DE2621842A1 - STABILIZATION OF LIGHT-SENSITIVE POLYMERS - Google Patents

Description

CIBA-GEIGY AG, BASEL (SWITZERLAND)

Case 3-9914 / S / + Germany

DR. ERLEMD DINN ^

ΡΑΤ-.Λ'ΤΛί-'VVALT £ G _; : ? -. E ivi H FsI

uhu. '; i,;.:.; a33E 25

Stabilization of light-sensitive polymers

The invention relates to the stabilization of organic polymers against light degradation by adding new 4-siloxy derivatives alkylated piperidines.

AWAY. Shapiro et al. describe, inter alia, radicals in Polymer Science USSR Volume A 14, (1973), page 3034 ff 4-Siloxpiperidinoxyl derivatives of the formula

CH.

0-N

(4-ri)

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where η is 1, 2 or 3 and R is an alkyl or phenyl radical. These compounds act as stabilizers against the thermal and photodegradation of polypropylene. These radical compounds are colored deep red and their addition too Plastics causes discoloration of the substrates. For this reason, these connections have so far not been technical Gained importance.

In DOS 2 204 659 there are compounds of the formula

CH_ CH " 5/5

-Ή y -oR ^X R ^

-R-

and their use as stabilizers for polymers. In this general formula are among others also Orthosilicates included, where R is a Si atom and η 4 and X can be hydrogen or alkyl.

It has now been found that 4-siloxy derivatives of 2,2,6,6-tetraalkylated Piperidines have an excellent stabilizing effect in light-sensitive polymers and also have advantages over the known orthosilicates, for example better compatibility in certain Polymer substrates. __._.,. .

• These compounds are defined by the general formula I.

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Χ — Ν

Si — IT

(D

2

R and R independently of one another are alkyl with 1-4 carbon atoms, or together with the carbon atom to which they are bonded are, a cyclopentane or cyclohexane ring or

a 2,2,6,6-tetramethylpiperidine ring, 3
R is hydrogen, methyl, phenyl or vinyl, 5

R and ₀ R independently of one another are hydrogen, methyl, phenyl, vinyl, alkoxy with 1-8 carbon atoms, alkoxyalkoxy with 3-10 carbon atoms, cyclohexoxy, aralkoxy with 7-8 carbon atoms, phenoxy or substituted phenoxy (in which the Substituents can be chlorine, alkyl C 1-4 or alkoxy C 1-4), or a radical of the formula

Ν — Χ

3 4
represent, and when R and R are hydrogen, methyl, phenyl or vinyl, R is also a radical of the formula

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can represent, wherein η is an integer from 1-10, and

X is hydrogen, alkyl with 1-12 carbon atoms, alkenyl with 3-6 carbon atoms, alkoxyalkyl with 3-14 carbon atoms, aralkyl with 7-8 carbon atoms or an aliphatic ^ acyl group with 1-4 carbon atoms , or one of the groups -CH ₂ COOR ⁶ , -CH ₂ -CH (R ⁷ ) -OR ⁸ or -COOR ⁹ , in which

R alkyl with 1-8 carbon atoms, alkenyl with 3-6 carbon atoms, phenyl, aralkyl with 7-8 carbon atoms or cyclohexyl,

R hydrogen, methyl or phenyl,

R is hydrogen or an aliphatic, aromatic, araliphatic or alicyclic acyl group up to 18 carbon atoms, optionally in the acyl radical by chlorine, alkyl with 1-4 carbon atoms, alkoxy with 1-8 carbon atoms and / or hydroxyl can be substituted, and

R is alkyl with 1-8 carbon atoms, benzyl, phenyl or cyclohexyl.

As far as these piperidine derivatives are basic, they form with Acids salts and these salts can be used as stabilizers in the same way.

1 2

If R or R denotes an alkyl group with 1-4 C atoms, this can be, for example, methyl, ethyl, propyl> Be isopropyl, n-butyl, or isobutyl.

4 5
When R or R represents an alkoxy group having 1-8 carbon atoms, so for example the methoxy, ethoxy, isopropoxy, butoxy, hex oxy or octoxy may be; R or R as an alkoxyalkoxy group can be, for example, methoxyethoxy, ethoxypropoxy, propoxybutoxy, butoxyethoxy, hexoxyethoxy or tert-butoxyethoxy, preferred

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wise an alkoxyethoxy group.

4 5
If R or R is aralkoxy with 7 or 8 carbon atoms, it can be a benzyloxy or phenethoxy group.

4 5

If R or R is a substituted phenoxy group, this can be replaced by chlorine, alkyl with 1-4 carbon atoms or Alk-

4 5

oxy can be substituted with 1-4 carbon atoms and R or R can then e.g. chlorophenoxy, toluyloxy, xylyloxy, 4-tert.-butylphenoxy, Be 3-ethoxyphenoxy or 4-methoxyphenoxy.

If X is alkyl with 1-12 C atoms, it can be, for example, methyl, ethyl, n-propyl, η-butyl, n-hexyl, n-octyl, n-decyl or be n-dodecyl.

If X is alkenyl with 3-6 C atoms, it can be, for example, allyl, 2-butenyl or 2-hexenyl; preferably alkenyl with 3 or 4 carbon atoms, especially allyl.

If X is alkoxyalkyl with 3-14 carbon atoms, it can be, for example, 2-methoxyethyl, 2-ethoxyethyl, 2-n-butoxyethyl, 3-n-butoxypropyl, 2-octoxyethyl or 2-dodecyloxyethyl, preferably but be alkoxyethyl.

If X is aralkyl with 7 or 8 carbon atoms, it can be, for example, benzyl or phenethyl, preferably benzyl.

If X is an aliphatic acyl group with 1-4 C atoms, for example it can be an acetyl, propionyl, butyryl, formyl, acrylic or crotonyl group.

If X is a group -CH ₂ COOR or COOR, then R

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and R be alkyl groups with 1-8 carbon atoms, e.g. methyl, ethyl, isopropyl, η-butyl, isobutyl, tert-butyl, isopentyl or n-octyl, or alkenyl groups with 3-6 carbon atoms such as allyl, 2- Butenyl or 2-hexenyl. R and R can also be phenyl or cyclohexyl or aralkyl with 7-8 carbon atoms such as benzyl or phenethyl
Alkyl groups with 1-4 carbon atoms.

6 9 such as benzyl or phenethyl. Preferably R and R are

7 8 7

If X is a group -CH ₂ -CH (R) -OR, then R can be hydrogen, methyl or phenyl, preferably hydrogen,

and R can be hydrogen or an aliphatic, aromatic araliphatic ^ or alicyclic acyl group with up to 18 Be carbon atoms, e.g. acetyl, propionyl, butyryl, octanoyl, dodecanoyl, stearoyl, acrylyl, benzoyl, 4-chlorobenzoyl, Toluyl, 4-isopropylbenzoyl, 2,4-dichlorobenzoyl, 4-methoxybenzoyl, 3-butoxybenzoyl, 2-hydroxybenzoyl, 3,5-di-tert-butyl-4-hydroxybenzoyl, ß- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl, phenyl acetyl, cinnamoyl, hexahydrobenzoyl, 1- or 2-naphthoyl or decahydronaphthoyl radicals.

Acid addition salts of compounds of the formula (I) can be those of inorganic acids such as sulfuric acid and hydrochloric acid or phosphoric acid, or of organic carboxylic acids such as formic, acetic, valeric, stearic, oxalic, Adipine, sebacic, maleic, benzoin, 4-tert-butylbenzene, 3,5-di-tert-butyl-4-hydroxybenzoic, salicylic or terephthalic acid, or of sulfonic acids such as methanesulfonic acid or p-toluenesulfonic acid, or of phosphorus-containing organic Acids such as diphenylphosphoric acid or phenylphosphonic acid.

Preference is given to compounds of the formula I in which X is water

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substance, alkyl with 1-4 carbon atoms, acetyl, acrylic or crotonyl

12 3

is, R and R are methyl groups, R is hydrogen, methyl

4 5
or phenyl and R and R independently of one another are methyl, phenyl or the radical

K-X

mean. Of these compounds, in turn those are particularly preferred in which X is hydrogen or methyl and

3
R are methyl or phenyl.

The following list gives examples of compounds of the formula I which can be used according to the invention without that this is associated with a restriction to the connections listed.

2,2,6,6-tetramethyl-4-trimethylsiloxypiperdine 1,2,2,6,6-pentamethyl-4-trimethylsiloxypiperidine 2,2,6,6-tetramethyl-4-triphenylsiloxypiperidine 1,2,2,6,6-pentamethyl-4-triphenylsiloxypiperidine 1-acetyl-2,2,6,6-tetramethyl-4-triphenylsiloxypiperidine Dimethyl bis (2,2,6,6-tetramethylpiperidin-4-oxy) silane Dimethyl bis (1,2,2,6,6-pentamethylpiperidin-4-oxy) -silane diphenyl-bis- (2,2,6,6-tetramethylpiperidin-4-oxy) -silane Diphenyl bis (1,2,2,6,6-pentamethylpiperidin-4-oxy) -silane

Diphenyl bis (1-allyl-2, '2,6,6-tetramethylpiperidin-4-oxy) silane

Diphenyl bis (1-acetyl-2,2,6,6-tetramethylpiperidin-4-oxy) -silane

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Diphenyl bis (1-butyl-2,2,6,6-tetramethylpiperidin-4-oxy) -silane

Diphenyl bis (1-benzyl-2,2,6,6-tetramethylpiperidin-4-oxy) -silane

Methyl phenyl bis (2,2,6,6-tetramethylpiperidin-4-oxy) silane

Methyl phenyl bis (1,2,2,6,6-pentamethylpiperidin-4-oxy) silane Methyl bis (2,2,6,6-tetramethylpiperidin-4-oxy) silane Methyl bis (1,2,2,6,6-pentamethylpiperidin-4-oxy) silane

Methyl bis (1-acetyl-2,2,6,6-tetramethylpiperidin-4-oxy) -silane Phenyl bis (2,2,6,6-tetraraethylpiperidin-4-oxy) silane Phenyl bis (1,2,2,6,6-pentamethylpiperidin-4-oxy) silane Tris- (2,2,6,6-tetramethylpiperidin-4-oxy) -silane Tris (1,2,2,6,6-pentamethylpiperidin-4-oxy) silane Tris- (1-allyl-2, 2,6, 6-tetrair, ethylpiperidin-4-oxy) -silane Methyl tris (2,2,6,6-tetramethylpiperidin-4-oxy) silane

Methyl tris (1,2,2,6,6-pentamethylpiperidin-4-oxy) silane

Methyl 1-tris- (1-allyl-2,2,6,6-tetramethylpiperidin-4-oxy) -silane

Methyl tris (1-benzyl-2,2,6,6-tetramethylpiperidine-4-oxy) silane

Methyl tris (1-acetyl-2,2,6,6-tetramethylpiperidin-4-oxy) silane Phenyl-tris- (2,2,6,6-tetramethylpiperidin-4-oxy) -silane Phenyl-tris- (1,2,2,6,6-pentamethylpiperidin-4-oxy) -silane

Phenyl-tris- (1-acety1-2,2,6,6-tetramethylpiperidin-4-oxy) -silane 2,2,6 , o-tetramethyl-1-phenyl-dimethylsiloxypiperidine 1,2,2,6,6 -pentamethyl -4-phenyl-dimethylsiloxypiperidine

1,3-bis (2,2,6,6-tetramethylpiperidin-4-oxy) -1,1,3,3-tetramethyl-disiloxane

1,3-bis (1,2,2,6,6-pentamethylpiperidin-4-oxy) -1,1,3,3-tetramethyl-disiloxane.

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1-Acryl-2,2,6, o-tetramethyl ^ -triphenylsiloxypiperidine 1-crotonyl-2,2,6,6-tetramethyl-4-triphenylsiloxypiperidine

1-ß-hydroxyethyl-2,2,6, δ-tetramethyl ^ -trimethylsiloxypiperidine

1-ß-BenzoyIoxyethyl-2,2,6,6-tetramethyl-4-trimethylsiloxypiperidine

1-ß-acetyloxyethyl-2,2,6, o-tetramethyl ^ -trimethylsiloxypiperidine

l-ethoxycarbonylmethyl ^^^ jö-tetramethyl ^ -triphenylsiloxypiperidine

1-ethoxycarbonyl-2,2,6, δ-tetramethyl ^ -triphenylsiloxypiperidine.

The 4-siloxypiperidines of formula I can be prepared by silylation of the corresponding 4-hydroxypiperidines of the formula II

CH ₃ CH ₃

X — IT — OH

R ¹ R ² (II)

with silane derivatives of the formula Y-Si (R ³ ) (R ⁴ ) (R ⁵ ), (Y) ₉ Si (R ³ ) (R ⁴ )

3 or (Y.) oSiR, where Y is a known measure for O-silylations capable group, for example halogen, alkoxy, dialkylamino or acyloxy. Above all, that is preferred Silylation using the above silane derivatives, in which Y is chlorine, and which are known by the term chlorosilanes.

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Examples of such chlorosilanes are methyltrichlorosilane, dimethyldichlorosilane, methyl phenyl dichlorosilane, diphenyl dichlorosilane, methyldichlorosilane, phenyltrichlorosilane, phenoxy-dimethyl-chlorosilane or 1,1,3,3-tetramethyl-l, 3-dichlorodisiloxane or mixtures of Ui <J - Dichloropolysiloxanes.

The silylation with chlorosilanes is usually carried out in inert solvents such as hydrocarbons or ethers, e.g. in benzene, toluene, cyclohexane, diethyl ether or tetrahydrofuran carried out. Stoichiometric amounts of a tertiary Amines are usually added as HCl scavengers, such as triethylamine, tributylamine, dimethylaniline or pyridine. The tertiary amine can also be used in excess yes it can also be used as a solvent.

The latter method is advantageous when a compound of the formula II in which X is hydrogen is to be silylated and wherein N-silylation is to be avoided.

According to the invention it has been found that the 4-Silcxypiperidines of the formula I are able to protect a large number of organic polymers against photodamage and thereby have good compatibility with the polymeric substrates. Polymers that are stabilized in this way are e.g. the following:

1. Polymers of mono- and diolefins, such as polyethylene (which can optionally be crosslinked), polypropylene, polyisobutylene, polymethylbutene-1, polymethylpentene-1, Polyisoprene or polybutadiene.

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2. Mixtures of the polymers mentioned under 1), e.g. mixtures of polypropylene with polyethylene or with polyisobutylene.

3. Copolymers of mono- and diolefins, such as ethylene-propylene copolymers, Propylene-butene-1 copolymers, Pro * - pylene-isobutylene copolymers, ethylene-butene-1 copolymers as well as terpolymers of ethylene with propylene and one

Diene, such as hexadiene, dicyclopentadiene or ethylidene norbonene.

4. Polystyrene.

5. Copolymers of styrene or cc-methylstyrene with dienes or acrylic derivatives such as styrene-butadiene, styrene-acrylonitrile, Styrene-acrylonitrile-methyl acrylate; Mixtures of high impact strength made from styrene copolymers and another polymer such as a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; as well as block copolymers of styrene, such as styrene-butadiene-styrene, styrene-isoprene-styrene or Styrene-ethylene / butylene-styrene.

6. Graft or graft copolymers of styrene, such as styrene including polybutadiene, styrene and acrylonitrile on polybutadiene as well as their mixtures with the copolymers mentioned under 5), as they are known as so-called ABS polymers.

7. Halogen-containing polymers, such as polyvinyl chloride, polyvinylidene chloride, Polyvinyl fluoride, polychloroprene, chlorinated rubbers and copolymers such as vinyl chloride vinylidene chloride, Vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.

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8. Polymers that differ from «., /! - unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitrile.

9. Polymers that are different from unsaturated alcohols and Derive amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, maleate, polyvinyl butyral, polyallyl phthalate, polyallyln; elamine and their copolymers with other vinyl compounds, such as ethylene / vinyl acetate copolymers.

10. Homo- and copolymers of epoxies, such as polyethylene oxide, polypropylene oxide or their copolymers with bisgycidyl ethers.

11. Polyacetals, such as Polyoxyiuethylene and Polyoxyäthylen, and those polyoxymethylenes known as Cornonoir.eres Contain ethylene oxide.

12. Polyphenylene oxides.

13. '>,. Polyurethanes and polyureas.

14. Polycarbonates.

15. Polysulfones.

16. Polyamides and copolyamides, which are different from Diaaiinen and dicarboxylic acids and / or of aminocarboxylic acids or the. derive corresponding lactams, such as polyamide 6, polyamide 5/6, polyamide 6/10, polyamide 11, polyamide 12.

17. Polyesters, which are different from dicarboxylic acids and dialcohols and / or derived from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate. Polybutylene terephthalate, Poly-1,4-dimethylol-cyclohexane terephthalate.

18. Crosslinked polymers, which are made up of aldehydes on the one hand and phenols, ureas and melamines on the other derive, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.

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¹⁹ · Alkyl resins, such as glycerol-phthalic acid resins and their mixtures with melamine-formaldehyde resins ... 20, Unsaturated polyester resins, which are derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, as well as vinyl compounds as crosslinking agents, as well as their halogenated, ' flame-retardant modifications.

²¹ · Cross-linked epoxy resins derived from polyepoxides, for example from bis-glycidyl ethers or from cycloaliphatic diepoxides.

22. Natural polymers such as cellulose, rubber, procaine, as well as their polymer-homologous chemically modified Derivatives such as cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose.

23. Silicone resins, rubbers and oils.

Of these polymers, groups 1-6, 13 and 17 are to be emphasized, since the stabilizers according to the invention have a particularly striking effect in these substrates.

The compounds of the formula I are calculated for the substrates in a concentration of 0.01 to 5% by weight on the material to be stabilized.

Preferably 0.02 to 1.0, particularly preferably 0.05 to 0.5 wt .-% of the compounds, calculated on the material to be stabilized, incorporated into this. The incorporation can, for example, by mixing in at least one of the compounds of the formula I and, if appropriate, further additives according to the methods customary in the art or during the shaping, or by applying the dissolved or dispersed compounds to the polymer, optionally take place with subsequent evaporation of the solvent.

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The compounds of the formula I can also be added before or during the polymerization, with by stabilized a possible incorporation into the polymer chain Substrates can be obtained in which the stabilizers are not volatile or extractable.

Examples of further additives with which the stabilizers can be used together are to to name:

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1. Antioxidants

1.1. Simple 2,6-DinI k ylphenole such as 2,6-di-tert-butyl-4-methyl phenol, 2-tert-butyl-4,6-di-methyl phenol, 2,6-di-tert.biityl-4 -raethoxymethylphenol, 2,6-dioctadecyl-4-methylphenol.

1.2. Derivatives of alkylated hydroquinones , such as, for example, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-arayl hydroquinone, 2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl -4-hydroxy-anisole, 3,5-di-tert-butyl-4-hydroxy-anisole, tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite, 3,5-di-tert. butyl 4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.3. Hydr'oxylierte Thiodiphenvläther , such as

2,2'-thiobis- (6-tert-butyl-4-methylphenol), 2,2'-thiobis- (4-octylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol, 4,4'-thiobis-CSjO-di-sec. amylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-bis (2,6-diethyl-4-hydroxyphenyl) ~ disulfide.

1.4. . Alkylidene bisphenol e, such as'

2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2.2 ^l -methylene bis (6-tert-butyl-4-ethylphenol), 4,4'-ethylenebis (6-tert butyl ~ 2-methylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,6-di- (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4 methylphenol, 2,2'-methylenebis [4-raethyl-6- (amethylcyclohexyl) phenol], l, l-bis (3,5-dimethyl-2-hydroxyphenyl) butane, l, l-bis- (5 * -tert .butyl-4- ■ hydroxy-2-methylphenyl) -butane, 2.27Bis- (3,5-di-

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tert-butyl-4-hydroxyphenyl) propane, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,2-bis (5-tert. butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylcapto-butane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane, ethylene glycol bis - [3,3-bis- (3'-tert-butyl-4 ¹ -hydroxyphenyl) -butyrate J.

1.5. 0-, N- and S-Benzy! Compounds , such as' for example

• 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzy1-ether, 4-hydroxy-3,5-diniethylbenzyl-mercaptoacetic acid octadecyl ester, Tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate.

1.6. Hydroxybenzylated malonic esters , such as 2,2-bis- (3,5-di-tert-butyl-2-hydroxybenzyl) -malonic acid dioctadecyl ester, 2- (3-tert-buty1-4-hydroxy-5-methylbenzyl) -malonic acid dioctadecyl ester, 2.2-

- Bis- (3,5-di-tert-butyl-4-hydi-oxybenzyl) -malonic acid didodecyl nercaptoethyl ester, 2,2-bis- (3,5-di-tert-butyl-4-hydroxybenzyl) -malonic acid di-f4- (l, 1,3,3- ' tetraine thy! butyl) phenyl] ester.

1.7. ' Hydroxybenzyl Arorr.aten , such as

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

1.8. s-triazine compounds , such as, for example, 2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -s-triazine, 2-octyltnercapto-4,6-bis- (3,5 -di-teft.butyl-4-hydroxy-anilino) -s-triazine, 2-octylmercapto-4,6-bis- (3,5-di-tert-butyl-4-

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hydroxyphenoxy) -s-triazine, 2,4,6-tris- (3,5-ditert .butyl-4 ~ hydroxyphenoxy) -s-triazine, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenylethyl) -s ~ triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate.

1.9. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid , V7ie e.g.

1,3,5-tris- (3,5-di-tert-butyl-4-hydroxyphenyl-propionyl) -hexanhydro-s-triazine, N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenyl-propionyl) -hexamethylenediamine.

1.10. 'Este r der ß- (3, 5-di-tert .buty: L-4-hvdroxy phep.vl ·) -

propionic acid with mono- or polyhydric alcohols, such as with

Methanol, ethanol, octadecanol, I ₁ 6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentyl glycol, pentaerythritol, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylhexanediol Sthan, trimethylolpropane, tris-hydroxyethyl isocyanurate, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane.

1.11. " Ester of the S- (5-tert .butvl-4-hvdroxv-3-: net'hvlphen vl ·) -

propionic acid with mono- or polyhydric alcohols, such as with

Methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, Diethylene glycol, thiodiethylene glycol, neopentyl glycol, Pentaerythritol, 3-thia-undecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolethane, Trimethylolpropane, trishydroxyethyl isocyanurate, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane.

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1.12. Esters of 3,5-di-tert-butyl-4-hydroxyphGnylessig; - Acid with mono- or polyhydric alcohols such as with

Mathanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, Diethylene glycol, thiodiethylene glycol, neopentyl glycol, Pentaerythritol, 3-thia-undecanol, 3-thiapentadecanol, Triinethylhexanediol, Trimethyloläühan, Trimethylolpropane, tris-hydroxyethyl isocyanurate, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2, 2, 2] octane.

1.13. Acylaminophenols V7ie e.g.

N- (3,5-di-tert-butyl-4-hydroxyphenyl) -stearic acid amide, K, N ¹ -di (3,5-di-tert-butyl-4-hydroxyphenyl) -thiobisacetamide.

1.14. B enzylphosnhonate such as

3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid-. dimethyl ester, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid diethyl ester, 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid dioctadecyl ester, 5-tert-butyl-4-hydroxy-3-methylbenzyl-phosphonic acid dioctadecyl ester.

1.15 AminoaryI derivatives such as

Phenyl-1-naphthylamine, phenyl-2-naphthylamine, K, N ¹ -di-phenyl-p-phenylenediamine, N, N ¹ -di-2-naphthylp-phenylenediamine,

N, N ¹ -Di-sec.but3 ^T lp-phenylenedianiine, 6-ethoxy-2 _J 2,4-trimethyl-1,2-dihydroquinoline, 6- - dodecyl-2,2,4-trimethyl-1,2- dihydroquinoline, mono-

tind dioctyliminodibenzyl, polymerized 2,2,4- ■ Trimethyl-1,2-dihydroquinoline. Octylated di-

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phenylamine, nonylated diphenylamine, ft-phenyl-N ¹ -cyclohexyl-p-phenylenediamine, N-phenyl-N'-isopropylp-phenylenediamine, N, N'-di-sec.octyl-p-phenylenediamine, N-phenyl-N ' -sec.octyl-p-phenyl-endiaπlin, N ₁ N'-di- (1,4-dimethylpentyl) -p-phenyl-endiaΓnine, N, N'-dimethyl-Ν, Ν ¹ -di- (sec Octyl) -p-phenylendiamine, 2,6-dimethyl-4-methoxyaniline, 4-ethoxy-N-sec-butylaniline, diphenylamine-acetone condensation product, aldol-1-naphthylamine, phenothiazine.

2. UV absorbers and light stabilizers

2.1. 2- (2'-Hydroxyphenyl) -benzotriazoles , such as the

5'-methyl-, 3 ', 5'-di-tert-butyl-, 5'-tert-butyl-, 5' - (I, 1,3,3-tetramethylbutyl) -, 5-chloro-3 ', 5'-di-tert-butyl-, 5-chloro-3'-tert-butyl-5'-methyl-, 3'-sec-butyl-5'-tert-butyl-, 3'-α-methylbenzyl-5'- methyl, 3'-α-methylbenzyl-5 ¹ -methyl-5-chloro, 4'-hydroxy, 4'-methoxy, 4'-octoxy, 3 ', 5'-di-tert-amyl, 3'-methyl-5 ¹ -carbomethoxyethyl, 5-chloro-3 ', 5'-di-tert-amyl derivative.

2.2. 2 \ 4-bis (2 '-hydroxyphenyl) -a ^ ky ^ -triazine ,.: · Such as

6-ethyl-, 6-heptadecyl-, 6-undecyl derivative.

2.3. 2-Hydroxybenzophenones , such as 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2 ', 4 * -trihydroxy-, 2'-Hydroxy-4,4'-dimethoxy derivative. £

2.4. 1,3-bis- (2'-hydroxybenzoyl) -benzenes , such as

"1,3-bis (2'-hydroxy-4'-hexyloxy-benzoyl) benzene, 1,3-bis (2'-hydroxy-4'-octyloxy-benzoyl) -benzene, 1,3-bis- (2'-hydroxy-4'-dodecyloxy-benzoyl) -benzene.

"609850/1042

2.5. Esters of optionally substituted benzoic acids, such as

Phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, Bis (4-tert-butylbenzoyl) resorcinol, Benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester or -octadeeylester or -2-methyl-4,6-di-tert-butylphenylester.

2.6. Acrylates , such as

Ethyl a-cyano-β-diphenylacrylate or isooctyl ester, methyl α-carbomethox3 ⁷ -cinnamate, methyl α-cyano-β-methyl-p-methoxy-cinnamate, N- (β-carbomethoxyvinyl) -2 -meChylindolin.

2.7. Kickel compounds such as "-Nickelkoinplexe des 2,2'-thio-bis [4- (1,3,3,3-tetramethylbutyl) -phenol], like the 1: 1 or the 1: 2-KotnpleXj optionally with additional Ligands such as n-butylamine, triethanolamine or N-cyclohexyldi-ethanolarain, nickel complexes of bis [2-hydroxy-4- (1,1,3,3-tetramethylbutyl) phenyl] sulfone, such as the 2:! Complex, optionally with additional ligands such as 2-ethylcaproic acid, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-ditert.butylbenzyl-phosphonic acid monoalkyl esters such as methyl, ethyl or butyl esters, nickel complexes of ketoximes such as 2-hydroxy-4-methylphenyl Undecyl ketone oxime, nickel 3,5-di-tert-butyl-4-hydroxybenzoate, nickel isopropyl xanthate.

2.8. Sterically hindered amines, such as A-benzoyloxy ^^. Öjö-tetramethylpiperidine, 4-stearoyloxy-2, -2 _> "6,6-tetramethylpiperidine, bis-

6 0 9850/1042

26218Λ2

(2,2,6, β-tetramethylpiperidyl) sebacate, 3-n -oetyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro [4.5 I-decane-2,4-dione.

2.9. Oxalic acid diazides , such as

4,4 ^l -di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5 ¹ -di-tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl -oxanilid, 2-ethoxy-2 ^r, ethyl-oxanilide, N, N '~ bis (3-dimethylamiriOpropyl) -oxalamj-d, 2-ethoxy 5-tert-butyl-2'-ethyl-oxanilind and its mixture with 2-ethoxy-2'-ethyl-5,4 ¹ -di-tert-butyl-oxanilide, mixtures of ortho- and para-methoxy and o- and p-ethoxy-disubstituted oxanilides.

3. Metal deactivators , such as

Oxanilide, isophthalic acid dihydrazide, sebacic acid bis-phenylhydrazide, bis-benzylidene-oxalic acid dihydrazide, N ₁ N'-diacetyl-adipic acid dihydrazide, Ν, Ν ^1- bis-salicyloyl-oxalic acid dihydrazide, N, N ¹ -bis-salicyhydrazide, N, N 1 '-Bis-CS.S-di-tert.butyl-4-hydroxyphenylpropionyl) hydrazine, N-salicylal-N ^r salicylidene hydrazine, S-salicyloylamino-l ^^ - triazole.

4. Phosphites , such as. Triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tri- (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, 3,9-di-isodecyloxy-2,4,8 _} 10-tetroxa-3,9-diphospha-spiro [5,5] undecane, tri- (4 ~ hydroxy-3,5-di-tert-butylphenyl) phosphite.

5. Peroxide-destroying compounds , such as esters of jS-thio-dipropionic acid, for example lauryl, stearyl, myristyl or tridecyl

60 9850/104 2

ester, mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole .

6. Polyamide stabilizers such as copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

7.. Basic co-stabilizers , such as

Melamine, benzoguanamine, polyvinylpyrrolidone, dicyandiamide, Triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, Alkali and alkaline earth salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate, K palmitate, antimony catecholate or tin catecholate.

8. PVC stabilizers , such as

Organic tin compounds, organic lead compounds, barium-cadmium salts of fatty acids.

9. " Nucleation agents , such as ζ.B.

4-terL.Butylbenzoic acid, adipic acid, diphenylacetic acid.

10. Urea derivatives , such as
N-cyclohexyl-N'-1-naphthyurea, N-phenyl-NN ¹ · dicyclohexylurea, N-phenyl-N'-2-naphthylurea , N-phenylthiourea, N, N'-dibutylthiourea .

11. Other additives , such as

Plasticizers, lubricants, emulsifiers, fillers, soot, asbestos, kaolin, talc, glass fibers, pigments, Optical brighteners, flame retardants, antistatic agents,

609850/1042

The use of the stabilizers of the formula I in combination with the antioxidants given in the above list is particularly effective in polyolefins.

When combining such known plastic additives with the compounds of the formula I, synergistic Effects occur, especially with groups 2 and 3 mentioned in the above list «

The following examples illustrate the preparation of the compounds of formula I and their use as stabilizers for polymers. The parts specified therein are weight parts, Percentages are percentages by weight.

6 09850/1042

Examples 1-9

38 g (0.15 mol) of diphenyldichlorosilane are stirred into a solution of 50 g (0.5 mol) of 2,2,6,6-tetramethyl-4-hydroxypiperidine in 500 g of dry triethylamine at 85 ^° C. within 15 minutes added dropwise. Then for 1 hour at 90 ^c C is heated. The triethylamine hydrochloride precipitated during the reaction is filtered off. It weighs 41 g, which corresponds to an almost quantitative implementation. The filtrate is subjected to fractional distillation. At 195 ° and 0.001 Torr, the diphenyl-bis- (2,2,6,6-tetramethylpiperidin-4-oxy) -silane (compound no. 1) passes over as a light yellow liquid which crystallizes in the original. Mp 69-71 ° C. Yield 66g = 90%.

Analysis (C ₀₀ H, _c N _o 0 _o Si)

Calculated C 72.82. H 9.36 N 5.66 Si 5.67% Found C 72.7 H 9.6 N 5.5 Si 6.0%.

Using the same method, 2,2,6,6-tetramethylpiperidinol-l with the corresponding stoichiometric amounts of

a) trimethylchlorosilane

b) phenyltrichlorosilane

c) methyltrichlorosilane

d) dimethyldichlorosilane

e) methyl-phenyl-dichlorosilane

f) methyldichlorosilane

g) trichlorosilane

h) triphenylchlorosilane

implemented and thereby the following compounds of formula I obtain

609850/1042

as-

a) 2,2,6,6-tetramethyl-4-trimet: hylsiloxy-piperidine (Compound No. 2), a colorless oil, Sdp.-, ₂ 85-87 ° C, yield 94%..

b) Phenyl-tris- (2,2,6,6-tetramethylpiperidin-4-oxy) -silane (Compound No. 3), colorless oil, bp 192-195 ° C / 0.001 Torr, yield 85%.

c) methyl-tris- (2,2,6,6-tetramethylpiperidin-4-oxy) -silane (Compound No. 4), OeI, bp 155-160 ° C / 0.001 torr, yield 70%.

d) dimethyl-bis (2,2,6,6-tetramethylpiperidin ~ 4-oxy) silane (compound no. 5), bp. 110-115 ° C / 0.001 torr; mp. 51-53 ^C C, yield 70%.

d) Methyl-phenyl-bis- (2,2,6,6-tetramethylpiperidin-4-oxy) silane (compound no. 6), oil, bp. 160-165 ^c C / 0.001 torr; yield 80%.

f) Methyl bis (2,2,6,6-tetramethylpiperidin-4-oxy) -silane (Compound No. 7), bp 115-12O ⁰ CZO ^ OOl Torr, mp 35-37 ° C, yield 53%.

g) Tris- (2,2,6,6-tetramethylpiperidin-4-oxy) silane (compound No. 8), bp 170 ° C / 0.001 Torr, yield 47%.

h) 2,2,6,6-Tetramethyl 1-4-triphenyl-siloxypiperidine (compound

No. 9), m.p. 109 ° C.
Example 10 and 11

10.9 g (0.1 mol) of trimethylchlorosilane are stirred into a solution of 17.1 g (0.1 mol) of l, 2,2,6,6-pentamethyl-4-hydroxypiperidine and 10.1 g (0.1 mol) of triethylamine in 200 ml dripped dry tetrahydrofuran. To complete the reaction, the mixture is then refluxed for 1 hour. The precipitated triethylamine hydrochloride is filtered off, the filtrate evaporated and the oily residue in the Vacuum distilled. 21.7 g (90%) of 1,2,2,6,6-pentamethyl-4-trimethylsiloxypiperidine are obtained (Compound No. 10), that

609860/1042

Distilled at 100-101 ° C / 12 Torr as a colorless oil.

Instead of tetrahydrofuran, benzene, dioxane or xylene can be used as the solvent for the reaction without that the yield changes noticeably.

If, in the above example, 29.4 g of triphenylchlorosilane are used instead of the trimethylchlorosilane, 39.8 g (90.5%) of 1,2,2,6,6-pentamethyl-4-triphenylsiloxypiperidine (compound no . 11) as a crystalline substance which melts at 109-110 ⁰ C.

Example 12

34.2 g (0.2 mol) 1,2,2,6,6-pentamethyl-4-hydroxypiperiaine ' and 20.2 g (0.2 mol) of triethylamine are in 250 g of benzene solved. 20.3 g (0.1 mol) of l, 3-dichloro-l, l, 3,3-tetramethyldisiloxane are added dropwise to this solution with stirring. Afterward is heated to reflux for 2 hours. After cooling, the precipitated hydrochloride is filtered off and the filtrate evaporated. The viscous residue is taken up in hexane to remove the last residues of triethylamine hydrochloride to separate. The hexane solution is evaporated and the residue is dried in vacuo. This leaves 40 g (85%,) 1,3-bis- (1,2,2,6,6-pentamethylpiperidin-4-oxy) -1,1,3,3-tetramethyldisiloxane (Compound No. 12) as a viscous mass.

Analysis (

Calculated C 60.0 H 11.09 N 5.95 Si 11.88% Found C 60.3 H 11.5 N 5.7 Si 12.4%

609.850 / 1042

Example 13

100 parts of polypropylene powder (Moplen, Fiber Grade, from Montedison) are mixed with 0.2 parts of ß- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester as an antioxidant and 0.25 or 0 , 5 parts of a stabilizer of the following ^{homogenized in the Brabender plastograph at 200 °} C. for 10 minutes. The mass obtained in this way is removed from the kneader as quickly as possible and pressed into a 2-3 mm thick plate in a toggle press. Part of the raw pressed part obtained is cut out and pressed between two high-gloss hard aluminum foils with a hand-hydraulic laboratory press for 6 minutes at 260 ° and 12 tons of pressure to form a 0.5 mm thick foil, which is immediately quenched in cold water. The 0.1 mm thick test film is produced from this 0.5 mm film under exactly the same conditions. Sections of 60 44 mm each are punched out of this and exposed in the Xenotest 150. These test specimens are removed from the exposure apparatus at regular intervals and checked for their carbonyl content in an IR spectrophotometer. The increase in the carbonyl extinction on exposure is a measure of the photoxidative degradation of the polymer (see L. Balaban et al., J. Polymer Sci. Part C, 22, 1059-1071 (1969); JF Heacock, J. Polymer Sci. Part AI, 22_, 2921-34 (1969); DJ Carlsson and DM. Wiles, Macromolecules 2 ^, 587-606 (1969)) and experience has shown that it is associated with a decrease in the mechanical properties of the polymer. For example, the film is completely brittle when it reaches a carbon extinction of approx. 0.300.

The protective effect of the stabilizers according to the invention is can be seen from the following table 1:

6-0 9850/1042

Table 1

stabilizer
(Example no.) Exposure time
hours I.
CO absorbance
(5.85 μ) without 1050 0.30 1 0.25% 8000 0.05 5 0.25% 5200 0.03 11 0.5% 23 ¹ OCO 0.3 12 0.5% 8000 <o.oi

609850/1042

Claims (1)

Patent claims! / ■ / or an SMure addition salt thereof, v / orin 2 R and R independently of one another are alkyl with 1-4 carbon atoms, or together with the carbon atom to which they are bonded are, a cyclopentane or cyclohexane ring or a 2, 2, 6,6-tetramethylpiperidine ring, 3
R is hydrogen, methyl, phenyl or vinyl, 5 R and R independently of one another are hydrogen, methyl, phenyl, vinyl, alkoxy with 1-8 carbon atoms, alkoxyalkoxy with 3-10 carbon atoms, cyclohexoxy, aralkoxy with 7-8 carbon atoms, Phenoxy or substituted phenoxy (where the substituents are chlorine, alkyl C 1-4 or alkoxy Can be C 1-4), or a radical of the formula CH 3 represent 4, and when R and R are hydrogen, methyl, phenyl or vinyl, R is also one 609 8 * 50/1042 Remainder of the formula _J η can represent where η is an integer from 1-10, and Hydrogen, alkyl with 1-12 carbon atoms, alkenyl with 3-6 carbon atoms, alkoxyalkyl. with 3-14 carbon atoms, arslkyl with 7-8 carbon atoms or an aliphatic acyl group with 1-4 carbon atoms, or one of the groups -CH ₂ COOR ⁶ , -CH ₂ -CH (R ⁷ ) - OR ⁸ or -COOR ⁹ means in which Alkyl with 1-8 carbon atoms, alkenyl with 3-6 carbon atoms, phenyl, aralkyl with 7-8 carbon atoms or cyclohexyl, Hydrogen, methyl or phenyl, hydrogen or an aliphatic, aromatic, araliphatic ^ or alicyclic acyl group with up to 2u 18 carbon atoms, optionally in the aryl radical substituted by chlorine, alkyl with 1-4 carbon atoms, alkoxy with 1-8 carbon atoms and / or hydroxyl can be, and Alkyl with 1-8 C atoms, benzyl, phenyl or cyclohexyl is. 2. The method according to claim 1, characterized by the addition of a compound of the formula I in which X is hydrogen, alkyl having 1-4 carbon atoms, acetyl, Acrylic or crotonyl,
R ¹ and R ^{2 are} methyl 609 8 * 5 0/1042 R. Hydrogen, methyl or phenyl and 4 5
R and R independently of one another are methyl, phenyl or the remainder CH N-X mean. 3. The method according to claim 1, characterized by the addition of a compound of the formula I in which X is water 12 3 substance or methyl, R and R methyl, R methyl or phenyl and R and R independently of one another are methyl, phenyl or the radical CH Ή— X mean. 4.. Process according to claim 1, wherein the organic polymer is a polyolefin or a styrene homo- or copolymer is. 5. The method according to claim 1, wherein the organic polymer is a polyurethane or polyamide. ■ 609850/1042 6. The method according to claim 1, wherein one or more known and customary additives can be added together with the stabilizer of the formula I. 7. Organic polymer stabilized against light degradation, characterized by a content of 0.01 to 5% by weight a compound of the formula I of claim I. 8. Stabilized polymer according to claim 7, the one Stabilizer of the formula I of claim 2 contains. 9. Stabilized polymer according to claim 7, wherein the polymer is a polyolefin or a styrene homo- or copolymer is. 10. Stabilized polymer according to claim 7, wherein the Polymer is a polyurethane or a polyamide. 11. Stabilized Po ^ mer according to claim 7, which also contains other common additives. 12. A stabilized polymer according to claim 11, which also contains one or more conventional antioxidants. (D links the Formula I. CH- CII R ³ /
. Χ — Κ " > ■ —0 — Si — R ⁴ . S.
R ^ R ⁵ 609850/1042 or their acid addition salts, x-7orin 2 R and R independently of one another are alkyl with 1-4 carbon atoms, or together with the carbon atom to which they are bonded, a cyclopentane or cyclohexane ring or a 2,2,6,6-tetramethylpiperidine ring, R "hydrogen, methyl, phenyl or vinyl, 5 R and R independently of one another are hydrogen, methyl, phenyl, vinyl, alkoxy with 1-8 carbon atoms, alkoxyalkoxy with 3-10 carbon atoms, cyclohexoxy, aralkoxy with 7-8 carbon atoms, Phenoxy or substituted phenoxy (in which the substituents are chlorine, alkyl C 1-4 or alkoxy Can be C 1-4), or a radical of the formula CH M-X represent, and when R ″ and R are hydrogen, methyl, phenyl or vinyl, R is also a radical of formula -0 — Si can represent, wherein η is an integer from 1-10, and Hydrogen, alkyl with 1-12 carbon atoms, alkenyl with 3-6 carbon atoms, alkoxyalkyl with 3-14 carbon atoms, 609 8'5 0/1042 Aralkyl with 7-8 carbon atoms or an aliphatic acyl group with 1-4 carbon atoms, or one of the groups -CH ₂ COOR ⁶ , -CH ₂ -CH (R ⁷ ) -OR ⁸ or -COOR ⁹ , in which R alkyl has 1-8 carbon atoms, alkenyl with 3-6 carbon atoms, phenyl _t aralkyl with 7-8 carbon atoms or cyclohexyl, R hydrogen, methyl or phenyl, R is hydrogen or an aliphatic, aromatic, araliphatic or alicyclic acyl group up to 18 carbon atoms, which may be in the aryl radical by chlorine, alkyl with 1-4 C-x ^ .tomen, alkoxy with 1-8 C atoms and / or hydroxyl can be substituted, and R alkyl with 1-8 C-acomes, benzyl, phenyl or cyclohexyl is. 14. Compounds according to claim 13 of the formula I, in which X hydrogen, alkyl with 1-4 carbon atoms, acetyl, acrylic or crotonyl, R ¹ and R ^{2 are} methyl 3
R is hydrogen, methyl or phenyl and R and R independently of one another are methyl, phenyl or the remainder CH mean. 609850 / 10-4 2 15. Compounds according to claim 13 of the formula I, wherein X is hydrogen or methyl R ¹ and R ^{2 is} methyl 3
R methyl or phenyl 4 5 R and R independently of one another are methyl, phenyl or den rest CH IT-X CH. 16. Procedure formula 1 Establishing connections of the Si-R (I) R- wherein 1 2 R and R independently of one another are alkyl with 1-4 carbon atoms, or together with the carbon atom to which they are bonded are, a cyclopentane or cyclohexane ring or a 2,2,6,6-tetramethylpiperidine ring, 3
R is hydrogen, methyl, phenyl or vinyl, R and R independently of one another are hydrogen, methyl, phenyl, vinyl, alkoxy with 1-8 carbon atoms, alkoxyalkoxy with 3-10 carbon atoms, cyclohexoxy, aralkoxy with 7-8 carbon atoms, Phenoxy or substituted phenoxy (in which the substituents are chlorine, alkyl C 1-4 or alkoxy 609850/1042 - 34 * - Can be C 1-4), or a radical of the formula represent, and when R and R are hydrogen, methyl, phenyl or vinyl, R is also a radical of formula R- N-X can represent, wherein η is an integer from 1-10, and Hydrogen, alkyl with 1-12 carbon atoms, alkenyl with 3-6 carbon atoms, alkoxyalkyl with 3-14 carbon atoms, aralkyl with 7-8 carbon atoms or an aliphatic acyl group with "1-4 carbon atoms, or one of the groups -CH ₂ COOR ⁶ , -CH ₂ -CH (R ⁷ ) -OR ⁸ or -COOR ⁹ , denotes in which Alkyl with 1-8 carbon atoms, Alken} ^r l with 3-6 carbon atoms, phenyl, aralkyl with 7-8 carbon atoms or cyclohexyl, hydrogen, methyl or phenyl, hydrogen or an aliphatic, aromatic, araliphatic .or alicyclic acyl group with up to 18 carbon atoms, which may be substituted in the aryl radical by chlorine j alkyl with 1-4 carbon atoms, alkoxy with 1-8 carbon atoms and / or hydroxyl 609850/1042 can, and R is alkyl with 1-8 carbon atoms, benzyl, phenyl or cyclohexyl, characterized in that - = das-s. one mole a compound of the formula II - CH,
X-H> -OH. II O / he with one mole of a compound Y-Si (R) (R ^) (R) or with 0.5 mole of a compound (Y) ₀ Sl (R) (R ') 3 or with 0.33 mol of a compound (Y) -Si (R) to- TOO / CT sets, in which X, R, R * ", R, R", R are those given above Has meaning and Y is halogen, alkoxy, dialkylamino or acyloxy. 17. The method according to claim 16, wherein Y is chlorine. 18. The method according to claim 17, characterized by the addition of a tertiary amine in an amount of at least 1 mole per mole of compound II. 19. The compound according to claim 13, 2, 2, 6,6-tetramethyl-4-triphenylsiloxypiperidine. 20. The compound according to claim 13, 1,2,2,6,6-Penta ~ methyl-4-triphenylsiloxypiX) eridiri. 21. The compound according to claim 13, diphenyl-bis (2,2,6,6-tetramethylpiperidin-4-oxy) -silane. 22. The compound according to claim 13, diphenylbis (1, 2, 2, 6, 6 "pentamethylp3.peridin-4-oxy) -silane. 23. The compound according to claim 13, dimethyl bis (2,2,6,6-tetramethylpiperidin-4-oxy) silane. 609850/1042 ORfGlNAL INSPECTED