DE2150327A1 - Stabilizer mixtures - Google Patents

Description

CLBA-GEIGY AG, CH-40Ö2

CLBA-GEIGY

Dr. F. Zumstoin Sr. - Dr. E. Assmann Dr.R.Koeni (jabaroor - Dir · '· f'hy ··. R ;. Holzhauer

Dr. r. ZumsUin jüti. ■ P α t β η I ei π ν / α it β 8 Munich 2, Brüuhaussiraße 4/111

3-3416 / GC 482

Germany

S t ab il i s at ormi s dmr gen

The present invention relates to physical mixtures which (a) a compound of the formula

HO-

and (b) a compound of the formula

.3

.HO— ((J> —CH ₂ CH ₂ COO-

209816/15

contain, in which R and Ir independently of one another are methyl, isopropyl, sec, -butyl or tert-butyl groups;

ο Ii.

E and E independently of one another isopropyl, sec-butyl or tert-butyl groups, and

X and Y non-identical alkylene groups with 3 "to 18 carbon atoms, the zv / ei have free, non-geminal valence bonds mean.

The mixtures according to the invention thus contain 3- (3j5-dialkyl-4-hydroxyphenyl) propionic acid esters of at least two non-identical alkanediols * The alkanediols have 3 to Carbon atoms, preferably 3 to 12 carbon atoms, and most preferably 5 to 9 carbon atoms and can structurally z * B * with respect to their carbon atom content from each other be different * The alkanediols can have the same number of carbon atoms in the hydrocarbon chain and differ with regard to a branch, that is. one alkanediol is the structural isomer of the other. Finally, the alkanediols can have the same carbon content and the same branching, but two centers of asymmetry own . and thus represent diastereoisomers. the Groups X and Y are derived from the hydrocarbon radicals of the alkanediols and correspond to these in terms of structure,

The ratio of the two components of these mixtures can range from 1: 1 to 9: 1. If X and Y are only related differ in the diastereoisomerism, this ratio is preferably about 1: 1, whereas otherwise a ratio from about 1: 3 to 3: 1 is preferred.

In addition to the difference in hydrocarbon structure of the alkanediol, the two components can additionally differ with regard to the substituents E and E on the one hand and the substituents E ^ and E on the other hand

Preferred are compounds in which the groups E and E ^ Methyl or tert-butyl groups and the groups E and E tert-butyl groups mean·

209816/1594

Typical alkene groups for X and Y are 2,2,4-trimethyl ~ 1,6-hexylene-, 2,4,4-trimethyl-1,6-hexylene-, 2-ethyl ~ 1,3-hexylene-, 2,2-dimethyl-1,3-hexylene-, 2,2,4-trimethyl-i, 3-pentylene--, 2,2-dimethyl-1,3-propylene-, Pentyl-1,2-ethylene-, 1-hexyl-1,12-dodecylene-, 3-ethyl-2,4-heptylene-, 2-ethyl-2-butyl-1 ^ -propylene-, 2,2-diethyl-1,3-propylene, 2-methyl-2-propyl-1,3-propylene, 1,4-dimethyl-1,4-butylene, 1,2,3-triethyl-1,3-propylene and 1,3-dimethyl-1,3-propylene groups.

The esters of the 3j5-dialkyl-4-hydroxyphenylalkanecarboxylic acids with Alkane polyols are described in U.S. Patent (Patent Application Ser. Ko. 861 475) ". Many of these connections represent crystalline or glassy pesticides that are effective stabilizers against thermo-oxidative aging, i.e. pesticides represent antioxidants. V / f also only have these antioxidants limited solubility in solvents, which are technically used in large quantities, such as in aliphatic Hydrocarbons.

These properties represent an advantage for many applications, but a disadvantage for others. It is therefore particularly difficult to use these compounds in industrial processes in which the additives have to be pumped, metered and supplied in fluid porin, as is the case, for example, in solution polymerization processes Case is.

The mixtures of the invention are not just for stabilization of organic material particularly suitable, but they also represent liquids that are pumped, dosed and can be fed, or which are very soluble in organic solvents, so that they are in the form of highly concentrated Solutions can be used.

The mixtures according to the invention can be obtained by one compounds of the formula

2098 1'6 / 159A BATH

HO-

wherein Z is a methoxy or ethoxy group, with mixtures of alkanediols of the formulas

HO-X-OH
and
f HO-X-OH ₁

optionally in the presence of a solvent in the presence an acidic or basic catalyst. You can also by acylating alkanediol mixtures with the appropriate Acid chloride, i.e. in which the group Z represents a chlorine atom. Alternatively, these materials can can be prepared by using alkanediol mixtures the free acid, i.e. in which the group Z is a hydroxyl group means, reacts in the presence of an esterification catalyst. In all of these procedures, the total amount of the alkanediol mixture is so large that about two moles of the acid, ester or acid chloride are used per mole of the mixture.

If the mixtures according to the invention are prepared by the above process, the group R has the same meaning

■ χ ρ

as group E ^ and group E the same as group ⁴

Alternatively, "the two components can be manufactured separately, physically mixed and subjected to a fusing stage.

The organic material that is stabilized against thermo-oxidative decomposition with the mixtures according to the invention

20 9 8 V6 / 1-5 9 4

can is mainly polymeric material, v / ie polyolefins, Preferred oc-olefin polymers, such as polypropylene, optionally cross-linked polyethylene, polyisobutylene, polymethylbuteii-1, Polymethylpentene-1, polybutene-1, polyisoprene, polybutadiene; Copolymers of monomers, such as ethylene / propylene copolymers, Propylene / butene-I copolymers, propylene / Isobutylene copolymers, styrene / butadiene copolymers as well as terpolymers of ethylene and propylene with dienes, such as hexadiene, dicyclopentadiene or ethylidene-norbornene; Mixtures of the above-mentioned homopolymers, such as mixtures, of polypropylene and polyethylene, polypropylene and polybutene · -1, polypropylene and polyisobutylene. Are preferred Propylene and mixtures of propylene and copolymers containing propylene units; Copolymers and Graft polymers of styrene and butadiene with acrylonitrile, acrylic acid esters and methacrylic acid esters, optionally with Vinyl esters or vinyl chloride; natural polymers, such as rubber; and polycondensation products, v / ie polycarbonate, Polyamides, polyesters, polyacetals and polyurethanes. In addition, according to the invention, high molecular weight monomeric materials, such as mineral oils, esters, e.g. animal and vegetable fats, oils and waxes and oils and waxes based on a synthetic ester stabilized.

Me mixtures are in a concentration of 0.01 to 5 wt .-%, based on the material to be stabilized, preferably in an amount of 0.05 to 1.5 wt .-% and in particular in an amount of 0.1 to 0.8% by weight incorporated into the substrates.

Incorporation into the melt or the solution of the polymers can be used before or after the polymerization, before or after the shaping, e.g. by mixing the mixtures according to the invention gon, optionally with the addition of other additives according to the usual Procedure. The dissolved or the dispersed compounds can also be applied to the polymers are, where appropriate, then the solvent is evaporated. It is a particular advantage that the

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BATH

mixtures according to the invention in the form as they are, or in the form of concentrated solutions, if necessary at elevated temperatures, pumped through lines and measured out Amounts in the polymerization process or the subsequent one Application processes can be fed.

Other additives that can be used together with the mixtures according to the invention can be used include the following:

(i) Andioxydants of the hydroxyaryl and amino aryl classes, such as _v

2,2'-thio-bis- (4-methyl-6-tert-butylphenol) 4,4'-thio-bis- (3-methyl-6-tert-butylphenol) 2,2'-methylene- bis- (4-methyl-6-tert-butylphenol) 2,2'-methylene-bis- (4-ethyl-6-tert-butylphenol) 4,4'-methylene-bis (2-methyl ~ 6-tert-butylphenol) 4,4'-butylidene-bis- (3-methyl-6-tert-butylphenol) 2,2'-methylene-bis- [4-methyl-6- (α-methyl cyclohexyl ) -phenol] 2 _s 6-di ~ (2-hydroxy-3-tert-butyl-5-methylbenzyl) -4-methylphenol 2j6-di-tert-butyl-4-methylphenol

1,1,3-Tris- ^ -methyl ^ -hydroxy ^ -tert. -butyl-phenyl) -butane 1,3,5 ~ trimethyl-2,4,6-tris- (3,5-di-tert-butyl ~ 4-hydroxy-

benzyl) benzene.

2 _i 4-bis-octylmercapto-6- (4-hydrocyan-3,5-di-tert-butylanilino) -s-triazine

2,4-bis- (4-hydroxy-3 s 5-di-tert-butylphenoxy) -6-octylmer capt os-triazine

1,1-bis- (4-hydroxy-2-methyl-5-tert-butyl-phenyl) -3-dodecyl- mercapto-butane

4-Hydroxy-3,5-di-tert-butylbenzyl-phosphonic acid esters, such as the dimethyl, diethyl or dioctadecyl esters 2- (3-methyl-4-hydroxy-5-tert-butylbenzyl) malonic acid dioctadecyl ester

S- ^ 3i5 ~ dimethyl-4-hydroxyphenyl) -thioglycolsäure-octadecyl ester of 2,2-bis ^(3,5-di-tei> tert-butyl-4-hydroxybenzyl) -malon acid ~ j as the Didodecylester, the bioctadecyl ester and the 2-dodecyl mercapto ethyl ester,
Phenyl-1-naphthylamine

209 8 16/1594
BAO

Phenyl-2-naphthylamine

N, 1ί '-diphenyl-p-phenylenediamine

N, If '-Di-2-naphthyl-p-phenylenediamine

N, N'-di-sec-butyl-p-phenylenedi amine

6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline Mono- and di-octyliminodibenzyl "and

polymerized 2,2,4-trimethyl-1,2-dihydroquinoline.

(ii) UV absorbers and light stabilizers, v; ie:

(a) 2- (2'-Hydroxyphenyl) benzotriazoles, for example the 5'-methyl, 3 ^1, 5'-di-tert-butyl-, 5'-tert-butyl-, 5-chloro-5 ^f , 5'-di-

tert-butyl-, 5-chloro-3'-tert-butyl-5 ^f -methyl-, J ', 5 ^f -di ~ tert. amyl, 3'-methyl-5'-β-inethoxycarbonylethyl, 5-chloro-3 'and 5'-bi-tert.-amyl derivatives;

(b) 2,4-bis (2'-hydroxyphenyl) -6-alkyl ~ s-triazines, e.g. the 6-ethyl or 6-undecyl derivatives;

(c) 2-Hydroxy-benzophenones, e.g. the ^ - hydroxy,

4-octoxy, 4-decyloxy, 4-dodecyloxy, 4,2 ', 4 -'-trihydroxy or 2 '-hydroxy-4-, 4-' -dimethoxy derivatives;

(d) 1,3-bis- (2'-hydroxybenzoyl) -benzenes, e.g. 1,3-bis- (2'-hydroxy-4- '-hexyloxybenzoyl) -benzene, 1,2-bis- (2'- hydroxy-4 · ^1- octyloxybenzoyl) benzene, 1,3-bis (2'-hydroxy-4- ¹ -dodecyloxybenzoyl) benzene;

(e) Aryl esters of optionally substituted benzoic acids, viie, for example, phenyl salicylate, octylphenyl salicylate, benzoylresorcinol, bibenzoylresorcinol, the 2,4 ~ I) i-tert.-butylphenyl or octadecyl esters of 3 _i 5-bi-tert.-butyl-4 - ~ hydroxybenzoic acid.

(f) acrylates, e.g.

a-cyano-ß, ß-diphenylacrylic acid ethyl or isooctyl ester, a-methoxycarbonyl cinnamon acid methyl ester, a-cyano-ß-methyl-p-iaethoxy-cinnamic acid methyl or butyl ester, N- (β-carbomethoxy-vinyl) -2-methyl-indoline;

(g) nickel compounds, e.g.

209 816/159 /,

BATH

Nickel complexes of 2,2'-thio-bis- (4 ~ tert-octylphenol), such as the 1: 1 and 1: 2 complexes, optionally with other ligands, like n-butylamine,

Nickel complexes of bis (4 "tert.-octylphenyl) sulfone, \\ ^T ± e the 2: 1 complex, optionally with other ligands, such as 2-ethyl caproic acid,

Nickel dibutyldithiocarbamate, nickel salts of 4 ~ hydroxy-3,5-dij-tert. -butylbenzyl-phosphonic acid monoalkyls, such as the Methyl, ethyl or butyl esters, nickel complexes of 2-Ey ~ droxy-4-methylphenyl-undecyl-ke toxim;

(h) oxalic acid diamides, e.g.

4,4'-di-octyloxyoxanilide

2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide 2,2'-di-dodecyloxy-515'-di-tert. -butyl oxanilide

(iii) phosphites such as

Triphenyl phosphite

Diphenyl alleyIpho sphit

Phenyl dialkyl phosphite

Trinonylphenyl phosphite,

Trilauryl phosphite

Trioctadecyl phosphite

3,9-di-isodecyloxy-2,4,8,1O, tetraoxa-3j9-diphosphaspiro- (5,5) - "undecane

Tri- (4-hydroxy-3,5-di-tert-butylphenyl) phosphite.

(iv) cell forming agents such as ^ -tert-butylbenzoic acid, Adipic acid and phenylacetic acid.

(v) peroxide decomposing agents, e.g.

Esters of ß-thio-dipropionic acid, e.g. the lauryl, stearyl, Myristyl or tridecyl ester; Salts of 2-Iiercaptobenzimiaazole, e.g. the zinc salt and diphenylthiourea.

(vi) metal deactivators, e.g.

Oxanilide, dicarboxylic acid dihydrazide, dicarboxylic acid-bis-phGiiylhydrazide, Salicylic acid hydrazide, li-salicyloyl-N '-sa.licy.1 j den-

2098 16/1594

hydrazine, bis-salicyloyl-dicarboxylic acid dihydrazides, bis-acylated Dicarboxylic acid dihydrazides and salicyloylhydrazinOtriazines.

(vii) Other additives, such as antistatic agents, flame retardants, Asbestos, glass fibers, kaolin, kaolin, propellants, pen, plasticizers, coloring agents, dyes, pigments, vulcanization accelerators and other additives commonly used in the rubber industry, agents to add to the Freeze point ~ to lower, anti-corrosion and! Anti-rust agents, Dispersants and anti-foaming agents.

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

Example 1

64 g of a mixture of about 70 wt .-% 2,4,4-Trimcthyl-1,6-hexane-diol and about 30 wt. ~% 2,2,4-trimethyl-1,6-hexane-diol were combined with 234 g of 3 ~ (3> 5-di-tert-butyl-4-hydroxyphenyl) · - where propionsäviremethylester in a three-necked flask provided with a fractionating column and were melted under introduction of nitrogen at 80 ⁰ C. 0.8 g of lithium amide were then added to this melt. The mixture was then heated first under normal pressure and finally under vacuum (about 12 mm Hg) until no more methanol distilled over. Then 2 g of glacial acetic acid was added to the reaction mixture and the mixture was filtered. After filtering, a pale yellow, clear, viscous liquid was obtained, consisting essentially of a mixture of about 70% by weight of 2,4,4-trimethyl-1,6-hexanediol-bis-C3- (3,5-di tert-butyl-4-hydroxyphenyl) propionate] and about 30% by weight of 2,2,4-trimethyl-1,6-hexanediol-bis-C3,5-di-tert-butyl _: - 4 ~ hydroxyphenyl) propionate] (stabilizer no. 1).

Analysis: C ₄₅ II ₆₈ O ₆

Calc .: C 75.84 H 0.07 Ο 14.10

found C 75.5 H 10.2 0 14.3

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215 Q 3 2 7

Example 2

By replacing the trimethylhexane diol isomer mixture γοια, Example 1, with a mixture of 1 ^l hreo-2 ~ 1; lryi - '1,3-hexanediol and erythro ~ 2 ~ ethyl-1,3-hexanediol in a ratio of about 1: 1 and a mixture of 2,2,4-trimethyl-1,5-peiitandiöl and 2,2-diynethyl-1,3-hexanediol in a ratio of efea 4: 6 was obtained after going through the steps described above a mixture of about 50% E: rythro-2-ethyl-1,3-hexane-aiol-bis- [3 ~ (3,5-di-tert-butyl-4-hydroxyphenyl) ~ propicnatJ and about 50 ^c , o Threo-2-ethyl-1,3-hexanediol-bis [3- (3,5-di-tert-butyl ~ 4 ~ hydroxyphenyl) propionate] (stabilizer no. 2) or a mixture from about 40% 2 2.4 _{J-trimethyl-1} 3-pentanediol _i-C3-bis (3 _l 5 ~ di-tert-butyl-4-hydroxyphenyl) ~ propionate] and 60% etxira 2 _S 2-di- ' methyl-1,3-hexanediol-bis-C3 ~ (3 »5-di-tert-butyl-4-hydroxyphenyl) -PiOpio3iatl (stabilizer ITr. 3) in the form of yellowish viscous liquids.

Analysis ί C.pIL-gGg - calculated for the stabilizer Hr. 2 calc.s C 75.63 H-. 9.97
Found: G 75.6 H 10.1

Example 3

If you replace the 3- (3i5-di-tert-butyl-4-hydroxyphenyl) -propion-J! . acid methyl ester of Example 1 by an equimolar amount of 3- (3-methyl-4-hydroxy-5-tert-butylphenyl) propionic acid and v / if the process described in Example 1 is otherwise ended, a mixture is obtained of 2,2,4- "and similar -2,4,4-2? rimethyl-1,6-hexanediol- bis [3- (3-ethyl-4-hydroxy-5-tert, butylphenyl) propionate] in a ratio of about 3 ^: 7 in the form of a clear, pale yellow viscous liquid (stabilizer no. 4).
/ aialysis: C-nHcgOg

Calcd .: C 74.46 H 9.45 O 16.08
Found: C 73.9 H 9 * 5 0 16.5

B e i s ρ i e 1 4 ...

If you replace 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid

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reraethylester of Example 1 by an equimolar amount of 3- (3> 5-Diisopropyl-4-hydi'oxyphenyl) -propionic acid met hy 1 e ster or by methyl 3- (3,5-di-sec-butyl-4-hydroxyphenyl) propionate and if you otherwise use the procedure described in Example 1

drive on, so you get depending on the starting material a mixture of the 2,2,4- and 2,4,4 ~ tri-ethyl-1,6 ~ hexai> diol-bis- [3- (3i5-diisopropyl-4-hydroxyphenyl) -propionate] (Stabilizer No. 5) or a mixture of the 2,2,4- and 2,4,4-trimethyl-1,6-hexanediol-Ms- [3- (3,5-di-sec-butyl ~ 4-hydroxyph " nyl) propionate] (Stabilizer No. 6).

Example -5

In the reaction of 38 g of 1,2-propylene glycol and 59 S -from 1,6-He-xan-diol (4-hydro-3,5-Diiaethyl; qy - phenyl) 208 g of 3- "propionic acid methyl ester in accordance with the in Method described in Example 1, a mixture of equimolar amounts of 1 ₅ 2-Pxo ^ ylenglykol-bis C 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and obtained after the reaction has ended 1,6-hexane-diol-bis-C3 ~ (3 »5-di-tert-butyl-4-hydroxyphenyl) propionate] (stabilizer no.7) in the form of a pale yellow syrupy liquid.

Examples

To a mixture of 3 ^ 5 parts by weight of 1,12-octadecanediol, 2.00 parts by weight of 1,9-nonanediol and 90 parts by weight of pyridine were added at a temperature of 5 to 10 ° C in the course of 1 1/2 hours 16, 3 Gewiehtsteile 3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionyl chloride, the mixture stirred for 16 hours at room temperature ,, and during at 5O ⁰ C for 1 hour and then poured the reaction mixture into a mixture of 100 Parts by volume of 6N hydrochloric acid and 800 parts of water. This mixture was extracted five times with 200 parts by volume of diethyl ether and the combined extracts were washed three times with dilute hydrochloric acid, five times with water and twice with saturated trium chloride solution. After drying over sodium sulfate, the solution was concentrated under reduced pressure.

20 98 16/159 k
BATH

215032?

©! Ige residue assisted by a mixture of i, 12 ~ Öcta-Öeeändiül * bis-t 3- (5> 5-di * fceri. -Butyl - ^ - l ^ üroxypheiiyi) -p-röpio- & at3 and 1 ^^ Nonanediol-biB ^ t ^ -CJi ^ -di-tert.-butyl ^ -liydro - ^ - · phetiyl) -prop £ oiiät3 (stabilizer Ur »8) ·

Example 7

j Solubility in aliphatic hydrocarbons

Bleach parts by weight of η-hexane and one of the stabilizers indicated in the following TABLE I were mixed, followed by stirring the mixture for one hour under Hühren at 35 ⁰ C / and then one hour at 20 ⁰ C in a thermostat and filtered *. The amount of stabilizer contained in the filtrate, which is a saturated solution of the stabilizer in η-hexane, was determined by concentration and evaporation and VJiegea of the residue. The solubilities of the stabilizers prepared according to Examples 1 Mb J in a typical hydrocarbon are given in grams per 100 g of solvent in Table I below.

Table I.

Stabilizer no.; Solubility (g / 100 g hexane.) 1
2
3 100 ■
100
100
100

Examples

Stabilization of polypropylene

(a) Preparation of the test samples

100 parts of polypropylene (melt index 3.2 g) were made. 10 / iiioiberi kneaded at 200 ⁰ C with one of the stabilizer systems given in the following Table II in a Brabender Plastographrm. The mass obtained was then at a temperature of 260 ⁰ C with the aid of a plant press r, u sheets with eircr thickness

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BATH

of 1 mm, then pressed into strips with the dimensions 1 χ 17 cm were cut.

(b) Investigation

The effectiveness of the additives was determined by aging represents sheets in the heat in an air circulating oven at 135 ⁰ C and 129 ° C.

The beginning of the visible degradation of the test sample was taken as the end point of the investigation.

(c) Results

Table II

Stabilizer system Time in .days to decomposition 149 ° C chile stabilizer 135 ° C <1 0.2% stabilizer 1
0.1% stabilizer 1
+ 0.3% dilaurylthio
dipropionate 1 59
45 0.2% stabilizer 2
0.1% stabilizer 2
+ 0.3% dilaurylthio
dipropionate
0.2% stabilizer 4
0.1% stabilizer 4
+ 0.3% dilaurylthio
dipropionate 158
228 32
32
44
54 156
142
143
197

2 09816/159 4

7 «

Example 9

Stabilization of synthetic rubber (FPDM )

(a) Preparation of the test samples

100 parts of EPDH-Kautschule (composition: 46.5 % ethylene, 50 % propylene and 3 * 5 ° / ° Ä'thyliden-norbornen), which did not contain any stabilizer, were mixed with 0.1 part of one of the additives given in the table below kneaded in a Brabender plastograph for 30 minutes at 150 ⁰ C and 60 rpm.

(b) Examination by processing in a plastograph

During kneading, 1 g samples were taken after 10, 20 and 30 minutes and checked for the amount that was insoluble in toluene
is examined (gel content). 1 g of the material to be examined was dissolved in 50 ml of toluene for 20 hours at room temperature
stirred and filtered through glass wool. The piltrate was concentrated by evaporation and the residue was. The difference between the original weight and the second weight corresponds to the gel content. The gel content is given as a percentage of the original weight of the test sample in Table III.

The oxidative damage to the polymers during processing shows itself through a network and thus through a. Increase in gel content.

Table III

Stabilizer Mr. Gel content after processing during 20 min. 30 min. without stabilizer
1
2 10 min. 29 %
1 %
2% 39 %
24 %
28 % 10 %
<1 %
<1 % ■

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2160327

ieiepifel ok

In a reaction vessel that with eiiieai Führer, fine Dean-Stark Trap and an opening for a stick was given 5B5 kills Ie 5- (3 »iHDi ~ te £ t * ^ bütyi-'i-hydro: ^ henyi) p ester * 99 parts of a JÜi ^ Ö-HrUehittig of the isomers thyi ~ 1,6-he3candiöi And 2i2,4-Triiiiethyi-i, 6-he: K: andiol ühd 1,33 Parts of lithitiiiiliydiid * The reaction parts became currency 1 1/2 hours "at atmospheric pressure under nitrogen

Finally G / -weiterer heated during 4 hours at a pressure of 0 ^ 2 to 0.5 öiia äuf 1Ί0 to 12O ⁰ C. Then, after cooling, 100 parts by volume of hexane were added and the mixture was heated with stirring and filtered. The FiItrat was with Ij? Completely divide glacial acetic acid with stirring and finally treated with an excess of sodium carbonate with stirring. After filtering again, the filtrate was freed from the solvent and the volatile impurities by heating in a vacuum. The residue consisted of a 3Oi7Ö-ttischung of 2,4Vl-ttrincthyl-i, 6-hexanediol-bis-C3- (3 _i 5-tert ~ ai * -bUtyi-4-hydroxyphenyl) -propionat3 and 2,2,4- TriTaothyli, 6-hexanediol bis ~ t 3 »5-di-tert-butyl - ^ - hydroxyphenyl) propio ~ iate], which was in the form of a syrup.

Example 11 Stabili si augmentation v on polyamic id-6

100 parts] Polyamide-6 granules are mixed with 0.5 parts of trisnonylphenyl phosphite and 0.5 parts of one of the

(.GeI.τ mat) belle additive listed mixed, processed in a Labormischsr j and afterwards at 260 ° C for 1 mm - pressed Prüflatten "The plates are in a convection oven at 14O ° C accelerated aging untex-v orfen?. The stabilizing effect of the additives is assessed on the basis of the brittleness of the films.

09816/1594

OBIGINAt

Stabilizer no. Brittle after 1
2 18 hours
30 hours
30 hours
JO hours

Example 12

Stabilization of polyurethane

100 parts of one-component polyurethane ("Estane 5707", BF Goodrich & CoO, 1> 0 parts of 2- (2 ^I -hydroxy-5 "methylpliGnyl) -benztriazole and 1 part of one of the additives listed in the table below are used in 3OO parts of a 1 μl acetone-dimethylformamide mixture dissolved.

a glass plate are made from these solutions with a film drawing device about 400 u thick films are drawn, which after about 10 minutes of forced air drying at 140 ° C to films with a final thickness of 100 u dry out. The stabilizers are therefore in the films in a concentration of 1.0%. Samples of these films are checked until the onset of visually perceptible yellowing exposed to a xenotest device on a white cardboard base. The effectiveness of the additives is determined by the resistance to yellowing Test subjects assessed.

Stabilizer no. Exposure time for German
yellowing in hours 1
2
4th 3OO
800
800
600

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Example 13

If so, from PoIyac et al

100 parts of unstabilized homopolyacetal (polyforraaldehyde, origin: Societa Italiana Resine) are mixed with 1.5 parts of calcium te ar at and 0.2 parts of one of the additives mentioned in the table below, processed on a two-roll mill for 15 minutes and the rolled sheet peeled off . 10 mg each of the stabilized samples are heated ^{to 220 ° C. on the dish of a sensitive thermobalance.} The weight loss of the samples is recorded continuously.

Stabilizer Mr. Weight loss in % 10 mins 15 minutes 1
2
4th 5 minutes 22nd
2
2
2 31
4th
4th 12th
1
1
1

Example 14 Stabilization of Polymethyl Methacrylate

100 parts of polymethyl methacrylate ("Eesarit 40CO") v / ground at 1.5 Share an additive listed in the table below intensively mixed. The mixture obtained is extruded in a laboratory extruder and then granulated. The received The granulate is then regranulated 25 times. After the 5th, 15th and 25th extrusions, a sample of the granules becomes one 1 mm thick plate, which is assessed by its color.

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Additive ETr. Color of the plastic according to. 15 extrusions 25 extrusions 1
2 5 extrusions deep yellow
color3-os
colorless Brown
slightly yellowish
slightly yellowish yellow
colorless
colorless

209816/1594

Claims (1)

Claims = sis 1 =; · -: - »it: ■« s = s 1.
she Stabilizerini loops, characterized in that (a) an A ^r bond of the formula "HO- . H -C) I ClI.COO- X- .2 and (b) an A he ^r "bond of 3? ormcl JlO-- -CU ..Cf ₁ COO- 2 " contain, viorin H and Br independently of one another methyl, isopropyl, sell-butyl or tert-butyl groups, R and E independently of one another isopropyl, sec-butyl or tert-butyl groups, and 31 and Y not identical alkylene groups have 3 Ms 18 carbon atoms, the z, vei Treie nioiit-gsjninal Yalenzbindungen v; iron, mean. 2. Stabilizer mixture according to claim 1, characterized in that that R and R ^ methyl or tert-butyl groups, 209816/1594 BADOBtQfNAt E and R tcrt.-butyl groups and X and X non-identical alkylene groups with ■ 3 to 12 carbon atoms "mean", 5 · Stabilizers, Schmiss geraäß "claim 1, characterized in that that E, It, E ^ and E "are tert-butyl groups and X with Y not identical alkylene groups with 5 to 9 carbon atoms mean" 4. Stabilizer mixture according to claim 1, characterized in that gG- 'indicates that they are made from 2,2,4-tri-ethyl-1, b-hexanediol-bic-C 3- (3,5-di-tert. ~ Butyl - /) - hydroxyphenyl) propionate J and 2,4 ·, 4 ~ Triraethyl-1,6-hexanedi-bis-C 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ordered. 5 ·. ". Stabilizer mixture according to claim 1, characterized in that sio
(3, i? -Di-tert »" butyl-4 · hydroxyphenyl) propionate] and 0? Hreo-2-ethyl-1,3-hexanediol-bis-L3- (3i 5-di-tert. - -butyl-4-hydrox ^ phc) iyl) - 'propionate consists.' 6. Use of the Stabilizermischuncen according to claim 1 üum stabilization of organic material _v which is normally subject to clem thermo oxy d ative degradation. 7. Use according to claim 6, characterized in that that the organic material is a polymer of ethylene, propylene ? ■ len and a Dien is. 8. Use according to claim 6, characterized in that that the organic material is a polyolefin. 9. Use according to claim 8, characterized in that that the polyolefin is polypropylene. 10. Use according to claim 8, characterized in that that the polyolefin is polyethylene. 209816/15 94 BAD ORfGfNAL