DE2540432A1 - SULFUR-CONTAINING ALKYLIDEN-BISPHENOLS AND THEIR USE AS STABILIZERS - Google Patents

Description

C!

DR. ERLENn Π: N NE PATENTANWALT 2 8 li R I M ί £ Ν

UHLANDSTRAbSE

Case 3-9585 / +
GERMANY

Sulfur-containing alkylidene bisphenols and their use as stabilizers

US Pat. No. 2,796,444 discloses 1,1'-bis (2-hydroxy-3,5-dia3kylphenyl) -methylenes known that contain a tertiary alkyl group in the 3-position and as antioxidants for rubber to serve. British Patent 1,116,127 describes 1,1-bis (3,5-dialkyl-2-hydroxyphenyl) -3-thioalkyl-propanes as stabilizers for polyolefins whose alkyl group is branched in the 3-position on the α-carbon atom.

The present invention relates to compounds of the general formula I.

609814/1 192.

(D

wherein
egg
is not branched in the α-position,

R, an alkyl group having 1 to 18 carbon atoms, the

R _{9 is} a linear or branched alkyl group with 1 to carbon atoms or a hydrogen atom,

R ^ and R_ each represent a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, and

Typically a linear or branched alkyl group with 1 to carbon atoms, the carbon chain being through Sulfur atoms can be interrupted, mean.

In formula I, preference is given to R-, an alkyl group not branched on the α-carbon atom and having 1 to 8, in particular 1 to 4, carbon atoms, and R _{2 is} an alkyl group having 1 to 4 carbon atoms.

The sulfur-interrupted alkyl radical R ^ is preferred constructed in such a way that at least 2 carbon atoms are bonded between two sulfur atoms. Particularly R is preferred, an alkyl radical, in particular having 4 to 16 carbon atoms.

R- is preferably a hydrogen atom or alkyl having 1 to 4 carbon atoms. R ~ and R is preferably independently each a methyl group or a hydrogen atom from one another, in particular R 'and R_ atom is a hydrogen or R ~ is a methyl group and R ₅ is a hydrogen atom.

609814/1192

Particularly valuable compounds of the formula I are those in which R represents the methyl or ethyl group and R _{0 is} preferably an alkyl radical having 1 to 4 carbon atoms, in particular likewise the methyl or ethyl group.

In formula I, R-t and R "are particularly preferably the methyl group and preferably R, for an alkyl radical having 4 to 16 carbon atoms.

The compounds of the formula I are new and are obtained by processes known per se by adding a phenol to the Formula II

OH

R ₂

(II)

where R, and R "have the same meaning as in formula I, • with a thioaldehyde of the formula III

HC - CH CH - S - R ₄ (III)

R ₅ R ₃

wherein R ₃ and R ₄ and R _{5 have} the same meaning as in formula I, is reacted in the presence of an acidic catalyst. Known methods are described, for example, in English patent specification 1,116,127. In general, about 2 moles of phenol are used for about 1 mole of thioaldehyde.

Possible catalysts are, for example: hydrogen chloride, sulfuric acid, zinc chloride, trifluoroacetic acid. The reaction can be carried out with or without a solvent.

6 0 9 8 U / 1 1 9?

2540A32

Suitable solvents are, for example: aliphatic and aromatic hydrocarbons, halogenated aliphatic and aromatic hydrocarbons, alcohols or Ether.

A liquid Lewis acid ether is preferred as the catalyst at- adduct used, which also serves as the reaction medium. Particularly good yields are then in this case achieved when at least 3 moles of the liquid catalyst is used per mole of reaction product.

As Lewis acids suitable for the formation of ether adducts may be mentioned: aluminum and boron trihalides, for example aluminum trifluoride, aluminum chloride and bromide and boron trifluoride and chloride.

Preferred catalysts are adducts of boron trifluoride and ethers, especially diethyl ether.

The aldehydes of the formula III are obtained by corresponding unsaturated aldehydes in the presence of a Base, such as triethylamine, adds mercaptans R, SH, where the radical R has the same meaning as in formula I.

Compounds of the formula I are for example:

1,1-bis- (3,5-dimethyl-2-hydroxyphenyl) -3- (n-dodecylthio) -n-butane

1,1-bis (3,5-dimethyl-2-hydroxyphenyl) -3- (n-butylthio) propane

1,1-bis- (3,5-dimethyl-2-hydroxyphenyl) -3- (n-octylthio) -n-butane

1,1-bis (3,5-dimethyl-2-hydroxyphenyl) -3- (n-octylthio) propane

1,1-bis-O-methyl-S-ethyl-2-hydroxyphenyl) -3- (n-octylthio) propane

6098U / 1192

l, l-bis (3-ethyl-5-methyl-2-hydroxyphenyl) -3- (n-octadecylthio) -n-butane

1,1-bis (3-methyl-5-n-butyl-2-hydroxyphenyl) -3- (n-octylthio) -n-butane

1,1-bis (3-methyl-5-tert-butyl-2-hydroxyphenyl) -3-n-octylthio) -n-butane

1,1-bis- (3-ethyl-5-n-octyl-2-hydroxyphenyl) -3-methylthio-

propane

1,1-bis (3-n-butal-5-tert-butyl-2-hydroxyphenyl) -3-nheptylthio) propane

1,1-bis (3-n-octyl-5-isopropyl-2-hydroxyphenyl) -3-n-hexadecylthio) -n-butane

1,1-bis (3-octadecyl-5-methyl-2-hydroxyphenyl) -3- (ethylthio) -n-butane

1,1-Bis-B-methyl-5- (2-ethylhexyl) -2-hydroxyphenyl] -3- (neikosylthio) -n-butane

1,1-bis (3-butyl-5-n-octyl-2-hydroxyphenyl) -3- (n-heptadecylthio) -n-butane

l, l-bis (3-isobutyl-5-n-octyl-2-hydroxyphenyl) -3- (2-ethylhexylthio) propane

1,1-bis (3-methyl-5-n-octyl-2-hydroxyphenyl) -3- (n-hexadecylthio) propane

1,1-bis- (3-methyl-5-ethyl-2-hydroxyphenyl) -2-n-hexyl-3- (n-tridecylthio) -n-butane

1,1-bis (3,5-dimethyl-2-hydroxyphenyl) -2-methyl-3- (noctylthio) propane

1,1-bis- (3,5-dimethyl-2-hydroxyphenyl) -3- (n-hexylthio) -n-nonane.

The compounds of the formula I are used as stabilizers for elastomers such as natural rubber, polybutadiene, Ethylene-propylene copolymers, propylene-butene-1 copolymers, Propylene-isobutylene copolymers, styrene-butadiene copolymers, as well as terpolymers of ethylene and propylene with a diene, such as hexadiene, dicyclopentadiene or ethylidene norbornene; as well as impact-resistant modified styrene

609BU / 1 192

polymers, such as acrylonitrile / butydiene / styrene, acrylonitrile / styrene, or acrylic ester copolymers, are used.

The compounds of the formula I according to the invention surprisingly have a better action than that structurally related compounds described in British Patent 1,116,127.

The compounds of Forms 1 I are the substrates in a concentration of 0.005 to 5% by weight, calculated on the material to be stabilized, incorporated.

Preferably 0.01 to 1.0, particularly preferably 0.02 to 0.5% by weight of the compounds, calculated on the basis of this stabilizing material, 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, before or during shaping, or by applying the dissolved or dispersed compounds to the polymer, optionally take place with subsequent evaporation of the solvent. The compounds of formula I. can also be added before or during the polymerization.

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

1. Antioxidants

1.1. Simple 2,6-DJaIkVlPhBnOIe , such as, for example, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol , 2,6-dioctadecyl-4-methylphenol.

8 0 9 8 14/119?

1.2. Derivatives of alkylated hydroquinones . such as 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl 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. Hydroxylated thiodiphenyl ethers , such as 2.2 ^l -thiobis- (6-tert-butyl-4-methylphenol), 2,2'-thiobis- (4-octylphenol), 4,4'-thiobis- (6-tert.- butyl-3-methylphenol, 4,4'-thiobis (3,6-di-sec. amylphenol), 4,4 ^f thiobis (6-tert-butyl-2-methylphenol), 4,4'-bis - (2,6-diraethyl-4-hydroxyphenyl) disulfide.

1.4. Alkylidene bisphenols , such as, for example, 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 4.4 ^l -methylene bis - (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-methyl-6- (amethylcyclohexyl) phenol], 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, l _v l-bis (5-tert-butyl-4-hydroxy-2-methy! phenyl) butane, 2.2 _T bis (3,5-di-

• 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-aodecylmercapto-butane, l, l, 5,5-tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane, ethylene glycol bis- [3,3-bis- (3'-tert-butyl-4 ¹ -hydroxyphenyl) butyrate].

1.5. 0-, N- and S-benzyl compounds , such as

'3,5,3' _t 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl-

- ether, ^ Hydroxy-S.S-dimethylbenzyl-niercaptoessigsMure-octadecylester, Tris (3,5-di-tert-butyl-4-hyd "roxybenzyl) amine, Bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate.

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

^: Bis- (3,5-di-tert-butyl-4-hydroxybenzyl) -malonic acid-

didodecyl mercaptoethyl ester, 2,2-bis- (3,5-di-tert. butyl-4-hydroxybenzyl) malonic acid di [4- (l, 1,3, '3-tetraraethylbutyl) phenylj ester.

1.7. Kydroxybenzvl-aromatics, such as l _f 3,5-tri- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, l, 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-octylmercapto-4,6-bis- (3,5 -di-tert-butyl-4-hydroxy-anilino) -s-triazine, 2-octylmercapto-4,6-bis- (3,5-di-tert-butyl-4-

hydroxyphenoxy) -s-triazine, 2,4,6-tris- (3,5-di-tert-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 the ß- (3,5-di-tert.b ^ tyl -4-hydroxyphenvl) -

propionic acid , such as

1,3 _f 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.

6098 1 4/119?

1.10. Esters of ß- (3, 5-di-tert-butyl-4-hydroxyphenyl) -pro ρ i ο r. it only contains mono- or polyhydric alcohols,

^w 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, triethylhexanediol, trimethylfollowane, Trimethylolpropane, tris-hydroxyethyl isocyanurate, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane.

1.11. Esters of g- (5-tert .butvl-4-hvdroxv-3-πlethvlDhenvl · ') ■ propionic acid with monohydric 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-trioxab icyclo [2,2,2] octane.

1.12. E ster of the 3,5-di-tert-butyl-4-hydroxvnhenylessigsSure mic 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, Trimethylhexanediol, trimethylol-sthan, trimethylolpropane, tris-hydroxyethyl isocyanurate, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo {2,2,2] octane. . '..

809814/1 192

- JLU -

2 * 40 * 32

1.13 benzyl phosphonates such as

3 _t 5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid ^w 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-1-hydroxy-S-methylbenzyl-phosphonic acid dioctadecyl ester.

1.14 amino acid derivatives such as Phenyl-1-naphthylamine, phenyl-2-naphthylamine, N ₁ N ¹ -di-phenyl-p-phenylenediamine, N, N ¹ -di-2-naphthyl-p-phenylenediamine, N, N ¹ -di-2-naphthyl- p-phenylenediamine, N, N'-di-sec.butyl-p-phenylenediamine, 6-ethoxy-2, 2 ^ -trimethyl-l ^ -dihydroquinoline, 6-

• Dodecyl-2,2 ^ -trimethyl-l ^ -dihydroquinoline, mono- and Dioctylirninodibenzyl, polyraerized 2,2,4-

• Trimethyl-l ^ -dihydroquinoline. Octylated di-

phenylamine, nonylated diphenylamine, N-phenyl-N ¹ -. cyclohexyl-p-phenylenediamine, N-phanyl-N ¹ -isopropylp-phenylenediamine, N ₅ N'-di-sec.octyl-p-phenylenediamine, N-phenyl-N'-sec.octyl-p-phenylenediamine, N, N ^! - Di- (1,4-diraethylpentyl) -p-phenylenediamine, N, N ¹ -dimethyl-N, N ¹ -di-Csec.octyl) -p-phenylenediamine, 2,6-dimethyl-4-raethoxyaniline, 4- Ethoxy-N-sec-butylaniline, diphenylatin-acetone condensation product, phenothiazine.

2. ' UV absorbers and light stabilizers

2.1. 2- (2 * hydroxyphenyl) benzotriazoles, such as the S'-methyl-, 3 ^1, 5'-di-tert-butyl-, 5'-tert-butyl-, 5 '- (l, l, 3 , 3-tetramethylbutyl) -, 5-chloro-3 ^f , 5'-di-tert-butyl-, S-chloro-S'-tert-butyl-S ¹ -methyl-, 3 ¹ -sec-butyl-5 ¹ -tert .butyl-, 3'-a-methylbenzyl-5'-methyl-, 3'-α-methylbenzyl-5'-methyl-5-chloro-, .4'-hydroxy-, 4'-methoxy-, 4'- Octoxy, 3 ', 5'-diert. amyl, 3'-methyl-5'-carbomethoxyethyl, 5-

Chloro-3 ¹ , 5'-di-tert-amyl derivative. 6 0 9 8 1 / ₊ / 119 2

-IL-

2.2. 2,4-bis- (2'-hydroxyphenyl) -6-alkvl-s-triazines , such as, for example

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

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

2.4. l _t 3-bis- (2'-hydroxybenzoyl) -benzenes , such as, for example, 1,3-bis- (2'-hydroxy-4 ¹ -hexyloxy-benzoyl) -benzene, 1,3-bis- (2'-hydroxy -4 ¹ -octyloxy-benzoyl) -benzene, 1,3-bis- (2'-hydroxy-4 ¹ -dodecyloxy-benzoyl) -benzene.

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 octadecyl ester or ^ -methyl ^ jo-di-tert-butylphenyl ester.

2.6. Acrylates , such as

et-cyano-ß.ß-diphenylacrylic acid-ethy ester or -isooctyl ester, a-carbomethoxy-cinnamic acid methyl ester, a-cyano-ß-methyl-p-methoxy-zinitol acid methyl ester or -butyl ester, N- (j5-carbomethoxyvinyl) -2-methylindoline.

2.7. Nickel compounds , such as

Nickel complexes of 2,2'-thio-bis [4- (l, l, 3,3-tetramethylbutyl) -phenol], like the 1: 1 or the 1: 2 iCopiplex, optionally with additional ligands. »Ie n-butylamine, triethanolamine or N-cyclohexyldi-ethanolamine, Nickel complexes of bis [2-hydroxy-4-.C1,1,3,3-tetramethylbutyl) -phenyl] -sulfons, -like 43er 2: 1 complex, if necessary with additional !, ligands such as 2-ethylcaproic acid, nickel dibutyldi-. jthiocarbamate, nickel salts of 4-hydroxy-3,5-di-

tert-butylbenzyl-phosphonic acid monoalkyl esters 'As from the methyl, ethyl or butyl ester, nickel complexes from ketoximes such as from 2-hydroxy-4-methyl-. phenyl imdecyl ketone oxime, nickel 3,5-di-tert-butyl-4-hydroxybenzoate, Nickel isopropyl xanthate.

2.8. Sterically hindered amines, such as 4-benzoyloxy-2,2,6,6-tetratnethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, bis-

(2,2,6,6-tetramethylpiperidyl) sebacate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro [4,5] decane 2,4-dione.

2.9. Oxalic acid diamides , such as

4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-ditert.butyl-oxanilide, 2-ethoxy-2 ', ethyl-oxanilide, N ^ N'-bis (3-dimethylaniinopropyl) oxalainide, 2-ethoxy-5-tert-butyl-2'-ethyl-oxaniline and its mixture with 2-ethoxy-2'-ethyl-5,4'-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, N 1} -diacetyl-adipic acid dihydrazide, N, N ^f -bis-salicyloyl-oxalic acid dihydrazide, N, N ¹ -bis-salicyloylhydrazide, N, N 1 -bis-salicyloylhydrazide (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, N-salicylal-N ^f salicylidene hydrazine, 3-salicyloylamino-1,2,4-triazole.

4. ' Phosphites , such as

Triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialky phosphite, Tri- (nony! Phenyl) phosphite, trilauryl phosphite, Trioctadecyl phosphite, 3,9-di-isodecyloxy-2,4,8, 10-tetroxa-3,9-diphospha-spiro [5.5]

25ΑΠΛ32 -is-

tindecane, tri- (4-hydroxy-3,5-di-tert-butylphenyl) - "phosphite.

5. Peroxide-destroying compounds , such as

Esters of ß-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl

ester, mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole.

6. Nucleating agents , such as

4-tert-butybenzoic acid, adipic acid, diphenylacetic acid.

7. Other additives , such as

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

-The production and use of the invention Compounds which can be used are described in more detail in the following examples. Parts mean parts by weight, and percentages mean percentages by weight.

S098U / 1 192

A) Establishing the connections

Examples 1-6: 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) -

3- (n-dodecylthio) -n-butane

24.4 g of 2,4-dimethylphenol and 46.9 g Bortrifluoridäthylätherat be at 0-5 ⁰ C within 10 hours of 27.2 g of 3- (n-dodecylthio) -butanal-1 was added and the reaction mixture after 24 hours at room temperature touched. A white crystal paste is formed, to which 70 ml of methanol are added while stirring and cooling. The suspension is ^{heated to 50 °} C. for half an hour, cooled again and the crystals are filtered off with suction.

For purification, successively washed with methanol, water and methanol again and at 40 ⁰ C.

This gives 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) -3- (n-dodecylthio) butane (Stabilizer No. 1) in the form of white crystals with a melting point of 106-1O8 ° C.

If in the preceding example the 3- (n-dodecylthio) -butanal-1 is replaced by one of the thia-aldehydes in the Table 1 below gives the corresponding thia-alkylidene-bisphenols.

0 9 8 14/1192

2 5 u Π u 3

Table 1

example

Rod.

No.

Thia aldehyde thio alkylidenebisphenol

Schme point

HC-CH ₀ CH ₀ -SnC, H _f

HC-CH CH-S - ^ - C ₄ H ₉ CH ₃

ii

HC-CH ₀ CH ₀ -S - ^ - C ₀ H _n - LL oil /

HC-CH ₀ -CH-SnC _Q H.,

Li oil/

HCCH ₂ -CH-Sn-CH ₀

CH ₀ ι L l, l-bis (3,5-dimethyl-2-hydroxyphenyl) -3- (η-butyltnio) propane

1,1-bis (3,5-dimethyl-2-hydroxyphenyl) -3- (n-butylthio) -n-butane

1,1-bis (3,5-dimethyl-2-hydroxyphenyl) -3- (n-octylthio) propane

1,1-bis (3,5-dimethyl-2-hydroxyphenyl) -3- (n-octylthio) -n-butane

1,1-bis- (3,5-dimethyl-2-hydroxyphenyl) -3- (n-dodecylthio) -n-hexane

110 '

103 ^;

104 ³

116 '

ca 5C (column chroma thogra 'erein

Ate ,,

In isolating the compounds of the above Examples 2-5 must, under certain circumstances, take into account the very different crystallization tendencies of the substances will. If necessary, ice water has to be added to the reaction mixture and the organic phase has to be neutral washed and dried, whereupon this either by evaporation and treatment with methanol or by column chromatographic purification can be converted into the crystalline products.

Example 7 l, l-bis (3-methyl-5-tert-butyl-2-

hydroxyphenyl) -3- (n-octylthio) -nbutane

If the 2,4-dimethylphenol is replaced in example 1 by 2-methyl-4-tert-butylphenol, l, l-bis- (3-methyl-5-tert-butyl-2-hydroxyphenyl) -3-n-octylthio) -n-butane is obtained with the same procedure (Stabilizer No. 6) in the form of a viscous oil, which is freed from by-products by column chromatography.

The elemental analysis agrees with the given formula Agree.

Example 8 1,1-bis (3-ethyl-5-tert-butyl-2-hydroxy-

phenyl) -3- (n-dodecylthio) -n-butane

In Example 1, the 2,4-dimethylphenol is replaced by 2-ethyl-4-tert.-butylph.enol, the 1,1-bis (3-ethyl-5-tert.-butyl-2-hydroxyphenyl) -3- (n-dodecylthio) is obtained with the same procedure -n-butane (Stabilizer No. 8) in the form of a viscous oil, which by column chromatography is freed from by-products.

609814/1192

254CU32

B) Application examples

Examples 9-13 Stabilization of polybutadiene

rubber

100 parts of polybutadiene (“Solprene 250” from Phillips), which is pre-stabilized with 0.36% 2,6-di-tert-butyl-p-cresol, are additionally each with 0.1 parts of the stabilizers given in Table 2 in a Brabender Piastographen at 150 ⁰ C and 60 rev / min, for 30 minutes kneaded. During this time the kneading resistance is continuously registered in the form of the torque. As a result of networking and subsequent degradation, a maximum torque occurs. The effectiveness of the stabilizers is expressed in a reduction in the maximum torque.

Another criterion for the protective effect of the incorporated stabilizers is that after the Brabender treatment gel content to be determined. For this purpose, 1 g of the sample is poured into 100 ml overnight at room temperature Toluene dissolved. These solutions are filtered through glass wool, the retained gel particles with little Washed toluene, the filtered solutions evaporated to dryness and dried to constant weight. The gel content of a sample is obtained from the following calculation:

Gel content in% = EA _{χ 1QQ}

E = total weight of the examined sample A = * weight of the dissolved fraction.

Known stabilizers were used as a comparison in Examples 9-11.

809814/1192

Table 2

at
game stabilizer Torque maximum
in grams χ meters Gelgehal
a) 9 without stabilizer 3625 44 10 1 1980 0 11 - 2,6-di-tert-butyl-4-
me thy1-1-hydroxypheny1 3350 35 12th 2.2 ^r -Methylene-bis- (6 -
tert-butyl-4-methyl
phenol 3550 33 13th l, l-bis (2-methyl-5-tert.-
butyl-4-hydroxyphenyl) -
3- (n-octadecylthio) -n-
butane 3250 35

Examples 14-16

Stabilization of polybutadiene rubber

100 parts of polybutadiene ("Solprene 250" from Phillips), which is pre-stabilized with 0.36% 2,6-di-tert-butyl-p-cresol, are additionally mixed with 0.1 part of one of the stabilizers given in Table 3 in a Brabender plastograph at 15O ⁰ C and 60 rev / min. homogenized for 10 minutes. The thus stabilized mixtures are pressed in a press at 12O ⁰ C for 5 minutes to 10 mm thick test specimens. The non-stabilized rubber test specimen serving as a comparison is produced in the same way.

6 0 9 8 14/1192

2S41U32

The Mooney value determined after storage in air at elevated temperatures is the criterion for the protective effect of the incorporated stabilizers. For this purpose, the test pieces are held on aluminum sheets in an air-circulating oven at 150 ⁰ C and tested for its Mooney after 20 hours. (DIN 53523, ASTM D 927-57 T) The Mooney value is understood to be the torque that has to be used to rotate a cylindrical disc (rotor) at a speed of 2 rpm. to rotate in a chamber filled with the sample. The reading of the value is done after 4 minutes running time of the rotor at a -temperature of 100 G ^0. Higher Mooney values mean crosslinking of the plastic and thus damage due to oven aging.

Table 3

stabilizer
No. Mooney value Torque without
1
5 128
48
48 1.08 kp χ m
0.40 kgf
0.40 kgf

Claims (11)

Patent claims DR. ERLEN D D INNE ._ PA T E N TAN VV ALT 2 8 Ü R E (M E N L "H L A N D S T R A L ·, S E 2 3 1. Compounds of the general formula I (D wherein R- an alkyl group with 1 to 18 carbon atoms which is not branched in the α-position, R _? a linear or branched alkyl group with Γ to 8 carbon atoms or a hydrogen atom, R and R ₁ . each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R, a linear or branched alkyl group having 1 to 20 carbon atoms, where the carbon chain can be interrupted by sulfur atoms mean. 2. Compounds according to claim 1, characterized in that that R is an alkyl radical with 4 to 16 carbon atoms is. 60981 4/1192 25-UU32 3. Compounds according to claims 1 to 2, characterized in that R is a methyl or ethyl group is. 4. Compounds according to claims 1 to 3, characterized in that R ₃ and R ₅ independently of one another denote a hydrogen atom or a methyl group. 5. Compounds according to claims 1 to 4, characterized in that R ₁ and R _{2 represent} the methyl group. 6. Process for the preparation of compounds of the general. Formula I, (D wherein R _{1 is} an alkyl group with 1 to 18 carbon atoms, in which the α-position is not branched, R2 is a linear or branched alkyl group with 1 to 8 carbon atoms or a hydrogen atom, R ₃ and R ₅ independently of one another represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and 609814/1 192 R, a linear or branched alkyl group with 1 to 20 carbon atoms, it being possible for the carbon chain to be interrupted by sulfur atoms, are characterized in that one
Phenol of formula II OH (II) wherein R ₁ and R «have the meaning given above, with a thiaaldehyde of the formula III HC CH — CH — SR ₄ (III) R ₅ R ₃ wherein R ₃ , R, and Rr have the meaning given above, is reacted in the presence of an acidic catalyst in a manner known per se. 7. The method according to claim 6, characterized in that the catalyst is a liquid Lewis acid etherate adduct which is used at the same time as the reaction medium. 8. The method according to claim 7, characterized in that boron trifluoride etherate is used as a catalyst
will. 9. The method according to claim 7, characterized in that at least 3 moles of catalyst per mole of reaction product can be used. 6098U / 1192 2540Λ32 10. A stabilized mixture consisting of a) an elastomer and b) 0.005 to 5% by weight of at least one of the compounds of formula I, based on the elastomer. 11. Mixture according to claim 10, characterized in that the compound of formula I is 1, l-bis- (3,5-dimethyl-2-hydroxyphenyl) -3- (n-dodecylthio) -n-butane is included. / I 609814/119?