DE2314091A1 - SUBSTITUTED PIPERAZINDIONOXYLES AND HYDROXYDE AND THEIR USE AS STABILIZERS FOR POLYMERIZE COMPOSITIONS - Google Patents

Description

Dr. F. Zumsteln sen. · Dr. E. Assmann Dr. R. Koenlgsberger · Dlpl.-Phys. R. Holzbauer - Dr. F. Zumsteln Jun.

PATENT LAWYERS TELEPHONE: COLLECTIVE NO. 335341

TELEX 939β7β

TELEGRAMS: ZUMPAT POST CHECK ACCOUNT: MUNICH 9Tl 39

BANK ACCOUNT: BANKHAUS H. AUFHAUSER

β MONKS 2.

BRAUHAUSSTRASSE 4 / W

xc / n

Case 3-8087 / gC 587

CIBA-GEIGY AG, Basel / Switzerland

Substituted piperazine dxonoxyls and hydroxides

and their use as stabilizers

for polymer compositions

The invention relates to substituted piperazine dxonoxyls and hydroxides and the use of these compounds for stabilization of organic polymer compositions

The invention thus relates generally to the stabilization of organic material which is normally subject to decomposition. The invention relates in particular to the protection of synthetic polymers against harmful degradation effects, such as discoloration and embrittlement, which are caused by the action of light, in particular by the action of ultraviolet light.

It is known that actinic radiation, especially in the area near ultraviolet, a deleterious effect on both the appearance and properties of organic polymers exercises. E.g. colorless or usually yellow

309840/1186

weakly colored polyesters when exposed to sunlight, which also applies to cellulose products such as cellulose acetate. Polystyrene discolors and cracks when exposed to active light , thereby losing the desirable physical properties of this material; on the other hand, vinyl resins such as polyvinyl chloride and polyvinyl acetate are stained and subject to degradation. The oxidation of polyolefins, such as polyethylene and polypropylene, by the surrounding air is considerably accelerated by ultraviolet light.

It has already been proposed to stabilize polymeric materials against the harmful effects of ultraviolet light by using various ultraviolet light absorbers. Thus 3,004,896 2-phenyltriazole derivatives have been proposed for this purpose in the US Patent, while the US patent 3,189,630 are intended to represent certain metal salts of hydroxybenzoic acids useful actinic stabilizers for synthetic polymers according to.

The invention now relates to a class of ultraviolet light stabilizers, namely substituted piperazine dionoxyls and hydroxides of the general formula I below

X-N

R R

3098A0 / 1186

wherein X

an oxygen atom or an OH group,

12th

R and R, which can be identical or different, alkyl groups with 1 to 12 carbon atoms or together with the carbon atom to which they are attached, a monoeyelic ring system with 5 to 12 carbon atoms,

η is an integer from 1 to 3,

R, when η represents 1, represents a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, preferably an octadecyl group or a benzyl group,

when η represents 2, an alkylene group having 1 to 20 carbon atoms, a p-xylylene group or a alkyl-substituted p-xylylene group of the general formula

CH.

- R

wherein the substituents R, R,

R and R water

substance atoms or low molecular weight alkyl groups with 1 to 5 carbon atoms, preferably methyl groups represent, and

when η is 3, a 1,3,5-mesitylene group or a 2,4,6-alkyl-substituted mesitylene group of general formula

-CH

-CH

309840/1186

wherein the substituents R, R and R are hydrogen atoms or low molecular weight alkyl groups with 1 to Represent 5 carbon atoms,

mean.

The term "alkyl group" as used for the substituents R and

R used includes straight or branched chain saturated hydrocarbon groups having 1 to 12 carbon atoms. Examples of such alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, Octyl and dodecyl groups. The monocyclic ring system or the cycloalkyl group having 5 to 12 carbon atoms includes e.g. Cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl groups and derivatives of these monocyclic ring systems which are mono- or disubstituted by low molecular weight alkyl groups. The preferred alkyl groups contain 1 to 5 carbon atoms and are preferably methyl groups while the preferred cycloalkyl groups are 5 to 8 carbon atoms and most preferably contain 5 or 6 carbon atoms.

The terms "alkyl group" and "alkylene group" as used for the group R include alkyl groups or alkylene groups having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl _? Pentyl, isopentyl, hexyl, octyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, methylene, ethylene, propylene, butylene, octylene, dodecylene, octadecylene or eicosylene groups . '

The substituents R ⁴ , R, R, R, R, R ₁ R ¹⁰ and the substituents of the monocyclic ring systems which are represented by the groups R

2
and R can be low molecular weight alkyl groups. These groups contain 1 to 5 carbon atoms and can be methyl, ethyl, propyl, butyl and pentyl groups.

The invention also relates to the use of the inventive «Μ · ΜΜΜ« ΑΜΜ9β »to stabilize synthetic organic Polymers normally under the action of

309840/1186

23U091

Ultraviolet light is subject to decomposition against the harmful effects of the ultraviolet light, whereby one 0.005 to 5% by weight, preferably 0.01 to 2% by weight of the compound of the general formula I according to the invention incorporated.

The piperazinedionoxyl and hydroxide compounds of the general Formula I can be used together with other light stabilizers, such as 2- (2-hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, Nickel complexes and benzoates.

The stabilizers according to the invention are suitable for protecting many synthetic polymers against the harmful effects of light. The substrates which can be stabilized with the stabilizers according to the invention include homopolymers, copolymers and mixtures of these materials, such as, for example, polystyrene including homopolystyrene and copolymers with acrylonitrile and / or butadiene; Vinyl resins obtained by the polymerization of vinyl halides or by the copolymerization of vinyl halides with unsaturated polymerizable compounds, for example vinyl esters, α, β-unsaturated acids, α, β-unsaturated esters and unsaturated hydrocarbons such as butadienes and styrene; Poly-ci-olefins, such as polyethylene with high and low density, crosslinked polyethylene, polypropylene, poly (4-methyl-pentene-1), polybutene-1 and the like including copolymers of poly-α-olefins such as ethylene / propylene Copolymers and the like; Polybutadiene; Polyisoprene; Polyurethanes such as those obtained from polyols and organic polyisocyanates; Polyamides such as hexamethylene adipamide; Polyesters such as polymethylene terephthalates; Polycarbonates such as those obtained from bisphenol A and phosgene; Polyacetals, polyethylene oxides, and polyacrylic resins such as polyacrylonitrile; Polyphenylene oxides such as those prepared from 2,6-dimethylphenol and the like. The compounds according to the invention are particularly preferably used in normally solid polymers of α-olefins having up to 3 carbon atoms, for example the polymers of ethylene, propylene and the copolymers of these monomers. 309840/1186

The polymers stabilized according to the invention can normal uses in which these plastics are used, and are particularly ^ for foils and Suitable for fibers. The inventive eewBes «* ··! ·· * · * · can be incorporated into the polymeric substance during the usual processing steps, e.g. by mixing in the heat, the compositions then being extruded, pressed into films, fibers, filaments, hollow spheres and the like, blown or otherwise deformed. If you make the polymer from a liquid monomer, such as im In the case of styrene, the stabilizer can be dispersed in the monomer prior to polymerization or prior to curing or solve.

In addition to the stabilizers according to the invention mentioned, the polymer compositions can contain further additives such as plasticizers, pigments, fillers, dyes, glass fibers or other fibers, thermal antioxidants and the like. For example, in most applications it is desirable to incorporate a sufficient amount of thermal antioxidants into the resin compositions to protect the polymer against thermal and oxidative decomposition. The required Anticxydansmenge is _s are used with the amount of actinic stabilizers according to the invention comparable. Usually about 0.005 to 5% by weight, preferably about 0.01 to 2% by weight, is used. Examples of such antioxidants are phosphite esters such as triphenyl phosphite and dicutyl phosphite, and alkylaryl phosphites such as dibutylphenyl phosphite and the like.

The best results are obtained with the preferred class of thermal antioxidants, with; the sterically hindered; Phenols. These compounds give, together with those according to the invention Stabilizers the best thermal stabilization and the least discoloration «Typical phenolic antioxidants of this type include the following compounds:

23U091

1. Phenolic compounds of the general formula

Q- (CH ₂ ) _w - A ₁

wherein

Q is a group of the formula

R

and ·

A is a group of formulas

-CR (COOR ¹¹ J ₂ or

COOR · '

I.

C (CH-) -Q

COOR · '

wherein

R is a hydrogen atom or a low molecular weight Alkyl group having 1 to 5 carbon atoms

R ^{1 is} a low molecular weight alkyl group with 1 to. Carbon atoms

R ¹ 'represents an alkyl group with 6 to 24 carbon atoms and w represents an integer from 0 to,
mean.

Examples of connections of the above kind are:

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Di-n-octadecyl-u- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate,

Di-n-octadecyl-a- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, that is described in Dutch patent specification 6 711 199, and

Di-n-octadecyl-a, a'-bis- (3-tert-butyl-4-hydroxy-5-methylbenzyl-malonate, which is described in Dutch patent specification 6,803,498.

2. Phenolic compounds of the general formula

Q-R,

wherein Q and R have the meanings given above.

Examples of connections of this type are:

2,6-di-tert-butyl-p-cresol,

2-methyl-4,6-di-tert-butylphenol
and the like.

, 3. Phenolic compounds of the general formula

wherein Q and w have the meanings given above.

Examples of connections of this type are:

2,2'-methylene-bis- (6-tert-butyl-4-methylphenol), 2,2'-methylene-bis- (6-tert-butyl-4-ethylphenol), 4,4 ⁽ -butylidene -bis- (2,6-di-tert-butylphenol), 4,4 '- (2-butylidene) -bis- (2-tert-butyl-5-methylphenol),

2,2'-methylene-bis- [6- (1-methyl-cyclohexyl) -4-methylphenol] and the same.

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4. Phenolic compounds of the general formula

R-O-Q,

wherein R and Q have the meanings given above,

Examples of connections of this type are:

2,5-di-tert-buty! Hydroquinone, 2,6-di-tert-butylhydroquinone and 2,5-di-tert-butyl-4-hydroxyanisole.

5. Phenolic compounds of the general formula

Q-S-Q, in which Q has the meanings given above.

Examples of connections of this kind are:

4,4'-thiobis (2-tert-butyl-5-methylphenol), 4,4'-thiobis (2-tert-butyl-6-methylphenol) and 2,2'-thiobis (6-tert-butyl-4-methylphenol)

6. Phenolic compounds of the general formula

0 Q- (CH ₂ ) _w -S- (CH ₂ ) _w -C-OR · ·

wherein Q, w and R ^{11 have} the meanings given above. ·

23H091.

Examples of connections of this type are:

Octadecyl (3,5 -dimethyl-4-hydroxybenzylthio) acetate and dodecyl (3,5-di-tert-butyl-4-hydroxybenzylthio) propionate,

7. Phenolic compounds of the general formula

j in which Q and w have the meanings given above and T denotes a hydrogen atom.

Examples of connections of this type are:

I ₁ 1,3-tris (3,5-dimethyl-4-hydroxyphenyl) propane, l, l, 3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane and

1,1,5,5-tetrakis- (3'-tert-butyl-4'-hydroxy-6-methylphenyl J- n-pentane.

8. Phenolic compounds of the general formula

QCH ₀

12 3

wherein B, B and B are hydrogen atoms, methyl groups or groups Q with the meaning given above, with the proviso that when the groups B * and B ^ have the meaning of

2
Q have, the group B has a hydrogen atom or a methyl

2 represents group, and if the group B is the meaning of

Q has the groups B and B "are ³ hydrogen atoms or methyl groups.

309 * 40/1188

23H091

Examples of connections of this type are:

1,4-di- (3,5-di-tert-butyl-4-hydroxybenzyl) -2 _r 3,5,6-tetramethylbenzene and

1,3,5-tri- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene.

9. Phenolic compounds of the general formula

S-D

(Q) -NH

wherein

Z is a group of the formula NHQ, -S-D or -0-Q, where Q has the meaning given above, and

D is an alkyl group having 6 to 12 carbon atoms or a group of the formula- (C _w Hp) -SR · ', in which R ^{11 has} the meanings given above,

mean.

Examples of connections of this type are:

2,4-bis (n-octylthio) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -l, 3, 5-triazine,

6- (4-Hydroxy-3-methyl-5-tert-butylanilino) -2,4-bis (n-octylthio) -1, 3,5-triazine,

6- (4-hydroxy-3,5-dimethylanilino) -2,4-bis- (n-octylthio) -1,3,5-triazine,

6- (4-hydroxy-3,5-di-tert-butylanilino) -2,4-bis (n-octyI-thioethylthio) -1, 3,5-triazine,

6- (4-Hydroxy-3,5-di-tert-butylanilino) -4- (4-hydroxy-3,5-di-tert-butylphenoxy) -2- (n-octylthio) -1.3, 5-triazine and

2,4-bis- (4-hydroxy-3,5-di-tert-butylanilino) -6- (n-octylthio ) -1, 3,5-triazine.

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The specified phenolic triazine stabilizers are described in more detail in US Pat. No. 3,255,191.

10. Phenolic compounds of the general formula

wherein Z ^{1 is} a group of the formulas -OQ, -SD or -S- (CH ₉ ) -SD, in which Q, D and w have the meanings given above.

Examples of connections of this type are:

2,3-bis- (3,5-di-tert-butyl-4-hydroxyphenoxy) -6- (n-octylthio) -1, 3,5-triazine,

2,4,6-tris- (4-hydroxy-3,5-di-tert-butylphenoxy) -1,3,5-triazine,

6- (4-Hydroxy-3,5-di-tert-butylphenoxy) -2,4-bis (n-octyl ~ thioäthylthio) -l, 3,5-triazine,

6- (4-Hydroxy-3-methylphenoxy) -2,4-bis (n-octylthio) -1,3,5-triazine,

6- (4-Hydroxy-3-tert-butylphenoxy) -2,4-bis (n-octylthioethylthio) - !, 3,5-triazine,

6- (4-Hydroxy-3-methyl-5-tert-butylphenoxy) -2,4-bis (n-octylthio) -1,3,5-triazine,

2,4-bis- (4-hydroxy-3-methyl-5-tert-butylphenoxy) -6- (n-octylthio) -1, 3,5-triazine,

2,4,6-Tri s- (4-hydroxy-3-methyl-5-tert.-butylphenoxy) -1, 3,5-triazine,

6- (4-Hydroxy-3,5-di-tert-butylphenoxy) -2,4-bis- (n-octy1-thiopropylthio) -1, 3,5-triazine,

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6- (4-Hydroxy-3,5-di-tert-butylphenoxy) -2,4-bis- (n-dodecylthioethylthio) -1, 3,5-triazine,

2,4-bis- (4-hydroxy-3,5-di-tert-butylphenoxy) -6-butylthio-1,3,5-triazine,

2,4-bis- (4-hydroxy-3,5-di-tert-butylphenoxy) -6- (n-octadecylthio) -1, 3,5-triazine,

2,4-bis- (4-hydroxy-3,5-di-tert-butylphenoxy) -6- (n-dodecylthio) -1,3,5-triazine,

2,4-bis- (4-hydroxy-3,5-di-tert-butylphenoxy) -6- (n-octyl- ' thiopropylthio) - !, 3,5-triazine,

2,4-bis- (4-hydroxy-3,5-di-tert-butylphenoxy) -6- (n-octylthioethylthio) -1,3,5-triazine and

2,4-bis- (4-hydroxy-3,5-di-tert-butylphenoxy) -6- (n-dodecylthioethylthio) -1,3,5-triazine.

The above phenolic triazine stabilizers are described in greater detail in U.S. Patent 3,255,191.

11. Phenolic compounds of the general formula

where ρ is an integer with a value from 1 to 4,

R ¹ · ^{1 is} a tetravalent radical such as an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aliphatic mono- or dithioether group having 1 to 30 carbon atoms or an aliphatic mono- or diether group having 1 to 30 carbon atoms and

ζ represent an integer from 0 to 6. ^K>

Examples of connections of this type are:

309840 / 1-88

'23H091

Subclass I.

n-octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, n-octadecyl-2- (3,5-di-tert-butyl-4-hydroxyphenyl) acetate, n-octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, n-hexyl-3,5-di-tert-butyl-4-hydroxyphenylbenzoate, n-dodecyl-3, 5-di-tert-butyl-4-hydroxyphenyl benzoate, Neo-dodecyl-3- (3,5-di-tert-buty 1-4-hydroxyphenyl) propionate, Dodecyl-ß- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, Ethyl α- (4-hydroxy-3,5-di-tert-butylphenyl) isobutyrate, Octadecyl a- (4-hydroxy-3,5-di-tert-butylphenyl) isobutyrate

Octadecyl a- (4-hydroxy-3,5-di-tert-butylphenyl) propionate.

Subclass II

2- (n-octylthio) ethyl 3,5-di-tert-butyl-4-hydroxybenzoate,

2_ (n-octylthio) ethyl-3,5-di-tert-butyl-4-hydroxyphenyl acetate,

2- (n-Octadecylthio) -Methyl-3,5-di-tert-butyl-4-hydroxyphenyl acetate,

2- (n-octadecylthio) ethyl 3,5-di-tert-butyl-4-hydroxybenzoate,

2- (2-Hydroxyäthylthio) -äthyl-3,5-di-tert-butyl-4-hydroxybenzoate,

2,2'-thiodiethanol bis (3,5-di-tert-buty1-4-hydroxyphenyl) acetate,

Diethylene glycol bis [3,5-di-tert-butyl-4-hydroxyphenyl) propionate],

"5

2- (n-Octadecylthio) ethyl-3- (3,5-di-tert-buty1-4-hydroxyph enyl) propionate,

2,2'-Thiodiäthancl-bis-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate,

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23T4091

Stearamido-N _s N-bis- [ethylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl propionate],

n-Butylimino-N, N-bis- [ethylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl ) propionate],

2- (2-stearoylethylthio) ethyl 3,5-di-tert-butyl-4-hydroxybenzoate,

2- (2-Hydroxyethylthio) ethyl 7- (3-methyl-5-tert-butyl-4-hydroxyphenyl) heptanoate and

2- (2-stearoyloxyethylthio) ethyl 7- (3-methyl-5-tert-butyl'-4-hydroxyphenyl) heptanoate.

Subclass III

1,2-propylene glycol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],

Ethyl glycol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) - propionate],

Neopentyl glycol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate],

Ethylene glycol bis (3,5-di-tert-buty1-4-hydroxyphenyl acetate),

Glycerol-l-n-octadecanoate-2,3-bis- (3,5-di-tert-butyl-4-hydroxyphenyl acetate)

Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], '

1,1, l-trimethylolethane-tris-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate,

Sorbitol hexa- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate,

1,2,3-butanetriol tri- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], ,.,

2-hydroxyethyl 7- (3-methyl-5-tert-butyl-4-hydroxyphenyl) heptanoate,

2-stearoyloxyethyl) -7- (3-methyl-5-tert-butyl-4-hydroxyphenyl) heptanoate and

309840/1186

" ¹⁶ ". 23H091

1,6-n-Hexanediol bis [3- (3 ·, S'-di-tert-butyl ^ -hydroxy phenyl) propionate].

The phenolic ester stabilizers of Subclasses I, II and III identified above are described in greater detail in U.S. Patents 3,330,859, 3,441,575 and 3,644,482.

12. Phenolic compounds of the general formula

OR

wherein Q and R ″ have the meanings given above and χ represents an integer of 1 or 2.

Examples of connections of this type are:

Di-n-octadecyl-3,5-di-tert-buty1-4-hydroxybenzylphosphonate,

Di-n-octadecy1-3-tert-butyl-4-hydroxy-5-methylbenzylphosphonate,

Di-n-octadecyl-1- (3,5-di-tert-butyl-4-hydroxyphenyl) ethane phosphonate,

Di-n-tetradecyl-3,5-di-tert-buty1-4-hydroxybenzylphosphonate, Di-n-hexadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphate, Di-n-docosyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate and Di-n-octadecyl-3,5-di-tert-buty1-4-hydroxybenzylphosphonate.

The di- (higher molecular weight) -alkylphenolphosphonates given above are described in more detail in U.S. Patent 3,281,505.

13. Phenolic compounds of the general formula

309840/1186 *

Vr ⁰

wherein w and Q have the meanings given above.

Examples of connections of this type are:

. Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and Tris (3-tert-butyl-4-hydroxy-5-ynethylbenzyl) isocyanurate.

The hydroxyphenylalkenyl isocyanurates mentioned are described in more detail in US Pat. No. 3,531,483 »:

The phenolic hydrocarbon stabilizers listed above are known and many compounds of this type are commercially available.

Although all of the above mentioned antioxidants in combination which can be used successfully with the ultraviolet light stabilizers of the present invention are the preferred antioxidants the hindered phenols of Groups 1, 8, 9, 10, 11, 12 and 13 mentioned above. The most preferred sterically hindered phenols are those of groups 1, 9, 11, 12 and 13.

309840/1186

23H091

The compounds according to the invention can be prepared by adding a substituted piperazinedione of the general formula II

R Ji R ¹

II

1 2
in which R and R have the meanings given above, with an organic mono-, di- or tri-halogen compound of the general formula R ^ (X), in which R, and η have the meanings given above and X is a halogen atom, preferably a chlorine atom or a bromine atom means converts. The alkylation reaction is carried out in such a way that one first prepares an alkali or alkaline earth metal salt of the compounds of the general formula II and reacts the salt obtained with the suitable organic halide in a solvent such as dimethylformamide, isopropanol or acetone at about 75.degree a compound of the general formula III

H-N

III

12 3
obtained, in which R, R, R and η have the meanings given above. To form the salts of the compounds of general formula II, bases such as KOH, NaOH, KOCH ₃ or KNH ^ can be used.

309840/1 188

set. The metal salts can be prepared in a separate step or in the solvent in which the subsequent Alkylation is carried out.

The oxidation of the compounds of general formula III to the substituted Piperazindionoxylen of the general formula I can using a HpO ^ / water / sodium tungstate / ethylenediaminetetraacetic acid process, a HpOp / water / phosphotungstic acid process as well as with peracids such as perbenzoic acid or peracetic acid.

The oxides can then be converted to the substituted piperazinedione hydroxides using standard methods known per se of the general formula I can be reduced.

The compounds of the general formula II in which the group

1 2
pen R and R form a monocyclic ring with the carbon atom to which they are bonded can be obtained by self-condensation of a cycloalkylamino-cyanohydrin according to that of R. Sudo and S. Ichihera in "Bu 11. Chem. Soc. Japan", 2i6_, 34 ( 1963) and subsequent hydrolysis according to the method of EFJ Duynstee et al., "Recueil de Chemie des Pay.3-Bas", 87 , 945 (1968). The cycloalkylaminocyanhydrin is obtained by sequential addition of hydrogen cyanide and ammonia to a cycloalkanone according to the method as described by WE Noland, RJ Sundberg and ML Michaelson ["J.Org. Chem.", 2ji, 3576 (1963)]. Although the literature references cited above relate in particular to the cycloalkyl derivatives, the procedures disclosed are also suitable for the alkyl derivatives, so that, for example, an alkanone such as acetone can be used instead of the above-mentioned cycloalkanone such as cyclohexanone.

Examples of organic halides with the salts of Compounds of the general formula II can be implemented include organic monohalides, such as methyl iodide, ethyl chloride, Propyl bromide, isopropyl chloride, butyl bromide, pentyl bromide, isopentyl chloride, hexyl bromide, octyl bromide, dodecyl

309840/1 186

~ ²⁰ ~ 23H091

bromide, tetradecyl chloride, hexadecyl bromide, octadecyl bromide, eicosyl bromide, benzyl chloride and the like, also organic dihalides, such as methylene bromide, dibromoethane, 1,3-dibromopropane, 1,3-dibromobutane, 1,4-dibromobutane, 1,8-dibromooctane, 1,12 -Dichlorododecane, 1,2-dichloroctane, 1,18-dibromoctadecane, 1,20-dibromicosane, p-dichloroxylylene, 2,3,5,6-tetramethyl-1,4-bischloromethylbenzene and the like, as well as organic trihalides, such as α, α ', α "- trichloromesitylene, 1, 3, 5-trimethyl-α, α ¹ , α" - trichloromesitylene, 1,2, 3-tribromobutane and the like. The preferred organic monohalides contain 6 to 6 carbon atoms. The preferred organic dihalides have 2 to 12 carbon atoms, while the preferred organic trihalides have 4 to 12 carbon atoms.

The following examples are intended to explain the invention further without, however, restricting it.

example 1

l-aminocyclohexanecarbonitrile

In a 200 ml three-necked flask fitted with a stirrer, a Thermometer, a reflux condenser fitted with a drying tube and a gas inlet pipe, 100 g (0.8 mol) of cyclohexanone cyanohydrin was added and the reaction mixture was cooled in an ice bath at 15 ° C. Then, gaseous anhydrous ammonia was passed through the gas inlet tube for 6 hours introduced into the reaction mixture. Then the reaction vessel became sealed and left to stand overnight.

The next day, anhydrous ammonia was again passed through the reaction mixture for hours at 25 ° C., whereupon dry nitrogen gas to remove excess ammonia was bubbled through the reaction mixture. The product was then dissolved in 250 ml of benzene, the benzene solution then became washed twice with 250 ml of water and dried over anhydrous Na SO. dried. Evaporation of the benzene gave the product in the form of a pale yellow oil.

309840/1186

23U091

Similarly, by using an equivalent amount of acetone cyanohydrin instead of cyclohexanone cyanohydrin 1-Aminoisobutyronitrile produced.

In the same way, using an equivalent amount of cyclodecanone cyanohydrin, 2-heptanone cyanohydrin or 10-nonadecanone cyanohydrin instead of cyclohexanone cyanohydrin 1-aminocyclodecanecarbonitrile, 2-amino-2-cyano-heptane or 10-amino-10-cyano-nonadecane.

Example 2 Bis (1-cyanocyclohexyl) amine

To a single neck, round bottom flask equipped with a nitrogen capillary inlet and an air condenser was added 48.2 grams (0.39 moles) of 1-aminocyclohexanecarbonitrile. The reaction mixture was then heated to a bath temperature of 75 to 100 ^° C. in an oil bath for 1 hour and evacuated using a water jet pump. The reaction was then continued for 24 hours, after which the mixture was cooled to room temperature, the pressure was equalized and the crystalline mass was triturated with ether and filtered off with suction, giving 19.1 g of white crystals with a melting point of 133 to 138 ° C.

In the same way, using an equivalent amount of 1-aminoisobutyronitrile instead of 1-aminocyclohexanecarbonitrile was obtained Bis- (l-cyanoisopropylamine).

In the same way, if, instead of l-aminocyclohexanecarbonitrile, one obtained an equivalent amount of 1-aminocydodecanecarbonitrile, 2-amino-2-cyanoheptane or 10-amino-10-cyano-n-nonadecane used, bis- (l-cyanocyclodecyl) -amine, bis- (2-cyanoheptylamine) or bis (10-cyanononadecyl) amine.

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: 23-09

Example 3

7,15-diazadispirof 5.1.5.3] hexadecane-14, 16-dione

To 406 g of 96 _{percent strength by weight H 3} SO ₄ contained in a 500 ml three-necked flask equipped with a stirrer, thermometer and powder funnel, 30.0 g were added with stirring and cooling over a period of about 2 hours powdered bis-d-cyanocyclohexyD-amine. The temperature of the reaction mixture was maintained at 0-5 ° C using an ice bath during the addition. The mixture was then allowed to warm to room temperature and stir overnight. The reaction mixture was then heated to 100 ° C for 1 hour, then cooled to about 15 ° C and poured onto 3000 g of ice. The aqueous mixture was neutralized to a p "value of about 7 by adding about 800 ml of 10N NaOH solution. The resulting precipitate was filtered off with suction, washed well with water and dried in a vacuum oven, giving a white powder with a melting point of 155 to 160 ° C,

Similarly, using an equivalent one obtained Amount of bis (1-cyanoisopropyl) amine instead of bis (1-cyanohexyl) amine 2,2,6,6-tetramethyl-3,5-diketopiperazine.

By using an equivalent amount of bis (1-cyanocyclodecyl) amine, Bis- (2-cyano-2-heptyl) -amine or bis- (10-cyano-10-nonadecyl) -amine instead of bis (1-cyanocyclohexyl) amine one 11,23-diazadispiro [9,1.9.3] tetracosane-22,24-dione, 2,6-dimethyl-2,6-dipentyl-3,5-diketopiperazine or 2,2,6,6-tetranonyl-3,5-diketopiperazine.

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23H091

Example 4

15-n-octadecyl-7, lS-diazadispirof5,1.5.3ihexadecane ~ 14 _t 16-dione

To a solution of 10.0 g (0.04 mol) of 7,15-diazadispiro- [5.1,5.3] hexadecane-14,16-dione in 150 ml of anhydrous methanol, which was present in a 500 ml flask, was added 2.6 g of an 86 percent by weight KOH solution (0.04 mol) and shake the mixture until a solution was obtained. The reaction mixture was then evaporated to dryness under reduced pressure. The residue was transferred to a 300 ml three-necked flask, the one with a stirrer, a thermometer, a reflux condenser provided with a drying tube, a dropping funnel and was equipped with a nitrogen inlet tube, with a low Amount of dry dimethylformamide used. About the potassium imide salt 150 ml of dry dimethylformamide were added under a nitrogen atmosphere. It was added to the stirred solution then a solution of 13.3 g (0.04 mol) of n-octadecylbr ~ .T) id in 50 ml of dimethylformamide. The reaction mixture was then slowly heated to 75 ° C. and at this temperature for 3 hours held. Then the reaction mixture was cooled and left to stand at room temperature overnight. The reaction mixture was then taken up with 500 ml of ether, whereupon the ethereal solution was washed well with water over anhydrous Well-jSO. dried and evaporated under reduced pressure became. The residue which crystallized out on standing was recrystallized from methanol, 14.3 g of the product being obtained in the form of white needles with a melting point of 39 to 40 ° C.

By using the procedure described above and replacing the n-octadecyl bromide with an equivalent amount of:

a) benzyl chloride

b) 2,3,5,6-tetramethyl-p-dichloroxylylene

c) 1,12-dibromododecane

d) 1,3,5-trimethyl-2,4,6-trisloromethylbenzene

e) 1,8-dibromooctane

f) 1,4-dibromobutane

g) methyl iodide or
h) octyl bromide

309640/1186

-24- 23H091

the following compounds were obtained:

a) 15-Benzyl-7,15-diazadispiro [5.1,5,3] hexadecane-14,16-dione, F = 91 to 94 ° C

b) 15.15 · - (2 ", 3", 5 ", 6" -tetramethyl-p-xylylidenyl) -bis- (7,15-diazadispiro [5.1.5.3] hexadecane-14,16-dione), F = 253 to 257 ° C

c) 15,15'-n-Dodecanmethylen-bis- (7, IS-diazadispiro [5.1.5.3] -hexadecane - 14,16-dione), F = 100 to 103 ⁰ C.

d) 15.15 ", 15" - (2,4,6-trimethyl-a, a ', a "-mesitylidene) -tris- (7,15-diazadispiro [5.1.5.3] hexadecane-14,16-dione ), F = 236 to 240 ° C

e) 15,15'-n-octamethylene-bis-C 7,15-diazadispiro [5,1.5,3Jhexadecane-14,16-dione )

f) 15,15'-tetramethylene-bis- (7,15-diazadispiro [5,1,5.3Jhexadecane-14,16-dione ), F = 178 to 181 ° C

g) 15-methyl-7,15-diazadispiro [5.1,5,3 jhexadecane-14,16-dione, F = 122 to 126 ° C or

h) 15-n-Octyl-7,15-diazadispiro [5.1,5.3] hexadecane-14,16-dione.

Example 5

By using the procedure given in Example 4 and replacing the 7,15-diazadispiro [5.1.5.3jhexadecan-14,16-dione by an equivalent amount of 2,2,6,6-tetramethyl-3,5-diketopiperazine hSd obtained the compounds given below

a) 4-n-octadecyl-2,2,6,6-tetramethyl-3,5-diketopiperazine, F = 52 to 54 ° C

b) 4-Benzyl-2,2,6,6-tetramethyl-3,5-diketopiperazine, F = 80 bis 84 ° C

c) 4,4 · - (2 ", 3", 5 », 6" -Tetramethyl-p-xylylidenyl) -bis- (2,2,6,6-tetramethyl-3,5-diketopiperazine)

d) 4,4 '- (n-Dodecanmethy1en) -bis- (2,2,6,6-tetramethyl-3,5-diketopiperazine), F a 73 to 75 ° C

e) 4,4 '- (2,4,6-trimethyl-a, a, a ^lf -mesitylidene) -tris- (2, 2, 6, 6-tetramethyl-3,5-diketopiperazine)

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f) 4,4 - (n-octamethylene) -bis- (2,2,6,6-tetramethyl-3,5-diketopiperazine)

g) 4,4 - (tetramethylene) -bis- (2,2,6,6-tetramethyl-3,5-diketopiperazine)

h) 4-methyl-2,2,6,6-tetramethyl-3,5-diketopiperazine or i) 4-n-Octyl-2,2,6,6-tetramethyl-3,5-diketopiperazine

Example 6

Using the procedure described in Example 4 and replacing the 7,15-diazadispiro [5.1.5.3] hexadecane-14,16-dione and the organic halides used there by the piperazinedione derivatives and organic ones given below Halides:

a) ll, 23-Diazadispiro [9.1.9.3] tetracosane-22,24-dione + n-octadecyl bromide

b) 2,6-dimethyl-2,6-di-n -pentyl-3,5-diketopiperazine + Benzyl chloride or

c) 2,2,6,6-Tetranony1-3,5-diketopiperazine + n-octyl bromide

the following substances were obtained:

a) 23-n-Octadecyl-II, 23-diazadispiro [9.1.9.3] tetracosane-22,24-dione ^

b) 4-Benzyl-2,6-dimethyl-2,6-di-n-pentyl-3,5-diketopiperazine respectively.

c) 4-n-Octyl-2,2,6,6-tetranony1-3,5-diketopiperazine

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Example 7

IS-n-Octadecyl ^ -oxyl - ?, 15-diazadispiro [5.1.5.3Jhexadecane-14,16-dione

In a 300 ml three-necked flask fitted with a stirrer, a Thermometer, a dropping funnel, and a drying tube equipped reflux condenser and a nitrogen inlet was, a solution of 9.0 g (0.018 mol) of 15-n-octadecyl-7,15-diazadispiro [5.1 «5.3] hexadeca-14,16-dione was added in 50 ml of methylene chloride. A solution of 7.21 g (0.358 Mol) m-chlorobenzoic acid (85% by weight) in 150 ml of methylene chloride added. The temperature of the reaction mixture was kept at 20-25 ° C. during the addition. The reaction mixture quickly turned light orange and the reaction was allowed to proceed for an additional 24 hours. After this Time the precipitated solids were suctioned off, whereupon the filtrate was continued using a short, silica gel filled column was cleaned. The filtrate was evaporated to give 6.7 g of an orange oil which was dissolved in Stand crystallized. The orange crystalline material was recrystallized from an acetone / acetonitrile mixture, the desired oxide in the form of pale orange colored crystals with a melting point of 58.5 to 6O.5 ° C.

Using the above procedure and replacing the 15-n-octadecyl-7,15-diazadispiro [5.1.5.3] hexadeca-14.16-dione by an equivalent amount of:

a) 15-Benzyl-7,15-diazadispiro [5.1.5.3Jhexadeca-14,16-dione

b) 15.15 '- (2 ", 3", 5 ", 6" -tetramethyl-p-xylylidenyl) -bis- (7,15-diazadispiro [5.1.5.3] hexadeca-14,16-dione)

c) 15,15 '- (n-dodecamethylene) -bis- (7,15-diazadispiro- [5,1,5,3] hexadeca-14,16-dione)

d) 15.15 ·, 15 "- (2,4,6-trimetyhyl-a, a ^!, a" ~ mesitylidene) -tris- (7,15-diazadipsiro [5.1,5.3] hexadeca-14,16-dione )

309840/1

e) 15.15 ^f - (n- <: ~ tamethylene) -bis- (7,15-diazadispiro [5.1.5.3] -hexadeca-14,16-dione)

f) 15.15 - (Tetratnethylen) -bis- (7,15-diazadipsiro [5.1.5.3] -hexadeca-14,16-dione)

g) 15-methyl-7,15-diazadispiro [5.1.5.3] hexadeca-14,16-dione h) 15-n-Octyl-7,15-diazadispiro [5.1.5.3] hexadeca-14,16-dione i) 4-n-Octadecyl-2,2,6,6-tetramethyl-3,5-diketopiperazine j) 4-Benzyl-2,2,6,6-tetramethyl-3,5-diketopiperazine

k) 4,4 · - (2 ", 3", 5 ", 6" -Tetramethyl-p-xyIylidenyl) -bis- (2,2,6,6-tetramethyl-3,5-diketopiperazine)

1) 4,4 '- (n -dodecamethylene) -bis- (2,2,6,6-tetramethyl-3,5-diketopiperazine )

m) 4,4 - (2,4,6-Trimethy1-α, α », a" -mesitylidene) -tris- (2,2,6,6-tetramethyl-3,5-diketopiperazine)

η) 4,4 · - (n-Octamethylene) -bis- (2,2,6,6-tetramethyl-3,5-diketopiperazine )

ο) 4,4 '- (Tetratnethylen) -bis- (2,2,6,6-tetramethyl-3,5-diketopiperazine )

ρ) 4-methyl-2,2,6,6-tetramethyl-3,5-diketopiperazine q) 4-n-Octyl-2,2,6,6-tetramethyl-3,5-diketopiperazine

r) 23-n-Octadecyl-ll, 23-diazadispiro [9 ^f . 1 '.9'. 3 '] tetracosane-22,24-dione

s) 4-Benzyl-2,6-dimethyl-2,6-dipentyl-3,5-diketopiperazine or t) 4-n-Octyl-2,2,6,6-tetranonyl-3,5-diketopiperazine

the following compounds were obtained:

a) 15-Benzyl-7-oxyl-7,15-diazadispiro [5.1.5. sjhexadeca- ^ l ^, 16-

dione, m.p. 74 to 75 ° C

b) 15,15 '- (2 ", 3 ^ll , 5", 6 ^u -tetramethyl-p-xylylidenyl) -bis- (7-oxyl-7,15-diazadispiro [5.1.5.3] hexadeca-14,16- dione), F = 175 to 177 ° C

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23H091

c) 15,15 '- (n-dodecamethylene) -bis- (7-oxyl-7,15-diazadispiro- [5.1.5.3] hexadeca-14,16-dione)

d) 15,15 ', 15 "- (2,4,6-trimethyl-a _! a ⁽ , α''- mesitylidene) -tris- (7-oxyl-7,15-diazadispiro [5.1.5.3] hexadeca- 14,16-dione)

e) 15,15 '- (n-octamethylene) bis (7-oxyl ~ 7,15-diasadispiro- [5.1.5.2] hexadeca-14,16-dione)

f) 15.15 '- (tetramethylene) bis (7-oxyl-7,15-diazadispiro- [5.1.5.3] hexadeca-14,16-dione)

g) 15-Methy1-7-oxyl-7,15-diazadispiro [5.1.5.3Jhexadeca-14,16-dione

h) 15-n-octyl-7-oxyl-7,15-diazadispire [5.1,5 "3jhexadeca-14,16-dione

i) 4-n-Octadecyl-1-oxyl-2, 2,6, δ-hetramethyl-S, S-diketopiperazine

j) 4-Benzyl-1-oxyl-2,2,6,6-tetramet.hy.l ~ 3,5-diketcpiperazine

k) 4,4 '- (2 ", 3", 5 ^t ', 6 "-Tetran: ethyl-p-xy: .yl ^ denyi J-rds- (1-oxyl-2,2,6,6- tetramethy1-3,5-diketcpiperazine)

1) 4,4 (η-dodecamethylene) -bis- (l-oxyi.-2, 2,6, 6-th tr ame thy 1-3,5-diketopiperasine;

m) 4,4 '- (2,4,6-trimethyl-a, a', a "~ mesitylidene) -tris- (1-oxyl-2,2,6,6-tetramethyl-3,5-diketcpiperazine)

η) 4,4 '- (n-octamethylene) -bis- (l-oxyl-2,2,6,6-tetramethyl-3,5-diketopiperazine)

ο) 4,4 ■ - (tetramethylene) -bis- (l-cxyl-2,2,6,5-tetramethyl-3,5-diketopiperazine)

ρ) 4-Methyl-1-oxyl-2, 2,6, 6-tetramet: iyl-3, 5-dikeropiperazine q) 4-n-Octyl-1-oxyl-2, 2,6, 6- tetra.T.e ^ nyl-S, 5-cike tcpiperaain

r) 23-n-Octadecyl-ll-cxyl-ll, 23-diazacifpirc [9, 1 , S, Ξ] tetracosane-22,24-dione

s) 4-Benzyl-1-oxyl-2, S-dimecnyl-2, 5 ~ dipen-: y 1-3, 5-diketopiperazine respectively.

t) 4-n-Octyl-1-oxyl-2, 2,6,6-teuranonyl-3, 5-diketcpi.perasin

3098 ^ 0 / 11S8

Example 8

IS-n-Octadecyl ^ -hydroxy - ?, 15-diazadispiror 5.1.5.3] hexadecane-14.16-dione

0.5 g of a catalyst was added to a solution of 6.2 g (0.012 mol) of 15-n-octadecyl-7-oxyl-7,15-diazadispiro [5.1.5.3] hexadecane-14,16-dione in warm glacial acetic acid (5% Pd on charcoal). The glacial acetic acid solution was placed in a Parr hydrogenation apparatus and hydrogenated for 1/2 hour at a hydrogen pressure of 3.16 kg / cm (45 psi). After this time, the reaction mixture was poured into water and extracted with 3 × 200 ml of ether. The ether extracts were combined, over anhydrous Na _? SO. dried and evaporated to give 4.0 g (65%) of a pale yellow colored solid. The solid was recrystallized from methanol, the desired hydroxylamine being obtained after drying in vacuo over PpO ₅ in the form of white crystals with a melting point of 54 to 58 ° C.

Using the above procedure and replacing the 15-n-octadecyl-7-oxyl-7,15-diazadispiro [5.1.5.3] hexadeca-14,16-dione an equivalent amount of the compounds given in Example 7 gave those given below Links:

a) 15-Benzyl-7-hydroxy-7,15-diazadispiro [5.1.5.3] hexadeca-14,16-dione

b) 15.15 · - (2 ", 3", 5 ", 6" -tetramethyl-p-xylylidenyl) -bis- (7-hydroxy-7,15-diazadispiro [5.1.5.3] hexadecane-14,16- dion)

c) 15,15 '- (n-dodecamethylene) -bis- (7-hydroxy-7,15-diazadispiro- [5.1.5.3] hexadecane-14,16-dione)

d) 15,15 ', 15 "- (2,4,6-trimethyl-a, a', a" -mesi tyliden) -tris-

(7-hydroxy-7,15-diazadispiro [5.1.5.3Jhexadecane-14,16-dione)

e) 15,15 '- (n-OctamethylerD-bis- (7-hydroxy-7,15-diazadispiro- [5.1.5.3] hexadecane-14,16-dione)

f) 15,15'-G'etramethylene) bis (7-hydroxy-7,15-diazadispiro- [5.1.5.3] hexadecane-14,16-dione)

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2 3 H 0 91

g) 15-methyl-7-hydroxy-7,15-diazadispiro [5.1.5.3] hexad. "an-14,16-dione

h) IS-n-octyl-V-hydroxy- ?, 15-diazadispiro [5.1,5.3] hexadecane-14,16-dione

i) 4-n-Octadecyl-1-hydroxy-2,2,6,6-tetramethyl-3,5-diketopiperazine

j) 4-Benzyl-1-hydroxy-2,2,6,6-tetramethyl-3,5-diketopiperazine

k) 4,4 '- (2 ", 3", 5 ", 6" -tetramethyl-p-xylylidenyl) -bis- (1-hydroxy-2,2,6,6-tetramethyl-3,5-diketopiperazine)

1) 4,4 '- (n-dodecamethylene) -bis- (l-hydroxy-2, 2,6,6-tetramethy1-3,5-diketopiperazine)

m) 4,4 '- (1,3,5-trimethylmesitylidene) -tris- (l-hydroxy-2,2,6,6-tetramethyl-3,5-diketopiperazir.)

n) 4,4 '- (n-octamethylene) -bis- (l-hydroxy-2,2,6,6-tetramethyl-3,5-diketopiperazine)

ο) 4,4 '- (tetramethylene) -bis- (l-hydroxy-2,2,6,6-tetramethyl-3,5-diketopiperazine)

ρ) 4-methyl-1-hydroxy-2,2,6,6-tetramethyl-3,5-diketopiperazine q) 4-n-octyl-1-hydroxy-2,2,6,6-tetramethyl-3,5-diketopiperazine

r) 23-n-Octadecyl-II-hydroxy-II, 23-diazadispiro [9.1.9.3 tetracosane-22,24-dione

s) 4-Benzyl-1-hydroxy-2,6-dimethyl-2,6-dipentyl-3,5-diketopiperazine respectively.

t) 4-n-Octyl-1-hydroxy-2,2,6,6-tetranonyl-3,5-diketopiperazine

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23U091

Example 9 Examination by exposure to artificial light

The degradation of most of them caused by ultraviolet light Polymers run so slowly at room temperature, even in the absence of stabilizers, that the investigation the stabilizer effect in general either at higher temperatures or in a device with the help of which under accelerated conditions can be exposed to artificial light, so that one can be done in a reasonable time got results. The investigations in which the Polyrisate treated with artificial light using an exposure device are described below :

a) Sample preparation

FoJi s with a thickness of 0.127 mm (5 mil)

Unstabilized polypropylene powder (Hercules Profax 6501) goes well with the additives given in the given Mixed quantities. The mixed material is then milled for 5 minutes at 182 ° C. on a two-roll mill. The ground sheet is then at 220 ° C and at a Pressure of 12.3 kg / cm (175 psi) pressed into a film 0.127 mm (5 mil) thick and in the press with Chilled water.

b) Test procedure

This examination is carried out using an exposure device constructed by American Cyanamid, which comprises 40 alternating fluorescent light lamps and ultraviolet light lamps (20 each). The slides with a 0.127 mm (5 mil) thick are placed on infrared spectrum sample holders Made of cardboard measuring 3x2 inches (7.62 5.08 cm) with an opening of 0.635 cm 2.54 cm (1/4 χ 1 inches) 'mounted and 2 inches (5.08 cm) from the lamps on a rotating drum arranged in the exposure device. Then the

309840/1186

Determines the time required for the development of 0.5 carbonyl absorption units, determined with an infrared spectrophotometer was required. The development of functional carbonyl groups in the polymer is proportional to that due to exposure to ultraviolet light induced decomposition.

The test results given below were determined according to the procedures described above. The additive amounts are as weight percent based on weight of the polymer.

309840/1186

Tabel

Time in hours to development

.χ of 0.5 carbonyl

Formulations of absorption units

0.5% IS-n-octadecyl-T-oxyl-VjlS
diazadispirof 5.1,5.3 Jhexadecan-14,16-dione 300

Ιδ-ΒβηζγΙ-Τ-οχγΙ-β, Ιδ-αίαΖ
dispiro [5.1.5.3Jhexadecane-14,16-dione 380

0.5% 4-n-octadecyl-1-oxyl-2,2,6,6-tetramethyl-3,5-diketopiperazine 860

0.5% IS-n-octadecyl-T-hydroxy-

7,15-diazadispiro [5.1.5.3J-hexadecane-14,16-dione 545

Comparison ⁺⁾ 225

Each of the samples examined and the comparative sample contained 0.2% by weight of di-octadecyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate as an antioxidant to prevent oxidative degradation of the polypropylene during processing.

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" ³⁴ " 23-09Ί

Instead of di-octadecyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate other sterically hindered phenolic antioxidants can be used in the compositions given above. tien are used, e.g. di-n-octadecyl-cx-O-tert.-butyl-4-hydroxy-4-methylbenzyl) malonate, 2,4-bis (n-octylthio) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1, 3,5-triazine, ^ Octadecyl 3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate, Pentaerythritol tetrakis {3- (3, 5-di-tert-butyl-4-hyciroxyphenyl) propionate] or tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate.

Example 10

a) A composition comprising an acrylonitrile / butadiene / styrene terpolymer and 1% by weight of 15.15 '- (n-dodecamethylene) bis (7-oxyl-7,15-diazadispiro [5.1.5.3Jhexadecane-14, 16-dione) resists embrittlement, caused by exposure to ultraviolet light, longer than a sample that does not contain the stabilizer.

b) A composition containing a polyurethane made from toluene diisocyanate and alkyl polyols and 1.0% by weight of 15-benzyl-7-hydroxy-7,15-diazadispiro [5.1.5.3] hexadecane-14,16-dione is against sunlight , sunlight, ultraviolet light and fluorescent light produced by fluorescent lamps are more stable than the unstabilized polyurethane.

c) A composition comprising a polycarbonate made from bisphenol-A and phosgene and 1% by weight of 4-n-octadecyl-l-oxyl-2,2,6,6-tetramethyl-3,5- contains diketopiperazine, withstands discoloration due to exposure to ultraviolet light for longer than a sample that does not contain the stabilizer.

d) A composition comprising a polyester (polyethylene terephthalate) and 0.2% by weight 15.15 '- (2 ", 3", 5 ⁿ , 6 "-tetramethyl-p-xylylidenyl) -bis- (7-oxyl- 7,15-diazadispiro [5.1.5.3] -

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" ³⁵ " 23U091

contains hexadecane, withstands discoloration from exposure to ultraviolet light for longer than one Sample that does not contain the stabilizer.

e) A composition containing polymethyl methacrylate and 0.25% by weight of 15,15'-n-dodecamethylene-bis-i7-hydroxy-7,15-diazadispiro [5.1.5.3] hexadecane-14,16-dione) contains, resists discoloration due to exposure to ultraviolet light for a longer time than Sample that does not contain the stabilizer.

Example 11

a) Stabilized linear polyethylene is prepared by incorporating 0.5% by weight of 15,15'-tetramethylene-bis-17-oxyl-7,15-diazadispiro [5.1.5.3Jhexadecane-14,16-dione). The stabilized composition resists the embrittlement caused by exposure to ultraviolet light longer than a sample that does not contain the stabilizer.

b) A stabilized polyamide (nylon 6,6) is made by incorporating 0.1% by weight of 15-n-octadecyl-7-hydroxy-7,15-diazadispiro [5.1.5.3] hexadecane-14,16-dione manufactured. The light stability of the stabilized composition is superior to that of a non-stabilized polyamide.

c) A stabilized polyphenylene oxide polymer (obtained by polymerizing 2,6-dimethylphenol) is through Incorporation of 0.5% by weight of 15-methyl-7-oxyl-7,15-diazadispiro [ 5.1.5.3] hexadecane, 14,16-dione. The stabilized composition resists embrittlement, caused by exposure to ultraviolet light for a longer time than a sample, di, e, den Does not contain stabilizer.

d) Stabilized crystalline polystyrene is made by incorporation from 0.1% by weight of 4,4 '- (n-dodecamethylene) -to-

2098AO / 1 1 Q θ

(l-oxyl-2,2,6,6-tetramethyl-3,5-diketopiperazine). The stabilized composition resists embrittlement, caused by exposure to ultraviolet light, better than a sample - containing the stabilizer does not contain.

Example 12

High impact polystyrene resin containing an elastomer (ie butadiene / styrene) is counteracted against the loss of elongation properties resulting from exposure to ultraviolet light by incorporating 0.3% by weight of 15-n-octadecyl-7,15-diazadispiro [ 5.1.5.3] hexadecane-14 _} 16-dione stabilized.

The non-stabilized resin is dissolved in chloroform, then the stabilizer is added, the mixture is poured onto a Glass plate and, after evaporation of the solvent, is given a film which, after drying, is peeled off, cut up and 7 minutes at a temperature of 163 C and a pressure of 141 kg / cm (2000 psi) to a sheet with a uniform 0.635 mm (25 mil) thick. The sheets are then cut into strips about 10.16 χ 1.27 cm (4 χ 0.5 inches) cut up. A portion of these strips are then measured using a strain gauge [Instron Tensile Testing Apparatus (Instron Engineering Corporation, Quincy, Massachusetts] examined with regard to the percentage elongation. The remaining strips are made in the same way as in Example 6b) described, introduced into the exposure device, with the difference that the time is determined, which is 50% Reduction in elongation leads. The stabilized polystyrene resin retains elongation properties longer than the unstabilized one Resin.

Similar results are obtained if instead of the above Stabilizer uses an equivalent amount of the stabilizers specified below:

309840/1186

a) 0.1% by weight 15.15 ·, 15 "- (2,4,6-trimethyl-a, a ·, <x ^M -esitylidene) -tris- (7-oxyl-7,15-diazadispiro [ 5.1.5.3] hexadecane-14,16-dione)

b) 0.2% by weight of 15.15 '- (n-octamethylene) bis (7-oxyl-7,15-diazadispiro [5.1.5.3] hexadecane-14,16-dione)

c) 1.0% by weight of 15-methyl-7-oxyl-7,15-diazadispiro- [5.1.5.3] hexadecane-14,16-dione

d) 0.1% by weight of 4-n-octadecyl-1-hydroxy-2,2,6,6-tetramethyl-3,5-diketopiperazine

e) 0.1% by weight 4.4 ^l - (2 ^ll , 3 ^M , 5 ^M , 6 "-tetramethyl-p-xylylidenyl) ■ to s- (1-oxy1-2,2,6,6-tetramethyl -3,5-diketopiperazine)

f) 0.5% by weight 4,4 '- (n-octamethylene) -bis- (7-hydroxy-2,2,6,6-tetramethyl-3,5-diketopiperazine)

g) 1% by weight of 4-n-octyl-1-oxyl-2,2,6,6-tetramethyl-3,5-diketopiperazine

h) 0.5% by weight of 23-n-octadecyl-ll-oxyl-ll, 23-diazadispiro- [9.I.9.3] tetracosane-22,24-dione

i) 0.5% by weight of 4-benzyl-1-oxyl-2,6-dimethyl-2,6-dipentyl-3,5-diketopiperazine

j) 0.5% by weight of 4-n-octyl-1-oxyl-2,2,6,6-tetranonyl-3,5-diketopiperazine

Antioxidants, e.g. di-n-octadecyl-a, a * -bis- (3-tert-butyl-4-hydroxy-5-methylbenzyl) -malonate, 2,4-bis- (4-hydroxy-3,5-di-tert-butylphenoxy) -6- (n-octylthioethylthio) -1,3,5-triazine, 2,4-bis- (3,5-di-tert-butylhydroxyphenoxy) -6- (n-octylthio) -1,3,5-triazine, Di-n-octadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate or octadecyl 3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) propionate, be incorporated.

301 * 40/1186

Claims (24)

Claims 1.) Substituted piperazine dionoxyls and hydroxides of the general formula wherein X is an oxygen atom or a hydroxyl group, 2 R and R, which can be the same or different, Alkyl groups with 1 to 12 carbon atoms or together with the carbon atom to which they are attached are bound, a monocyclic ring system with 5 to 12 carbon atoms, η is an integer from 1 to 3 and R, when η is 1, is a hydrogen atom, a Alkyl group having 1 to 20 carbon atoms or a benzyl group, when η is 2, an alkylene group with 1 to 20 carbon atoms, a p-xylylene group or an alkyl-substituted p-xylylene group of the general formula 309840/1186 CIL 23U091 wherein the substituents R ₁ R ₁ R and R are hydrogen atoms or low molecular weight alkyl groups having 1 to 5 carbon atoms, or when η is 3, a 1,3,5-mesitylene group or a 2,4,6-alkyl-substituted mesitylene group of general formula -CH wherein the substituents R, R and R are hydrogen atoms or represent low molecular weight alkyl groups with 1 to 5 carbon atoms, mean. 2.) Compounds according to claim 1, characterized in that 1 2
the groups R and R denote methyl groups or, together with the carbon atom to which they are attached, a monocyclic ring system with 5 to 6 carbon atoms. 3.) Compounds according to claim 1 of the general formula. ^ 309840/1186 23U091 wherein X is an oxygen atom or an OH group, η is an integer from 1 to 3 and R , when η denotes 1, is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a benzyl group, when η denotes 2, an alkylene group having 1 to 20 carbon atoms, a p-xylylene group or an alkyl-substituted p-xylylene group of the general formula I. CH. wherein the substituents R, R, c η R and R are hydrogen mean atoms or low molecular weight alkyl groups with 1 to 5 carbon atoms, or 309840/1186 " ⁴¹ " 23U091 when η is 3, a 1,3,5-mesitylene group or a 2,4,6-alkyl-substituted mesitylene group of the general formula 8 9 Ί0 in which the substituents R, R and R are hydrogen atoms or represent low molecular weight alkyl groups with 1 to 5 carbon atoms, mean, 4.) Compounds according to claim 2, characterized in that η has the values 1 or 2, where R represents an alkyl group with 6 to 18 carbon atoms or a benzyl group, when η denotes 1, or represents an alkylene group having 2 to 12 carbon atoms or a p-xylylene group, when η means 2. 5.) Compounds according to claim 1, characterized in that X is an oxygen atom or an OH group, 1 2 R and R are methyl groups or, together with the carbon atom to which they are attached, a cyclohexyl group, η 1 or 2 and R, when η denotes 1, is an octadecyl group or a benzyl group, or when η is 2, a group represented by the following formula 306140/1186 23H091 CH ₂ CH λ CH 3 \ sy \ / 3 CH, γ CH, CH ₀ ² represents
mean. 6. ) 15-n-Octadecy1-7-OXyI - ?, 15-diazadispiro [5,1.5.3Jhexadecane-14,16-dione. 7.) IS-n-octadecyl-V.-hydroxy-V, 15-diazadispiro [5. 1.5,3] hexa decane-14 , 16-dione. 8.) 15-Benzyl-oxyl-7.15 - diazaidspiro [5.1. 5. 3 j-hexadecane-14,16-dione. 9.) 15-Benzyl-7-hydroxy-7,15-diazadispiro [5.i.5,3] hexadecane-14, 16-dione. 10.) 15.15 "- (2", 3 ", 5", 6 "-tetramethyl-p-xylylidenyl) -bis- (7-oxyl-7,15-diazadispiro [5.1.5.3] hexadecane-14,16 -dion). 11.) 15.15 · - (n-Dodecamethylene) -bis- (7-oxy1-7,15-diazadispiro- [5.1.5.3] hexadecane-14,16-dione). 12.) 15.15 ^I - (n-Dodecamethylene) -bis- (7-hydroxy-7,15-diazadispiro- [5.1.5.3Jhexadecane-14,16-dione). 13.) 15.15 MTetramethylene) bis (7-oxyl-7,15-diazadispiro [5.1,5.3] -hexadecane -14 , 16-dione). 14.) 4-n-Octadecyl-1-oxyl-2,2,6,6-tetramethyl-3,5-diketopiper azine. 309840/1186 15.) IS-Methyl-T-oxyl-V, 15-diazadispiro [5.1.5.3] hexadecane-14,16-dione. 16.) 4-Benzyl-1-oxyl-2,2,6,6-tetramethyl-3,5-diketopiperazine. 17.) 4,4 '- (n-Dodecamethylene) -bis- (1-oxyl-2,2,6,6-tetramethyl-3,5-diketopiperazine). 18.) Use of the compounds according to claim 1 for stabilization of synthetic organic polymers that normally decompose when exposed to ultraviolet light subject. 19.) Use according to claim 18, characterized in that the synthetic organic polymer is polypropylene. 20.) Use of the compounds according to claim 1 for stabilization of synthetic organic polymers, which normally decompose when exposed to ultraviolet light subject. 21.) Use of the compounds according to claim 3 for stabilization of synthetic organic polymers, which normally under the action of ultraviolet light a Subject to decomposition. 22.) Use of the compounds according to claim 4 for stabilization of synthetic organic polymers, which normally under the action of ultraviolet light a Subject to decomposition. 23.) Use of the compounds according to claim 5 for stabilization of synthetic organic polymers, which normally under the action of ultraviolet light a Subject to decomposition. 309840/1186 23U091 24.) Use of the compounds of claims 6 to 17 for stabilizing synthetic organic polymers, which normally decompose when exposed to ultraviolet light. 309840/1186