazone 3 ^ 93

23 di- (2,2,6,6-tetramethylpiperidinyl-4) -.
sebacoyl-di-hydrazone 5 119

24 Di- (2,2,6,6-tetramethylpiperidinyl-4) -thiopropionyl-di-hydrazone 7 263

Example 25

A mixture of 31.20 parts of p-tert-butylbenzoic acid hydrazide and 31.0 parts of triacetone in 500 parts of ethanol was refluxed for 24 hours. After the ethanol had been separated off by distillation under reduced pressure, a white solid was obtained which was recrystallized twice from ethyl acetate to give 13.80 parts of 2,2,6,6-tetramethylpiperidinyl-4-p-tert-butylbenzoylhydrazone with a melting point of 165 to 166 ° C and the following analytical values:
Analysis:

ber .:
found:

Example 26

A mixture of 15.80 parts of 2-ethylhexanecarboxylic acid hydrazide and 23.0 parts of triacetone amine in 250 parts of methanol was refluxed for 15 hours. After removing the methanol distillation under reduced pressure gave a reddish oil which slowly solidified. The two times Recrystallization from ethanol gave 7.10 parts of 2,2,6,6-tetramethylpiperidinyl-4-2'-ethylhexanoylhydrazone in the form of a white solid with a melting point of 91 to 93 ° C and the following

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^C 20 ^H 31 3 H 9 , 46 N 12, 74 C 72, 99 9 , 54 12, 52 73, 46

the analysis values:
Analysis: Ο.πΗ ,, Ν, Ο

Calcd .: C 69.11 H 11.26 N 14.22 Measured values: 69.42 11.38 14.02

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Claims (1)

- 21 claims 1. Compounds of the general formula I H ₃
V CH ₃ CH-3 CH ₂ (I) H-NC-N.NH.C.R CH ₃ CH ₃ and their acid addition salts, in which E is hydrogen, a straight or branched-chain alkyl radical having 1 to 20 carbon atoms, where the alkyl chain can be interrupted by one or more sulfur atoms, a cycloalkyl radical with 5 to 12 carbon atoms, a cycloalkylalkyl radical with 6 to 12 carbon atoms, a phenyl radical, an n-phthalic radical, an arylalkyl radical with 7 up to 14 carbon atoms or an alkylaryl radical with 7 to 14 Carbon atoms, or in which B is a group of the formula II CH ₃ \ ^CH 2 /% - ^c -τ- (Y) -C.NH.N = C NH • CH ^(II) CH ₃ represents wherein Y is a divalent straight or branched chain Alkylene radical with 1 to 20 carbon atoms, in which the alkylene chain is interrupted by one or more sulfur atoms can be, or an arylene radical having 6 to 12 carbon atoms and a is 0 or 1, or in which E is a group of the formula III CH, - -WUH = C ^ NH (III) 209813/1824 means. 2. A compound according to claim 1, characterized in that R is hydrogen, an alkyl radical having 1 to 17 carbon atoms, a cyclohexyl group,> an aralkyl group with 7 to 14 carbon atoms, denotes a phenyl radical, an alkylphenyl radical having 7 to 10 carbon atoms or a naphthyl radical, or R is the formula II given in claim 1, wherein Y is an alkylene radical with 4- to. 10 carbon atoms means the through a sulfur atom may be interrupted, or in which Y is a phenylene radical means, and a represents 1. ™ 3 · Compound according to claim 1, characterized in that that R is an alkyl radical having 1 to 12 carbon atoms, a cycloalkyl radical with 6 carbon atoms, a cycloalkylalkyl radical or aralkyl group having 7 to 11 carbon atoms or an aralkyl group with 7 to 10 carbon atoms, or R denotes the group of the general formula II given in claim 1, wherein Y is an alkylene radical having 1 to 10 carbon atoms or Aryl enre st with 6 carbon atoms and a is 1. 4. A compound according to claim 1, characterized in that the compound is a phosphate, carbonate, sulfate, chloride, Citrate, acetate, stearate, maleate, oxalate or benzoate salt ) is. 5. Di- (2,2,6, e-tetramethylpiperidinyl- ^) - adipoyl-dihydrazone. 6. Di- (2,2,6,6-tetramethylpiperidinyl-4 -) - sebacoyl-dihydrazone. 7. Di- (2,2,6, e-tetramethylpiperidinyl- ^) -thiodipropionyl-di-hydrazone. 8. 2,2,6,6-TetΓamethylpiperidinyl-4-formylhydrazone. 9. 2,2,6,6-Tetramethylpiperidinyl-Zl-acetyl-hydrazone. 209813/182 4 2H6692 2,2,6, δ-tetramethylpiperidinyl ^ -isocaproylhydrazone. 2,2,6,6-tetramethylpiperidinyl-4-heptanoylhydrazone. 2,2,6,6-Tetramethylpiperidii ^ 1-4 ~ lauroylhydrazone. 2,2,6, e-Tetramethylpiperidinyl ^ -stearoylhydrazone. 2,2,6,6-Tetramethylpiperidinyl-4-isobutyroylhydrazone. 2,2,6,6-Tetramethylpiperidinyl-4-benzoylhydrazone. 2,2,6,6-tetramethylpiperidinyl-4-p-toluoyl-hydrazone. 2,2,6,6-tetramethylpiperidinyl-4-a-naphthoylhydrazone. 2,2,6,6-tetramethylpiperidinyl-4-phenylacetyl-hydra- 2,2,6, e-Tetramethylpiperidinyl - ^ - a-naplithylacetyl-2,2,6, e- 19. hydrazone 20. hydrazone. 21. 2,2,6,6-Tetramethylpiperiäinyl-4-cyclohexane-carbon- ' acid hydrazone. 22. Di- (2,2,6,6-tetramethylpiperidinyl-4) -isophthaloyldihydrazone. 23 · Di- (2,2,6,6-tetramethylpiperidinyl-4) -dodecane-1: 1O-dioyl-dihydrazone. 24. 2,2,6,6-Tetramethylpiperidinyl-4-p-tert-butylbenzoyl-hydrazone. 25. 2,2,6,6-Tetramethylpiperidinyl-4-2'-ethylhexanoylhydrazone. 26. Use of the compounds according to claim 1 for stabilization of organic material. 27. Use according to claim 27, characterized in that that the organic material is a polyolefin. 28. Use according to claim 27, characterized in that the polyolefin is a polyethylene of low or high density or polypropylene. 209813/1824 ■ 2H6692 ■ 29 · Use according to claim. 28, characterized in that that the polyolefin is polystyrene. 209813/1824