DD278140A1 - PROCESS FOR STABILIZING HIGH POLYMER LOW-MOLECULAR ORGANIC COMPOUNDS AND OILS - Google Patents

Abstract

The invention relates to a process for the stabilization of high polymers, low molecular weight organic compounds and oils. The aging of the materials mentioned as a result of the action of heat and the action of atmospheric oxygen and water in the presence of light and at elevated temperatures to be prevented or drastically delayed by the use of good loeslicher or well-tolerated, low volatility and little migrating in polymers stabilizers to the life the high polymers, low molecular weight organic compounds and oils to extend. In accordance with the invention, the stabilizers used are compounds which, by reacting calix ethers with glycidic ethers and substances bearing stabilizer groups, such as e.g. As amines, alcohols and carboxylic acids were obtained. Polymers are added to the stabilizers during post-processing or shaping. In liquid hydrocarbons they are dissolved.

Description

For this 1 page drawing and 1 page formulas

Field of application of the invention

The invention relates to the stabilization of high polymoron, low molecular weight organic compounds and oil gogen the degradation by oxidation and heat and by oxidation in the presence of light.

Characteristic of the prior art

The stabilizing effect of phonetic compounds such as 2,6-dietit.-butyl-4-methylphenol is known. It is also known that sterically hindered amines (HALS) in polymeric materials and low-molecular Omani compounds prevent the oxidation in Gegonwarl ve .ι l.icht or drastically delay. Because of their volatility, low molecular weight compounds wio have the 2,6-di-tert-butyl-4-methylphenol noo langzoite effect as stabilizers. Particularly high is the loss of effectiveness at temperatures above 400K, as they occur in the Verarboitungsphase of Poylmeren. It is known that by increasing the molecular weight of the stabilizers their volatility is reduced. According to SU 1109414 wordon opoxidiorto butadiene-isoprene copolymero with 3,5Di-tert-4-hydroxyphonyl-propionsäuro umgesotzt and the erhhaenen compounds used as stabilizers. A disadvantage is that the epoxidized starting compounds, hergastellt by oxidation of the copolymer with Porsäuren or Andoren peroxides, still contain a certain amount of olefinic double bonds. These are disadvantageous for c'as photooxidalive smelting of the polymer mixture. According to a number of patents (DE-OS 2821 579, EP-PS 76067, BE-PS 862958) weroen stabilizers used for polymers obtained by reacting the Glycidylvnrbindungen from glycerol, bisphenol A and from cyanuric acid with stabilizer group-carrying carboxylic acids or amines ,

These compounds have only the same Siabilisatorgruppen (only sterically hindered phonol groups or HAI S-Giuppen). Disadvantages of these compounds are that they are incompatible with polyolefins and other polymers and are therefore difficult to incorporate and have favorable activities on account of their polar character.

In low molecular weight organic compounds, these compounds are poorly soluble in the toil and poorly prevent auto-oxidation.

Object of the invention

Object of the invention is os, the aging of Hochpolvmeren, low molecular weight organic compounds and oils due to exposure before; Prevent heat or exposure to atmospheric oxygen in the presence of light and at elevated temperatures by using readily soluble or well-tolerated, low-volatility and little migrating in polymers stabilizers and thus to extend the life of said materials.

Explanation of the essence of the invention

The object of the invention is to develop new substances which cause an increase dor thermal, thermooxidative and dor photooxidativen stability of organic compounds at low and high temperatures and in the / u protective material easily einarbeitbar and redistributable. This invention is achieved by a process for stabilizing Kochpolym6ren, low molecular weight organic compounds and oils, in particular of polyolefins and Oiefincopolymeren, ABS and rubbers, against the thermooxidative, photooxidativor, and thormischen Abbai '.lurch incorporation of stabilizers, according to the invention as stabilizers compounds of general 't-'ormei

R ^3/1 ο

O - CH-CH-CH

be used, in dor

χ and y = -f-CR ⁵ H ⁶ -t- "with R ⁵ , R ⁶ = hydrogen. Alkyl, cycloalkyl, aralkyl, odor aryl and q - 1 to 3

odor χ and y = -CH ₂ -O-CH ₂ -; -CO- is,

Z = -O-; -S-; -NR ⁷ - with R '= hydrogen, alkyl, cycloalkyl, aralkyl, aryl or H ⁵ -CO groups,

R ', P ^? - hydrogen, alkyl or oin substituent gate alkyl radical Wf-CR ⁵ R ^e -} -, - in particular? with W = R ⁵ -O-CO-; R ⁶ R ⁶ N-CO-R ⁵ -C0-; Halogen-; R ⁵ R ⁶ -N-; Aryl and r = 1 to 30; a cycloalkyl radical or aryl radical,

OH (o, m, p)

- • CO + CIKR

With

R ⁸ R ⁹ R ¹⁰ R "- hydrogen, alkyl, cycloalkyl, aryl, aralkyl or a Hydroxvlrost and S = ΰ to 30 or

RKL- _R 10

V \

where R "is hydrogen, alkyl, cycloalkyl, aryl, aralkyl, hydroxyl, R ⁵ -O-, R ⁵ -C i- or R ³ = alkyl (C ₉ to C ₃₀₎ odor R ^I3 -CO- where R ' ³ = C ₉ to C ₃₀ K ¹ =' hydrogen, alkyl, cycloalkyl ', -CO- or

-GO-J-CR ⁵ R ⁶

(O, m, p)

a = 1 to 12 and

b = 0 to 11, where a + b = η = 2 to 12.

In particular, compounds of general formula I are used in which a + b = 4,6 or 8, where a = 1 to 8 and b - - 0

to 7 is.

A particularly good stabilizing effect in the polymer is achieved when so-called mixed-modified compounds of general Forrrel I are used with a = 2 to 8, in donen at least one radical R ³ or rust R * a compatibility with the substrate-promoting group, eg. B. alkyl radical R ¹³ - C ₉ to C, ₃ and the other Rosto R ^3, the stabilizer groups

6 5 6 1 / r ~ \ V-OH (o, m, p)

or.

are.

In high polymer, the compounds of formula I can also be used in combination with other excipients such as quonchorn, complex biuret, lubricants, UV absorbers and antistatic agents.

Dio stabilizers of general formula I are present in a concentration of 0.01 to 0.6 mass% in particular of 0.05 to 0.5 parts by mass in%, based on the amount of substrate, and in the polymer known Zusatzo in a concentration of 0.01 to 0.6% by massoantoilone, in particular from 0.05 to 0.3% by massoantoilone, bozogon by amount of substrate,

used.

Surprisingly, the compounds of formol I show low molecular weight single-molecule phenolone and low molecular weight photostabilizers as well as the calix (n-arenes themselves (formol I with b = η = 4,6,8; a = 0 and R ⁴ = H), especially the mixed-modifi ed ones Compounds having an excitability promoting the residue in the molecule have a significantly better antioxidant and photostabilizing effect in high polymer or antioxidant activity in low molecular weight

organic compounds.

Compounds dio particularly suitable as Stabilisatoron, z. Example, the following structures according to Formol I on:

a)? fb = η - 4, 6.8; where a = 1 to 8 and b = 0 to 7;

R ¹ - R ² - methyl-; t.-butyl; tert-amyl; iso-butyl; tert-octyl; iso-nonyl; -CH ₂ -CHj-W

x = y = -CH ₂ -

GH

CH

- NR ⁷ Λ 'nR ¹²

H-

with R '= R' ² - hydrogen; alkyl; -COC ₆ H ₆ ; -CO-CH ₃

CH- 'CH'

R ⁴ = hydrogen or R ⁵ -CO- with R ⁶ - alkyl; Phenyl, b) a + b = η = 4,6,8, where a = 1 to 8 and b = 0 to 7;

R '= R ² = methyl, t-amyl; iso butyl; t.-butyl, t.-octyl; isononyl ·; -CH ₂ -CH ₂ -W

X y CH ₂

-ZH ⁵ »-O-CO-f-CH

mitq = 0 to 2

R ⁴ = Wasse, Moff, -CO-R ⁵ with R ⁵ - alkyl-; Phenyl, c) a + b = η = 4, G, 8, where a = 2 to 8 and b = 0 to 6;

R '= R ² = methyl; t.-butyl; tert-amyl; iso-butyl; tert-octyl; iso-nonyl; -CH-CH ₂ -W

X = Y = -CH ₂ -,

being in the same molecule once

- Z - R-

-NE

and / at second

-ZR ³ = -N-R ' ³ with R' ³ = alkyl C ₁₂ to C ₁₈ ;

R ⁷ R ⁴ = hydrogen, R ⁵ -CO- with R ⁵ = alkyl; phenyl,

d) alb = 4,6,8, where a = 3 to 8 and b = 0 to 5;

R ¹ = R ² = methyl; · t-butyl; tert-amyl; isobutyl; tert-octyl; isononyl ·; -CH ₇ -CH ₇ -W;

X = V = -CH ₂ -;

being in the same molocule once

-ZR ⁵ = -NR ¹⁵

With

z-r5

- O - OO I OH ₂ J once _{? CH CH}

Ii ' $ 5

ZR ^{5 is} --N - NR ¹² .

OH, CH,

alkylG _Ar> to C "_Qi onceid io

t, -Bu OH

with q »0 bit 2 and

.-Bu

R ⁴ = Wassors.off, -CO-R ⁵ with R ^b = alkyl; phenyl

 These stabilizers according to the invention have been prepared from glycidyl ether chloride [c] n] areno (Kormel II).

0-CH ₂ -CH-CH ₂ ,

which are prepared by reacting calix (ni arene with F; :: chlorohydrine in the presence of a catalyst, by reversing with don corresponding carboxylic acids, alcohols, amines and mercaptans in various solvents, The formed secondary amine groups (-NH-) and hydroxyl groups ( -OH) can subsequently be reversed

be acylated with carboxylic acid chlorides or anhydrides.

Good polymer addition precursors are advantageously obtained when mixed modification with an aliphatic amine or with an aliphatic carboxylic acid of 1? to 18 carbon monohydric atoms (Section c and d), thereby obtaining molecules which, in addition to donating stabilizer groups (hindered amine, hindered phenol), have compatibility groups and very good effects as stabilizers.

The erfindungsrjernäßen compounds protect liquid hydrocarbons and especially high polymers such. As polyolefins, olefin copolymers, ABS and .Cautschuke against the thormooxidativen and photooxidative degradation.

The incorporation of the stabilizers takes place bokannterwoise for high polymers in the Austragsextruder, gegebononfalls together with other additives, wherein the best distribution of the excipient is achieved by a twin-screw extruder. Also oinu

Incorporation in the processing phase to the molding material is possible.

For the stabilization of liquid hydrocarbons, the compounds have been dissolved in the substrate.

The particular stabilizer according to the invention, in particular the mixed-modified compounds, is that they are very soluble and are compatible with polymers and have a good action with such a high molecular weight Stabilizers have such a low tendency to migrate from the polymer compared to bekannton low molecular weight phonolic antioxidants and amine light stabilizers.

embodiments

Preparation of Calix | n | Required for Stabilizer Production arenglycidether:

In einom heated Roakt'onsgefäß, equipped with stirrer, reflux condenser, thermometer and dropping funnel is the

respective starting calix [η] arone in a 10 to 50 (achon molaron excess of epichlorohydrin in the presence of 0.5 to 5.0 mass%, bozogon on CaNx [n] arene used, oror quorernary ammonium prebloration as Kntalysaior, preferably ) Totraothylammoniumbromid, at 340 to 400K suspondiort gobracht in oinom period of 5 to 25 hours to Rouhion and thereby leads into a homogono Phaso. Subsequently, 30 to 70% by weight of massoantoilo in alcohol, preferably isopropanol, and from 330 to 360K of 30 to 60% by weight of alkali metal hydroxide (sodium bis-potassium hydroxide), preferably as an aqueous solution containing 48 to 50% of massoantoilone in% Given roughness mixture. After boondetor addition of the alumina solution (30 to (50 min) the epichlorohydrin is boiled off in a vacuum of 2 to 2.5 kPa together with alcohol and water aco-otro The verbloibondo residue is dissolved in oinom hydrocarbon, preferably toluone or xylon, and boi 323 to 373 K) 348-350K, with Wossor gowaschon. Dio hydrocarbon phaso is abgotrennt from the aqueous Phaso, the solvent completely abdostilliort in a vacuum of 1.0 to 2.5 kPa. Dor residue is dried 0.5 to 1, OKPa

 In the examples following stabilizers were oingosotzt:

Stabilizer 1

15 g of tert-butylcalix [8 | arylglycidothor (Formula II, R '= R ² = tert-butyl; R ⁴ = H; χ- y = - -CH ₂ -; a ι b = 8) having an epoxide equivalent side (EA) = 425 Dissolved 50 ml of ethanol and heated to 60 C with stirring. Within 10 minutes, 6.2 g of 4-amino-2,2,6,6-totramothylpiporidine golöst in 10 ml of ethanol, the tompature increases to 343K. The mixture is then refluxed for 2 h, cooled to room temperature and the reaction solution is slowly grafted into 500 ml of cold water. It drops immediately from white to white-yellowish ore precipitate. This is isolated and dried in vacuo at room temperature

 Additional Pkt .: 463bis473K

 Yield: 15g £ 75%

Elemontaranalyso: C 74.62% H 9,72% N 5,29%

74.83% 9.79% 5.47%

Stabilizer 2

10 g of p-tert-butylcalix [6 |. Were added analogously to the instructions for stabilizer 1 aryl glycidyl ether (formula II, R ¹ = R ² = t-butyl; R ⁴ = H; χ = y -CH ₂ -; a + b = η = 6) with EA = 443 with 3,12g 4-amino- Reversed 2,2,6,6-totramothylpiperidine and worked up the reaction mixture

 Application-point: 413-423K Ausbouto: 6,2g A 50%

Elomontaranalyso: C 72.82% H 10.16% N 4.98%

72.98% 10.23% 4.93%

Stabilizer 3

7.6 g of p-tert-butyicalix (8-aryl glycidyl ether (formula II, R '= R ² = t-butyl; R ⁴ = H; χ = y = -CH ₂ -; atb = η = 8) with EE = 425 are dissolved in 100 ml of ethanol and heated under stirring to 333 K. To this solution is added a suspension of 1.25 g of primary eliphatic technical amine mixture with chain length C ₁₆ to C ₁₈ , in which reaction mixture fetiamin goes into solution of 10 min, 2.3 g of 4-amino-2,2,6,6-tetrnomothyl-piperidine are added dropwise and the mixture is refluxed for 2 hours After cooling to room temperature, it is added dropwise to 500 ml of water The precipitate is isolated, washed with H ₂ O and dried in a vacuum at room temperature

 Additional-Pkt .: 418bis423K Yield: 8,7g A 80%

Sabilisator4

Analogously to the instructions for stabilizer 3, 11 g of p-tert.-butylcalix | 8 | aryl glycidyl ether (Formula II, R '= R ² = tert -butyl; R ⁴ = H; χ = y = -CH; -; a + b - η - 8) with EA = 425 dissolved in 100 ml of ethanol, with 2 ₆ g of primary aliphatic technical amine mixture with initial lengths of C ₆ to C ₁₈ in 20 ml of ethanol and 1.6 g 4-amino-2,2,6,6-tetramethylpiperidine and reacted.

Additional Pkt .: 399bis405K

Yield: 7.5g & 50%

Stabilizer 5

Analogously to the instructions for stabilizer 3, 10 g of p-tert-butylcalix [6] Arylglycidethor (formula II, R '= R ² = tert-butyl: R ⁴ = H; X = V = -Ch ₂ -; a + b = η = 6!) with EA - 443, dissolved in 100 ml of ethanol, with 1.6 g of primary aliphatic technical amine mixtures with Kottenlängen of C ₁₆ to C, _e reacted in 20 ml of ethanol and 2g 4-amino-2,2,6,6-tetramothylaminopiperidine in 20 ml of ethanol and worked up.

Session no .: 393 to 403 K

Exhaustion: 8,2g £ 60%

Stabilizer 6

In a 1.5 l sulphonation flask with stirrer, reflux condenser and internal thermometer 22.5 g of p-tert-butylcalix | 8 | arylglycidether (Formula II, V ¹ = R ² = t-butyl; R ⁴ = H; χ = γ = -CH ₁ -, a fb ^ n = 8) = mitEÄ dissolved in 150ml of xylene and heated to 490 Sioden. Thereafter, 7 g of salicylic acid and a further 50 ml of xylene were added. To the reaction mixture, 0.3 ml of triethylcimine were added as catalyst.

After a reaction time of five hours, the solvent was completely distilled off and the amorphous solid obtained was comminuted and dried in vacuo.

Editor's note: 383-398K

Yield: 18g ^ 61%

IR (KBr): tfco = 1690cm '

Stabilizer 7

Analogously to the rule for stabilizer 6, wordon 22, bg p-tert.-butylcalix (8) orylglycidylthor (Formol II; R '= R ² = t.-butyl; R ⁴ = H; x - Y - -CHj-; a ι b - η - 8) with EA - 490 with 14g of SB di-t-butyl-hydroxy-propionic acid in 200 ml of Xylon in

Gogenwart of 0.4 ml triethylamine i; mgosotzt and aufgourboitot.

Editor's note: 378-398K

Yield: 25 g ^ 68%

IR (KBr): V _co = 1750 cm '

Stabilisator8

Analogous to that for stabilizer 6 wordone 22.5 g of p-tert-butyl-cisyl-8-yl-arylglycidone (formol II, R '= R ⁷ -t-butyl-; R ¹ = H; χ y -CH ^ -; atb ~ η = 8) with EA = 490 with 7g3,5-di-tert-butyl-4-hydroxy-phonylpropionic acid in 250 ml in the presence of 0.1 ml of triethylamine umgosolzt and aufgoarboitot.

Erw. Pkt .: 408bis410K

Yield: 24g A 83%

IR (KBr): V _co = 1750 cm '

Stabilizer 9

Analogously to the rule for stabilizer 6 wordon 22.5% p-tert.-butylcalix | 8l arylglycidother (formol II, R '= R ² - t -butyl ·; R ⁴ = H; χ- ^ y = -CH ₂ -; a + b = η = 8) with EA = 490 with 3.50 g of 3,5-dietit.-butyl-4-hydroxyphonylpropionic acid in 200 ml of xylene in

Presence of 0.1 ml of triothylamine. After complete conversion of the acid wordone, 2.5 g of pure aliphatic technical aminomic with amounts of C ₁₆ to 20 g, followed by reflux for one hour or less. Subsequently

Wordon 5.0 g of 4-amino-2,2,6,6-totramothylpiperidine, whereupon 3 hours of refluxing ororth and the solvent was distilled off in vacuo and the resulting amorphous solid Gotrocknot.

Additional-Pkt .: 407bis415K

Yield: 22g A 69%

IR (KBr): V _co - 1750cm '

Stabilizer 10

Analogous to the rule for stabilizer 6 wordon 22.5 g ptort.Butylcalix | 8 | arylglycidethor (formula II, R '= R ² = t-butyl; R ⁴ --- H; χ = y = -CH ₂ -; a + b = η = 8) with EA = 490 with 1.75 g of salicylic acid in 200 ml of xylon in the presence of 0.1 ml of triethylamine

implemented.

After crude engine rotation, wordon 5.8 g of 4-amino-2,2,6,6-tetramothylpiporidine is added and heated for 4 hours under reflux.

The solvent is distilled off in vacuo and the orhaltone amorphous Foststoff dried.

Additional Pkt .: 456bis466K

Exhaustion: 17g A 65%

IR (KBr): T? _c0 = 1690cm '

Stabilizer 11

Analogously to the procedure for stabilizer 6, 22.5 g of p-tert-busylcalix | 8) arylglycidother (formula II, R ¹ = R ² -t-butyl-; R ⁴ -H; a + b = η = 8) with EÄ = 490 reacted with 1.75 g of salicylic acid in 200 ml of xylene in the presence of 0.1 ml of triethylamine. To

new red wordon wordon 2.55g oinos primary aliphatic aminomic with Kotton lengths of Ci ₈ to dj added,

heated at reflux for one hour; 4.7 g of 4-amino-2,2,6,6-tetramethylpiporidine are added and, where appropriate, heated Stundon at reflux. The solvent is distilled off in vacuo and the resulting amorphous solid is dried.

Application-point: 418bis436K

Yield: 26g a 90%

IR (KBr): V _co - 1690cm '

Examples 1 to 13

The stabilizers to be used in accordance with the invention were mixed in a laboratory rolling mill at 378 to 413K or a laboratory oxtrudor at 453 to 473K cylinder volume, the polymer sample was pressed to 0.05 mm dickon samples by means of a press between two aluminum platelets with a force of 616 · 10 ⁴ N 421K and in the xenon tester 450 with filtered Xonon arc light under irrigation (every 30min for 5min) bowittert.

Dor aging process was followed by IR spectrometer by measuring boi 1720cm '. The sample is considered damaged once the extinction of E = 0.1 is reached:

example polymer stabilizer Concentration (mass fractions in%) Et ₀ = 0.1 (hours) Comparative Examples 1 2 3 PE-ND PE-ND PE-ND without t.-8utylcalix [8laren t.-butylc3lix | 8] areneglycidyl ether 0 0.3 0.3 450 600 450 4 5 6 7 PE-ND PE-ND PE-ND PE-ND 1 3 4 6 0.3 0.3 0.3 0.3 850 1460 1130 650

example polymer stabilizer Concentration (massoantoilo in%) (Stundon) CD CT. O PE-ND PEND PE-ND 9 10 11 0.3 0.3 0.3 1220 980 1320 11 comparative saline jelly PE-NO t.-butylcalix- [6 | aron 0.3 580 12 13 PE-ND PEND 2 5 0.3 0.3 1040 1 110

Example 14 to 19

The stabilizers according to the invention are incorporated in the polymer matorial to be protected as described for boilediols 1 to 13 and pressed on a press from the rolled sheets or granules of 0.05 mm thickness. On the films ^w: rd by measuring the Sauorstoffaufnahmo under isobaric conditions at 446K determines the induction period of the oxidation.

example polymer stabilizer concentration induction (Massoanteiloin%) poriodo (min) Vorgloichsbeispielo: 14 PE-ND 2,6-di-tert-butyl-4- 0.3 18 mothylphenol 15 PEND t.-butylcalix | 8] arone 0.3 24 16 PE-ND without 0 18 17 FEND 7 0.3 232 13 PE-ND fi 0.3 150 19 PE-ND £) 0.3 40

Example 20 to 24

The inhibierondo effect of the liquid hydrocarbon oxidation precursors according to the invention was tested using the example of AIBN-initiated oxidation of totraline. In a thermostated Doppolmantolgefäß, which is connected to a thermostated glass cuvette, boi333K was oxidized with stirring 18ml tetralin and 2mlChloibenzen with lmolmol / m ³ azobisisobutyronitrile (AIBN) in oxygen. The oxygen uptake was measured by means of an automatically registering apparatus (M. Schulz, E. Wegwart, K. Both, Plaste and Kautschuk 21 [1974] 430). The vorwondoton compounds according to the invention were used in a concentration of Q, btr \ o / m ³ . The figure shows the inhibieronde effect compared to 2,6-di-tert-butyl-4-methylphonol.

example stabilizer Comparative Example 20 21 without 2,6-di-tert-butyl-4-niethylphenol 22 23 24 9 8 7

Claims (3)

claims: 1. A process for the stabilization of high polymers, low molecular weight organic compounds and oils, in particular of polyolefins and Olefincopoiymeren, ABS and rubbers against the thermooxidative, photooxidative and thermal degradation by incorporation of stabilizers in a concentration of 0.01 to 0.6 parts by weight in%, in particular from 0.05 to 0.5 parts by mass in%, based on the amount of substrate, which are optionally combined with other known stabilizers such as quenchers, complexing agents, lubricants, UV absorbers and antistatic agents, which are then in a concentration of 0.01 to 0 , 6 parts by mass in%, in particular from 0.05 to 0.3 parts by mass in%, based on the amount of substrate used, characterized in that as stabilizers compounds of the general formula R ^<j Z 0 II CH ₉ -CH-CH OR X τι y vs be used in the χ = y = -4-CR ⁵ R ⁶ -4- ₍ with R ⁵ ; R ⁶ = hydrogen; alkyl, cycloalkyl, aryl or aralkyl and q = 1 to 3 or x · _-, y = -CH ₂ -O-CH ₂ ; -CO-, Z = -O-; -S-; -NR ⁷ - with R ⁷ = hydrogen; alkyl; cycloalkyl; aryl; Aralkyl or R ⁵ -CO groups,
R ¹ , R ² = hydrogen; Alkyl or. a substituted alkyl radical WI-CR ⁵ R ⁶ - + - ,, in particular with W = R ⁵ -O-CO-; R ⁵ R ⁶ N-CO-; R ⁵ -CO-; Halogen-; R ⁵ R ⁶ N-; Aryl and r - 1 to 30; a cycloalkyl or a substituted cycloalkyl radical or an aryl or substituted aryl radical, 0H (o, m _t p) With R ⁸ , R ⁹ , R ' ⁰ , R ¹¹ = hydrogen; alkyl; cycloalkyl; aryl; Aralkyl or Hydroxyl and and s = 0 to 30 or _H 10 with R ¹² = hydrogen; alkyl; cycloalkyl; aryl; hydroxyl; R ' ^J -CO-; R ⁵ -O-or R ³ = alkyl radical {C _{9 to} C 30) or R ' ³ ~CO- with R' ³ -C _{9 to} C 30 R ⁴ = hydrogen; alkyl; cycloalkyl; R ⁵ -CO- or - CO a = 1 to 12 and b - 0 to 11, where a + b = η = 2 to 12. 2. The method according to claim 1, characterized in that are used as stabilizers compounds of formula I in which a + b = 4,6 or 8, where a = 1 to 8 and b · - 0 to 7. 3. The method according to claim 1 and 2, characterized in that in the same molecule of the compound of general formula I with a = 2 to 8 at least one radical R ³ or the radical R ^{4 is} a compatibility with the substrate-promoting group, for. B. an alkyl radical C ₉ to C ₃₀ ;