CA1072122A - Alkylidene-bisphenols containing sulphur, and their use as stabilisers - Google Patents
Alkylidene-bisphenols containing sulphur, and their use as stabilisersInfo
- Publication number
- CA1072122A CA1072122A CA235,337A CA235337A CA1072122A CA 1072122 A CA1072122 A CA 1072122A CA 235337 A CA235337 A CA 235337A CA 1072122 A CA1072122 A CA 1072122A
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- tert
- butyl
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- carbon atoms
- alkyl group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/375—Thiols containing six-membered aromatic rings
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
1,1-Bis-(3-alkyl-2-hydroxyphenyl)-3-alkylthio-propanes to -pentadecanes in which the alkyl, which is in the 3-position, is not branched at the .alpha.-carbon atom, are good stabilisers for elastomers.
1,1-Bis-(3-alkyl-2-hydroxyphenyl)-3-alkylthio-propanes to -pentadecanes in which the alkyl, which is in the 3-position, is not branched at the .alpha.-carbon atom, are good stabilisers for elastomers.
Description
~07ZlZZ
1,1'-Bis-(2-hydroxy-3,5-dialkylphenyl)-methylenes which contain a tertiary alkyl group in the 3-position an~
which are used as antioxidants for rubber, are kno~n from U ~. Patent 2,796,444. British Patent 1,116,127 describesS
as s-tabilisers for polyolefines, 1,1 bis-(3,5-dialkyl-2-hydloxyphenyl)-3-thioalkyl-propanes in which the alkyl group, which is in the 3-position~is branched at the a-carbon atom.
The present invention relates to compounds of the general formula I
-OH OH
R5- C~ ~ (I)
1,1'-Bis-(2-hydroxy-3,5-dialkylphenyl)-methylenes which contain a tertiary alkyl group in the 3-position an~
which are used as antioxidants for rubber, are kno~n from U ~. Patent 2,796,444. British Patent 1,116,127 describesS
as s-tabilisers for polyolefines, 1,1 bis-(3,5-dialkyl-2-hydloxyphenyl)-3-thioalkyl-propanes in which the alkyl group, which is in the 3-position~is branched at the a-carbon atom.
The present invention relates to compounds of the general formula I
-OH OH
R5- C~ ~ (I)
2 / C \ R2 wherein Rl denotes an alkyl group which has 1 to 18 carbon atoms and which is not branched in the a-posi-tion, R2 denotes a linear or branched alkyl group having 1 to 8 carbon atoms, or a hydrogen atom, R3 and R5 each denote a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R4 denotes a linear or branched alkyl group having 1 to -20 carbon atoms wherein the carbon chain can be interrupted by sulphur atoms.
In the formula I, P.l is preferabl~r an alkyl group which has 1 to ~, particularly 1 to 4 carbon atoms, and which . `
~ - 2 - ~ ~
.
- -. - . : -' : . . . . .
:-.
- . ~ .
1072~2Z
is not branched a~ the a-carbon atom, and R2 is preferably an alkyl group having 1 to 4 carbon atoms.
The alkyl radical R~, which is interrupted by sul-phur, is preferably composed in such a way that at least 2 carbon atoms are linked between two sulphur atoms. R4 is particularly preferentially an alkyl radical, particularly an alkyl radical having 4 to 16 carbon atoms.
R3 is preferably a hydrogen atom or alkyl having 1 to 4 carbon atoms. Preferably, R3 and R5 are, indepen-dently of one another, each a methyl group or a hydrogen atom, in particular R3 and R5 are a hydrogen atom or R3 is a methyl group and R5 is a hydrogen atom.
Particularly valuable compounds of the formula I
are those in which Rl denotes the methyl or ethyl group and R2 preferably denotes an alkyl radical having 1 to 4 carbon atoms, particularly also the methyl or ethyl group.
In formula I Rl and R2 particularly preferentially represent the methyl group and R4 preferakly represents an alkyl radical having 4 to 16 carbon atoms.
The compounds of the formula I are new and are obtained by processes which are in tnemselves known, by reacting, in the presence of an acid catalyst, a phenGl of the formula II o~
i ~ (II) . ~ .
1072~ZZ
wherein Rl ~nd R2 have the same me~ling as in formula I, with a thioaldehyde of the formula III
HC - CH ~ CH - S - R4 (IIl) ~herein R3 and R4 and R5 have the same meani-ng as in formu a I. ~no~n processes are, for exampleS described in 3ritish Patent Specification 1,116,127. In general, about 2 mols of phenol are used here to about 1 mol of thioaldehyde.
Examples of catalysts which can be used are: hydro-gen chloride, sulphuric acid, zinc chloride or trifluoroacetic acid. The reaction can be carried out with or ~ithout a so -vent.
Examples of suitable solvents are: aliphatic and aromatic hydrocarbons 5 halogenated aliphatic and aromatic hydrocarbons, alcohols or ethers.
It is prefera~le to employ as the catalyst a liqu d Lewis acid e-therate-adduct which acts at the sa~e time as the reaction medium. Particularly good yields are achieved here if at least 3 mols of the liquid catalyst are used per mol of reaction product.
The following should be mentioned as Lewis acids ~rhich are suitable for -the formation of ether-adducts: aluminium trihalides and boron trihalides, for example alumini-~m tri-fluoride 9 trichloride Qnd -tribromide Qnd boron trifluoride and -crichloride.
.
:- : ~ . - - .
.. . . -: -- .
: ~ :
.
Preferred catalys-ts are adducts fo~.ned from boron tri~luoride and ethers, particularly diethyl ether.
The aldehydes of the ~ormula III are obtai,1ed by carrying out an addition reaction, in the presence of a base - -such as triethylamine, between mercaptans R4SH, the radical R4 ha~ing the same meaning as in formula I, and corresponding unsaturated aldehydes.
Examples o~ compounds of the formula I are~
bis-(3,5-dimethyl-2-hydro~-yphenyl)-3-(n-dodecylthio)-n-butane, 151-bis--(3,5-dimethyl-2-hydroxyphenyl)-3-(n-butylthio~-propane~ l,l-bis-(3,5-dimethyl-2-hydroxJphenyl)-3 (n-octyl-thio)-n-butane~ l,l-bis-(3,5-dimethyl-2-hydroxyphenyl)-3-(n-octylthio)-propane, 1,1-bis-(3-methyl-5 etihyl-2-hydroxy-phenyl)-3-(1l-Gctylthio)~propane, 1,1-bis-(3-ethyl-5-methyl-2-hydrox~pnenyi)-3-~n-octadecyl-thio)-n-butane, 1,l-bis-( ~me-thyl-5-1l-butyl-2-hydro~yphenyl)-3-(n-oGtylt~io)-rl-butane, 191-bis-(3-methyl-5-~ert.-butyl-2-hydroxyphenyl)-3-~-octylthio)-n-butane, l,l-bis-(3-2thyl-~-n-octyl-2-hydro~.y-phenyl)-3-methylthio-propane, 1,1-bis-(3-n-butal-5-tert.-butyl-2-hydroxyphenyl)-3-n-heptylthio)-propane, 1~1-bis-(3-n-octyl-5-isopropyl-2-hydroxyphenyl~- ~ n-hexadec-ylthio)-n butane, l,l-bis-(3-octadecyl 5-methyl-2-hydro~yphenyl)-3-~ethylthio)-n-butane, 1,1-bis-~3-methyl-5-(2-ethylhexyl)-2-hydro~yphenyl~--3-~n-eicosylthio)-n-butane, 1,1-bis-(3-butyl-5-n-octyl-2-hydroxJplleny~ 3~(n-heptadecylthio)-n-butane, 1,1-bis-(3-isobutyl-5-n-octyl-2-hydroxyphenyl)-3-(2-ethvl-hexylthio)-propane, 1,1-bis--(3-methyl-5-n-oct-yl-2-hyd-lo.~y-.
phenyl)-3-~n-hexadecylthio)-propane, 1,1-bis-(3-methyl-5-ethyl-2-hydroxyphenyl)-2-n-hexyl-3-(n-tridecylthio)-r.-butane, l,l-bis-(3,5-dimethyl-2-hydro~.~phenyl)-2-methyl-~-(n-octylthio)-propane and 1,1-bis~(3,~-dimethyl-2-hydroxy--phenyl)-3-(n-hexylthio)-n-nonane.
The compounds of the formula I are used as stabilisers ~or elastomers, such as, for example, natural rubber, poly-butadiene, ethylene-propylene copolymers, propylene-butene-l copolymers, propylene-isobu'ylene copoiymers, s~yr~ne-bvtadiene copolymers, and terpolymers of ethylene and propy-lene with a diene, such as, for example 3 hexadie~e, dicyclopentadiene or ethylidenenorbolnene; and styrene poly-mers which have been modified by rubber phases so ~s to be impact-resistant, such as acrylonitrile/butadiene/styrene, acrylonitrile/styreneS or acrylic ester copolymers.
In this field -the compo~nds of the formula I, accor-ding to the invention7 have, surprisingly, a better action than compovnds which are structura]ly closely related5 which are described in British Patent Specification 1,116~127.
The compounds oY the ~ormula I are incorporated in the substrates in a concentration of 0.005 to 5~ b-y weight, reia-tive to the material to be stabilised.
Preferably, 0.01 to 1.0, particularly preferably 0.02 to 0.5, % by weight of the compovlds~ relative to -the material to be stabilised, are incorporated in-to the latter. The incorporation can be carried out, for example, by mixin~ in at least one of the compoulLds of -the for~ula I and optionally ~ . ~
. ~ .
:
~urther additives by the methods customary in the art, before or during shaping, or by applying the compounds, dissol~ed or dispersed, to the polymer, where appropriate wl-th subseauent evaporation of the solvent. The compounds of the formula I
can also be added before o- during the polymerisation.
The ~ollowing may be mentioned as examples of ~urther additives ~ith ~hich the stabilisers can be conjointly employed:
1. Antioxidants 1.1. SimPle 2,6~dialky phenols, such as, for examplel 2,6-di-tert.-butyl-4-methylphenol, 2-tert.-butyl-4,6-dimethylphenol, 2,6-di tert ~butyl-4-me-tho~ymethylPhenol and 2,6~dioctadecyl-4-methylphenol.
1.2. ~ , such as, for example, 2,~-di-tert.-butyl-hydroquinone, 2,5-di-tert~-amyl-hydroquinone, 2,6-di-tert.-butyl-hydroquinone 9 2,5-di-tert.-butyl-4-hydrox~J-anisole, 3,5-di-tert.~butyl-4 hydrox~-anisole, tris-(395-di-tert.-butyl-4-hydroxyphenyl)phosphi~e,
In the formula I, P.l is preferabl~r an alkyl group which has 1 to ~, particularly 1 to 4 carbon atoms, and which . `
~ - 2 - ~ ~
.
- -. - . : -' : . . . . .
:-.
- . ~ .
1072~2Z
is not branched a~ the a-carbon atom, and R2 is preferably an alkyl group having 1 to 4 carbon atoms.
The alkyl radical R~, which is interrupted by sul-phur, is preferably composed in such a way that at least 2 carbon atoms are linked between two sulphur atoms. R4 is particularly preferentially an alkyl radical, particularly an alkyl radical having 4 to 16 carbon atoms.
R3 is preferably a hydrogen atom or alkyl having 1 to 4 carbon atoms. Preferably, R3 and R5 are, indepen-dently of one another, each a methyl group or a hydrogen atom, in particular R3 and R5 are a hydrogen atom or R3 is a methyl group and R5 is a hydrogen atom.
Particularly valuable compounds of the formula I
are those in which Rl denotes the methyl or ethyl group and R2 preferably denotes an alkyl radical having 1 to 4 carbon atoms, particularly also the methyl or ethyl group.
In formula I Rl and R2 particularly preferentially represent the methyl group and R4 preferakly represents an alkyl radical having 4 to 16 carbon atoms.
The compounds of the formula I are new and are obtained by processes which are in tnemselves known, by reacting, in the presence of an acid catalyst, a phenGl of the formula II o~
i ~ (II) . ~ .
1072~ZZ
wherein Rl ~nd R2 have the same me~ling as in formula I, with a thioaldehyde of the formula III
HC - CH ~ CH - S - R4 (IIl) ~herein R3 and R4 and R5 have the same meani-ng as in formu a I. ~no~n processes are, for exampleS described in 3ritish Patent Specification 1,116,127. In general, about 2 mols of phenol are used here to about 1 mol of thioaldehyde.
Examples of catalysts which can be used are: hydro-gen chloride, sulphuric acid, zinc chloride or trifluoroacetic acid. The reaction can be carried out with or ~ithout a so -vent.
Examples of suitable solvents are: aliphatic and aromatic hydrocarbons 5 halogenated aliphatic and aromatic hydrocarbons, alcohols or ethers.
It is prefera~le to employ as the catalyst a liqu d Lewis acid e-therate-adduct which acts at the sa~e time as the reaction medium. Particularly good yields are achieved here if at least 3 mols of the liquid catalyst are used per mol of reaction product.
The following should be mentioned as Lewis acids ~rhich are suitable for -the formation of ether-adducts: aluminium trihalides and boron trihalides, for example alumini-~m tri-fluoride 9 trichloride Qnd -tribromide Qnd boron trifluoride and -crichloride.
.
:- : ~ . - - .
.. . . -: -- .
: ~ :
.
Preferred catalys-ts are adducts fo~.ned from boron tri~luoride and ethers, particularly diethyl ether.
The aldehydes of the ~ormula III are obtai,1ed by carrying out an addition reaction, in the presence of a base - -such as triethylamine, between mercaptans R4SH, the radical R4 ha~ing the same meaning as in formula I, and corresponding unsaturated aldehydes.
Examples o~ compounds of the formula I are~
bis-(3,5-dimethyl-2-hydro~-yphenyl)-3-(n-dodecylthio)-n-butane, 151-bis--(3,5-dimethyl-2-hydroxyphenyl)-3-(n-butylthio~-propane~ l,l-bis-(3,5-dimethyl-2-hydroxJphenyl)-3 (n-octyl-thio)-n-butane~ l,l-bis-(3,5-dimethyl-2-hydroxyphenyl)-3-(n-octylthio)-propane, 1,1-bis-(3-methyl-5 etihyl-2-hydroxy-phenyl)-3-(1l-Gctylthio)~propane, 1,1-bis-(3-ethyl-5-methyl-2-hydrox~pnenyi)-3-~n-octadecyl-thio)-n-butane, 1,l-bis-( ~me-thyl-5-1l-butyl-2-hydro~yphenyl)-3-(n-oGtylt~io)-rl-butane, 191-bis-(3-methyl-5-~ert.-butyl-2-hydroxyphenyl)-3-~-octylthio)-n-butane, l,l-bis-(3-2thyl-~-n-octyl-2-hydro~.y-phenyl)-3-methylthio-propane, 1,1-bis-(3-n-butal-5-tert.-butyl-2-hydroxyphenyl)-3-n-heptylthio)-propane, 1~1-bis-(3-n-octyl-5-isopropyl-2-hydroxyphenyl~- ~ n-hexadec-ylthio)-n butane, l,l-bis-(3-octadecyl 5-methyl-2-hydro~yphenyl)-3-~ethylthio)-n-butane, 1,1-bis-~3-methyl-5-(2-ethylhexyl)-2-hydro~yphenyl~--3-~n-eicosylthio)-n-butane, 1,1-bis-(3-butyl-5-n-octyl-2-hydroxJplleny~ 3~(n-heptadecylthio)-n-butane, 1,1-bis-(3-isobutyl-5-n-octyl-2-hydroxyphenyl)-3-(2-ethvl-hexylthio)-propane, 1,1-bis--(3-methyl-5-n-oct-yl-2-hyd-lo.~y-.
phenyl)-3-~n-hexadecylthio)-propane, 1,1-bis-(3-methyl-5-ethyl-2-hydroxyphenyl)-2-n-hexyl-3-(n-tridecylthio)-r.-butane, l,l-bis-(3,5-dimethyl-2-hydro~.~phenyl)-2-methyl-~-(n-octylthio)-propane and 1,1-bis~(3,~-dimethyl-2-hydroxy--phenyl)-3-(n-hexylthio)-n-nonane.
The compounds of the formula I are used as stabilisers ~or elastomers, such as, for example, natural rubber, poly-butadiene, ethylene-propylene copolymers, propylene-butene-l copolymers, propylene-isobu'ylene copoiymers, s~yr~ne-bvtadiene copolymers, and terpolymers of ethylene and propy-lene with a diene, such as, for example 3 hexadie~e, dicyclopentadiene or ethylidenenorbolnene; and styrene poly-mers which have been modified by rubber phases so ~s to be impact-resistant, such as acrylonitrile/butadiene/styrene, acrylonitrile/styreneS or acrylic ester copolymers.
In this field -the compo~nds of the formula I, accor-ding to the invention7 have, surprisingly, a better action than compovnds which are structura]ly closely related5 which are described in British Patent Specification 1,116~127.
The compounds oY the ~ormula I are incorporated in the substrates in a concentration of 0.005 to 5~ b-y weight, reia-tive to the material to be stabilised.
Preferably, 0.01 to 1.0, particularly preferably 0.02 to 0.5, % by weight of the compovlds~ relative to -the material to be stabilised, are incorporated in-to the latter. The incorporation can be carried out, for example, by mixin~ in at least one of the compoulLds of -the for~ula I and optionally ~ . ~
. ~ .
:
~urther additives by the methods customary in the art, before or during shaping, or by applying the compounds, dissol~ed or dispersed, to the polymer, where appropriate wl-th subseauent evaporation of the solvent. The compounds of the formula I
can also be added before o- during the polymerisation.
The ~ollowing may be mentioned as examples of ~urther additives ~ith ~hich the stabilisers can be conjointly employed:
1. Antioxidants 1.1. SimPle 2,6~dialky phenols, such as, for examplel 2,6-di-tert.-butyl-4-methylphenol, 2-tert.-butyl-4,6-dimethylphenol, 2,6-di tert ~butyl-4-me-tho~ymethylPhenol and 2,6~dioctadecyl-4-methylphenol.
1.2. ~ , such as, for example, 2,~-di-tert.-butyl-hydroquinone, 2,5-di-tert~-amyl-hydroquinone, 2,6-di-tert.-butyl-hydroquinone 9 2,5-di-tert.-butyl-4-hydrox~J-anisole, 3,5-di-tert.~butyl-4 hydrox~-anisole, tris-(395-di-tert.-butyl-4-hydroxyphenyl)phosphi~e,
3,5-di-tert.-butyl-4-hydroxyphei1yl stearate and bis-(3,5-di-tert.-butyl-4-hydroxyphenyl) adipate.
1.3. Hydro~ylated ~h~odiPhenyl ethers, such as, for ex&mple~
2,2'-thio-bis-(6-tert.-butyl-4-methylphenol), 2,2'-thio-bis-(4-octylphenol), 4,4T-thio-bis-(6-tert.-butyl-3-methvlphenol),
1.3. Hydro~ylated ~h~odiPhenyl ethers, such as, for ex&mple~
2,2'-thio-bis-(6-tert.-butyl-4-methylphenol), 2,2'-thio-bis-(4-octylphenol), 4,4T-thio-bis-(6-tert.-butyl-3-methvlphenol),
4,4'-th o-bis~(3,6-di-sec.-amylphenol), 494'-thio-bis-(6-tert.-butyl-2-methylphenol) and 4,4' bis-(2 6-dimethyl-4-hydroxyphenol)-disulphide.-1.4. Alk~lide_e-bis~ el~ols, such as, for exampleg 2,2'-methylene-., .
' ' ' .
-.
bis-(6-tert.butyl-l~methylphenol), 272'-methylene-bis-(6-tert butyi-4-ethylphenol), 4,4'-methylene-bis-(6-tert.
butyl-2-methylphenol), 4,4'-methylene-bis-(2,6-di-tert.
butyl-phenol), 2,6-di-(3 ter-t.butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 2,2'-methylene-bis- r 4-methyl-6-(a-methylcyclo-hexyl)-phenol], l,l-bis-(3~5-dimethyl-2-hydrox~yphenyl)bltane, 2,2-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-dodec-Jlmercapto-butane, 1,1,5,5-tetra-(5-tert.butyl 4-hydroxy-2-me-thylphenyl)-pentane and ethylene-glycol-bis-[3,3-bis-(3'-tert.butyl-4l- -hydroxyphenyl)-butyrate].
1.5. O-, N- and_S-benzyl compounds, such as, for example, 3,5,3',5'-tetra-tert.butyl-494'-dihydroxydibenzyl ether, 4-hydroxy-3,5-dime-thylbenzy--mercaptoacetic acid oc-tadecyl ester, tris-(3,5-di-tert.butyl-4-hydroxybenzyl)-a~ine ~nd bis-(4-tert butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthal-ate.
1.6. H~droxyb~nzylated malon c esters~ such as, ~or example~
2,2-bis-(3,5-di~tert butyl-2-hydroxybenzyl)-malonic acid dioctadecyl ester~ 2-(3-tert.butyl-4-hydroxy-5-methylbenzyl)-malonic acid dioc-tadecyl es-ter, 2,2-bis-(3,5-di-tert.
butyl-4~hydroxyben7yl)-malonic acid di-dodecylmercapto-e'hyl ester and 2,2-bis-(3,5-di-tert.butyl-4-hydroxybenzyl)-malonic acid di-[4-(171,3,3-tetramethylbuty~)-phenyl]-ester~
1.7. Hydrox~benyl-aromatic compounds, such as, for example, 1,3,5-tri-(3,5-di-tert.butyl-4-hydroxybenzyl) 2~4 9 6-trime~hyl-.. , . ~ , . ..
.
1~72122 benzene, 1,4-di-t3,5-di-tert.butyl-4-hydroxybenzyl-2,3,5,6-tetramethylbenzene and 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-hydroxy-anilino)-s-triazine, 2-octylmercapto-4,6-bis-(3,5-di-tert.butyl-4-hydroxyanilino)-s-triazine, 2-octylm2rcapto-4,6-bis-(3,5-di-tert.butyl-4-hydroxy-phenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert.butyl-4-hydroxy-phenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert.butyl-4-hydroxyphenylethyl)-s-triazine and 1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxybenzyl) iso-cyanurate.
l.90Amides of ~-(3,5-di-tert.butyl-4-hydroxyphenyl)-pro-pionic acid,such as r for example, 1,3,5-tris-~3,5-di-tert.
butyl-4-hydroxyphenyl-propionyl)-hexahydro-s-triazine and N,N'-di-(3,5-di-tert.butyl-4-hydroxyphenyl-propionyll-hexamethylenediamine.
1.10. Esters of ~-(3,5-di-tert.but~l-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols, such as, for example, 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-thia-pentadecanol, trimethylhexanediol, trimethylolethane, trimethylolpropane, trishydroxyethyl isocyanurate and 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2,2,2]octane.
1.11. Esters of ~-(5-tert.butyl-4-hydroxy-3-methvlphenyl)-propionic acid with monohydric or polyhydric alcohols, such as for example, methanol, ethanol, octadecanol, 1,6-hexanediol, 1,3-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycolj ~07Z~ZZ
thiodiethylene glycol, neopentyl glycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, t~imethylhexanediol, trimethylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxy-methyl-l-phospha-2,6,7-trioxabicyclo[2,2,2]octane.
1~12. Esters of 3,5-ditert.butyl-4-hydroxyphenylacetic acid with nohydric or polyhydric alcohols, such as, for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, l,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentyl glycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, tri-methylhexanediol, trimethylolethane, trimethylolpropane tris-hydroxy-ethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-~2,2,2]octane.
1.13. Benzylphosphonates, such as, for example, 3,5-di-tert.butyl-4-hydroxybenzyl-phosphonic acid dimethyl ester, 3,5-di-tert.butyl-4-hydroxybenzyl-phosphonic acid diethyl ester, 3,5-di-tert.butyl-4-hydroxybenzyl-phosphonic acid dioctadecylester and 5-tert.butyl-4-hydroxy-3-methylbenzylphosphonic acid dioctadecyl ester.
1.14. Aminoaryl derivatives, such as, for example, phenyl-l-naphthylamine, phenyl-2-naphthylamine, N,N'-diphenyl-p-phenylene-diamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-di-sec.butyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline, monooctyliminodibenzyl and dioctyliminodibenzyl and polymerised 2,2,4-trimethyl-1.2-dihydroquinoline. Octylated 107ZlZZ
diphenylamine, nonylated diphenylamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenedia.~ine, N,N'-di-sec.octyl-p-phenylenediamine, N-phenyl '-sec.octyl-p-phenylenediamine, N,N'-di-(1,4-dimethylpentyl)-p-phenylene-diamine, N,N'-dimethyl-N,N'-di-(sec.octyl)-p-phenylenediamine, 2,6-dimethyl-4-methoxyaniline, 4-ethoxy-N-sec.butylaniline, the condensation product of diphenylamine and acetone, and phenothiazine.
2. W absorbers and light stabilisers 2.1. 2-(2'-Hydroxyphenyl~-benztriazoles, such as, for example, the 5'-methyl-, 3',5'-di-tert.butyl-, 5'-tert.butyl-, 5'-(1,1,-3,3-te-tramethylbutyl)-, 5-chloro-3',5l-di-tert.butyl-, 5-chloro-3'-tert.bu~yl-5'-methyl-, 3'-sec.butyl-5'-tert.butyl-, ~'~-methylbenzyl-5'-methyl-~ 3'-~-methylbenzyl-5'-methyl-5-chloro-, 4'-hydroxy-, 4'-me-thoxy-, 4'-octoxy-, 3'-,5'-di-tert.amyl-, 3'-methyl-5'-carbomethoxyethyl-or 5-chloro-3'-,5' d--tert.-amyl-derivative.
2.2. ~ ines~ such as, for example, the 6-ethyl-, 6-heptadecyl-or 6-undecyl-derivative.
2.3. 2-Hydroxy-benzophenones, such as,`for example, the 4-hydroxy-, 4-methox-y-, 4-octoxy-, 4-decyloxy-, 4-dodecvloxy-, 4-benzylox~, 4,2'g4'-trihydroxy- or 2'-hydroxy-454'-dimethcx-~-derivative.
2.4. 1,3-Bis- t 2'-hydrox-y-benzoyl)-benzenes 9 such as, for ex~ple~
1,3-bis-(2'-hydroxy-4'-hexyloxy-benzoyl)-be~zene, 1,3-bis-(2t-hydroxy-4'-octyloxy-benzoyl)-benzene and 1,3-bis-(2'-hydroxy-4'-dodecyloxy-benzoyl)-benzene.
" 107ZlZ2 2.5. Es.ers of G~-tionally substituted benzoic acids, such as, for example, phenyl salicylate, octylphenyl salicylate, diben-zoylresorcinol, bis-(4-tert.-butylbenzoyl)-resorcinol, benzoyl-resorcinol and 3,5-di-tert.-butyl-4-hydroxybenzoic acid 2,4-di-tert.butyl-phenyl ester, octadecyl ester or 2-methyl-4,o-di-tert.butyl-phenyl ester.
2.6. Acryla-tes, such as, for examPle~ a-cyano~ -diphenyl-acrylic acid ethyl ester or isooctyl ester, a-carbomethoxy-cinnamic acid methyl ester, a-cyano-~-methyl-p-me-thoxy-cir-rlamic acid methyl ester or butyl ester and N-(~-carbomethoxy--vi-nyl)-2-methyl-i-ndoline.
2.7. Nickel com~ouIlds, such as, for ex~mple5 nickel complexes of 2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or 1:2 complex, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohex~-l-di-ethanolamine, nickel complexes of bis-~2-hydroxy-4-(1,1,3,3-tetramethylbutyl)-phenyl]-sulphone, such as the 2:1 complex, optionally wi-th additional ligands such as 2-ethyl-caproic acid, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3~5-di-tert.butylbenzyl-phosphonic acid monoalkyl esters, such as of the methyl, ethyl or butyl ester, nickel complexes of ketoximes such as of 2-hydroxy-4-methyl-phenyl-urldecylketonoxime, nickel 3,5-di-tert.butyl-4~h-ydroxy-benzoate and nickel isopropylxanthate.
2.~. Sterically hindered amines, such as, for exampl2, L_ benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2~2,6,6-tetramethylpiperidine 9 bis-(252~6,5-tetramethylpip-. .
,:
''." ' ' .^ '- ' . . . ..
. . .
107Z~ZZ
eridyl) sebacate, and 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, for example, 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert.butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert.butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N,N'-bis-(3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert.butyl-2'-ethyl-oxanilide and its mixture with 2-etho~y-2'-ethyl-5,4'-di-tert.butyl-oxanilide and mixtures of ortho- and para-methoxy-as well as of o-ard p-ethoxy-dlsubstituted oxanilides.
3. Metal deactivators, such as, ~or exa~ple, oxanllide, isophthal-~c acid dihydrazide, sebacic acid bis-phenyl-hydrazide, bis-benzylidene-oxalic acid dihydrazide, N,N'-diacetyl-adipic acid dihydrazide, N,N'-bis-salicyloyl-oxalic acid dihydrazide, N,N'-bis-salicyloyl-hydrazine, N,N'-bis-(3,5-di-tert.butyl-4-hydroxyphenyl-propionyl)-hydrazine, N-salicylal~'-salicylidenehydrazine and 3-salicyloylamino-1,2,4-triazole.
4. Phosphites, such as, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyldial~yl phosphltes, tri-(nonyl-phenyl) phosphite, trilauryl phosphite, trioctadecyl phosphiteS
3,9-di-isodecyloxy-2,4,8,10-tetroxa 3,9-diphospha-sELro[5,53-undecane and tri-(4-hydroxy-3,5-di-tert.butylphenyl) phosphite.
' ' ' .
-.
bis-(6-tert.butyl-l~methylphenol), 272'-methylene-bis-(6-tert butyi-4-ethylphenol), 4,4'-methylene-bis-(6-tert.
butyl-2-methylphenol), 4,4'-methylene-bis-(2,6-di-tert.
butyl-phenol), 2,6-di-(3 ter-t.butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 2,2'-methylene-bis- r 4-methyl-6-(a-methylcyclo-hexyl)-phenol], l,l-bis-(3~5-dimethyl-2-hydrox~yphenyl)bltane, 2,2-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-dodec-Jlmercapto-butane, 1,1,5,5-tetra-(5-tert.butyl 4-hydroxy-2-me-thylphenyl)-pentane and ethylene-glycol-bis-[3,3-bis-(3'-tert.butyl-4l- -hydroxyphenyl)-butyrate].
1.5. O-, N- and_S-benzyl compounds, such as, for example, 3,5,3',5'-tetra-tert.butyl-494'-dihydroxydibenzyl ether, 4-hydroxy-3,5-dime-thylbenzy--mercaptoacetic acid oc-tadecyl ester, tris-(3,5-di-tert.butyl-4-hydroxybenzyl)-a~ine ~nd bis-(4-tert butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthal-ate.
1.6. H~droxyb~nzylated malon c esters~ such as, ~or example~
2,2-bis-(3,5-di~tert butyl-2-hydroxybenzyl)-malonic acid dioctadecyl ester~ 2-(3-tert.butyl-4-hydroxy-5-methylbenzyl)-malonic acid dioc-tadecyl es-ter, 2,2-bis-(3,5-di-tert.
butyl-4~hydroxyben7yl)-malonic acid di-dodecylmercapto-e'hyl ester and 2,2-bis-(3,5-di-tert.butyl-4-hydroxybenzyl)-malonic acid di-[4-(171,3,3-tetramethylbuty~)-phenyl]-ester~
1.7. Hydrox~benyl-aromatic compounds, such as, for example, 1,3,5-tri-(3,5-di-tert.butyl-4-hydroxybenzyl) 2~4 9 6-trime~hyl-.. , . ~ , . ..
.
1~72122 benzene, 1,4-di-t3,5-di-tert.butyl-4-hydroxybenzyl-2,3,5,6-tetramethylbenzene and 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-hydroxy-anilino)-s-triazine, 2-octylmercapto-4,6-bis-(3,5-di-tert.butyl-4-hydroxyanilino)-s-triazine, 2-octylm2rcapto-4,6-bis-(3,5-di-tert.butyl-4-hydroxy-phenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert.butyl-4-hydroxy-phenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert.butyl-4-hydroxyphenylethyl)-s-triazine and 1,3,5-tris-(3,5-di-tert.-butyl-4-hydroxybenzyl) iso-cyanurate.
l.90Amides of ~-(3,5-di-tert.butyl-4-hydroxyphenyl)-pro-pionic acid,such as r for example, 1,3,5-tris-~3,5-di-tert.
butyl-4-hydroxyphenyl-propionyl)-hexahydro-s-triazine and N,N'-di-(3,5-di-tert.butyl-4-hydroxyphenyl-propionyll-hexamethylenediamine.
1.10. Esters of ~-(3,5-di-tert.but~l-4-hydroxyphenyl)-propionic acid with monohydric or polyhydric alcohols, such as, for example, 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-thia-pentadecanol, trimethylhexanediol, trimethylolethane, trimethylolpropane, trishydroxyethyl isocyanurate and 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2,2,2]octane.
1.11. Esters of ~-(5-tert.butyl-4-hydroxy-3-methvlphenyl)-propionic acid with monohydric or polyhydric alcohols, such as for example, methanol, ethanol, octadecanol, 1,6-hexanediol, 1,3-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycolj ~07Z~ZZ
thiodiethylene glycol, neopentyl glycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, t~imethylhexanediol, trimethylolethane, trimethylolpropane, tris-hydroxyethyl isocyanurate and 4-hydroxy-methyl-l-phospha-2,6,7-trioxabicyclo[2,2,2]octane.
1~12. Esters of 3,5-ditert.butyl-4-hydroxyphenylacetic acid with nohydric or polyhydric alcohols, such as, for example, with methanol, ethanol, octadecanol, 1,6-hexanediol, l,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene glycol, thiodiethylene glycol, neopentyl glycol, pentaerythritol, 3-thia-undecanol, 3-thia-pentadecanol, tri-methylhexanediol, trimethylolethane, trimethylolpropane tris-hydroxy-ethyl isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo-~2,2,2]octane.
1.13. Benzylphosphonates, such as, for example, 3,5-di-tert.butyl-4-hydroxybenzyl-phosphonic acid dimethyl ester, 3,5-di-tert.butyl-4-hydroxybenzyl-phosphonic acid diethyl ester, 3,5-di-tert.butyl-4-hydroxybenzyl-phosphonic acid dioctadecylester and 5-tert.butyl-4-hydroxy-3-methylbenzylphosphonic acid dioctadecyl ester.
1.14. Aminoaryl derivatives, such as, for example, phenyl-l-naphthylamine, phenyl-2-naphthylamine, N,N'-diphenyl-p-phenylene-diamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-di-sec.butyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline, monooctyliminodibenzyl and dioctyliminodibenzyl and polymerised 2,2,4-trimethyl-1.2-dihydroquinoline. Octylated 107ZlZZ
diphenylamine, nonylated diphenylamine, N-phenyl-N'-cyclohexyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenedia.~ine, N,N'-di-sec.octyl-p-phenylenediamine, N-phenyl '-sec.octyl-p-phenylenediamine, N,N'-di-(1,4-dimethylpentyl)-p-phenylene-diamine, N,N'-dimethyl-N,N'-di-(sec.octyl)-p-phenylenediamine, 2,6-dimethyl-4-methoxyaniline, 4-ethoxy-N-sec.butylaniline, the condensation product of diphenylamine and acetone, and phenothiazine.
2. W absorbers and light stabilisers 2.1. 2-(2'-Hydroxyphenyl~-benztriazoles, such as, for example, the 5'-methyl-, 3',5'-di-tert.butyl-, 5'-tert.butyl-, 5'-(1,1,-3,3-te-tramethylbutyl)-, 5-chloro-3',5l-di-tert.butyl-, 5-chloro-3'-tert.bu~yl-5'-methyl-, 3'-sec.butyl-5'-tert.butyl-, ~'~-methylbenzyl-5'-methyl-~ 3'-~-methylbenzyl-5'-methyl-5-chloro-, 4'-hydroxy-, 4'-me-thoxy-, 4'-octoxy-, 3'-,5'-di-tert.amyl-, 3'-methyl-5'-carbomethoxyethyl-or 5-chloro-3'-,5' d--tert.-amyl-derivative.
2.2. ~ ines~ such as, for example, the 6-ethyl-, 6-heptadecyl-or 6-undecyl-derivative.
2.3. 2-Hydroxy-benzophenones, such as,`for example, the 4-hydroxy-, 4-methox-y-, 4-octoxy-, 4-decyloxy-, 4-dodecvloxy-, 4-benzylox~, 4,2'g4'-trihydroxy- or 2'-hydroxy-454'-dimethcx-~-derivative.
2.4. 1,3-Bis- t 2'-hydrox-y-benzoyl)-benzenes 9 such as, for ex~ple~
1,3-bis-(2'-hydroxy-4'-hexyloxy-benzoyl)-be~zene, 1,3-bis-(2t-hydroxy-4'-octyloxy-benzoyl)-benzene and 1,3-bis-(2'-hydroxy-4'-dodecyloxy-benzoyl)-benzene.
" 107ZlZ2 2.5. Es.ers of G~-tionally substituted benzoic acids, such as, for example, phenyl salicylate, octylphenyl salicylate, diben-zoylresorcinol, bis-(4-tert.-butylbenzoyl)-resorcinol, benzoyl-resorcinol and 3,5-di-tert.-butyl-4-hydroxybenzoic acid 2,4-di-tert.butyl-phenyl ester, octadecyl ester or 2-methyl-4,o-di-tert.butyl-phenyl ester.
2.6. Acryla-tes, such as, for examPle~ a-cyano~ -diphenyl-acrylic acid ethyl ester or isooctyl ester, a-carbomethoxy-cinnamic acid methyl ester, a-cyano-~-methyl-p-me-thoxy-cir-rlamic acid methyl ester or butyl ester and N-(~-carbomethoxy--vi-nyl)-2-methyl-i-ndoline.
2.7. Nickel com~ouIlds, such as, for ex~mple5 nickel complexes of 2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or 1:2 complex, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohex~-l-di-ethanolamine, nickel complexes of bis-~2-hydroxy-4-(1,1,3,3-tetramethylbutyl)-phenyl]-sulphone, such as the 2:1 complex, optionally wi-th additional ligands such as 2-ethyl-caproic acid, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3~5-di-tert.butylbenzyl-phosphonic acid monoalkyl esters, such as of the methyl, ethyl or butyl ester, nickel complexes of ketoximes such as of 2-hydroxy-4-methyl-phenyl-urldecylketonoxime, nickel 3,5-di-tert.butyl-4~h-ydroxy-benzoate and nickel isopropylxanthate.
2.~. Sterically hindered amines, such as, for exampl2, L_ benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2~2,6,6-tetramethylpiperidine 9 bis-(252~6,5-tetramethylpip-. .
,:
''." ' ' .^ '- ' . . . ..
. . .
107Z~ZZ
eridyl) sebacate, and 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, for example, 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert.butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert.butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N,N'-bis-(3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert.butyl-2'-ethyl-oxanilide and its mixture with 2-etho~y-2'-ethyl-5,4'-di-tert.butyl-oxanilide and mixtures of ortho- and para-methoxy-as well as of o-ard p-ethoxy-dlsubstituted oxanilides.
3. Metal deactivators, such as, ~or exa~ple, oxanllide, isophthal-~c acid dihydrazide, sebacic acid bis-phenyl-hydrazide, bis-benzylidene-oxalic acid dihydrazide, N,N'-diacetyl-adipic acid dihydrazide, N,N'-bis-salicyloyl-oxalic acid dihydrazide, N,N'-bis-salicyloyl-hydrazine, N,N'-bis-(3,5-di-tert.butyl-4-hydroxyphenyl-propionyl)-hydrazine, N-salicylal~'-salicylidenehydrazine and 3-salicyloylamino-1,2,4-triazole.
4. Phosphites, such as, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyldial~yl phosphltes, tri-(nonyl-phenyl) phosphite, trilauryl phosphite, trioctadecyl phosphiteS
3,9-di-isodecyloxy-2,4,8,10-tetroxa 3,9-diphospha-sELro[5,53-undecane and tri-(4-hydroxy-3,5-di-tert.butylphenyl) phosphite.
5. Compounds which destro~ peroxides 9 such as, for example, esters o ~-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercapto-benzimidazole and the zinc salt of 2-mercapto-benzimidazole.
. . . .
-. . . . .
-` ' ' '- ` I . '~ . . , - .
.
. . . . . . . - . . -:' ~.. ' ; ` :
107ZlZ2
. . . .
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.
. . . . . . . - . . -:' ~.. ' ; ` :
107ZlZ2
6 Nucleatin~ a~ents, such as, for example, 4-tert.butyl-benzoic acid, adipic acid and diphenylacetic acid.
7. Other additives, such as, for example, piasticisers, lubricants, emulsifiers, fillers, carbon black, asbestos, kaolin, talc, glass fibres, pigments, optical brighteners, ~lameproofing agents and antistatic agents.
The preparation and use of the compounds which can be used in accordance with the invention are described in greater detail in the examples which follow. In these, parts denote parts by weight and percentagesdenote percentages by weight.
A) Preparation of the compounds Examples 1-6: 1,1-Bis-(3,5-dimethyl-2-hydroxyphen-yl)-3-(n-dodecylthio)-n-butane.
27.2 g of 3-~n-dodecylthio)-butanal-1 are added, over the course of 10 hours at 0-5C, to 24.4 g of 2,4-dimethylphenol and 46.9 g of boron trifluoride ethyl-etherate and the reaction mixture is stirred for a fur'her 24 hours at room temperature. A white paste of crystals is formed, which is treated with 70 ml of methanol while stirring a~d cooling. The suspension is warmed to 50C for half an hour and cooled once more and the crystals are filtered off.
The product is purified by washing successively with methanol, water and again methanol and is dried at 40C.
This gives 1,1-bis-(3,5-dimethyl-2-hydro~Jphenyl)-3-(n-dodecylthio)-n-butane (stabiliser No. 1) in the form of white crystals of melting point 106-108C.
- . .
.. . .
- ... . .. . .
.. . .. . . .
' . .
The corresponding thia-alkyl.idene-bisphenols are obtained if the 3-(n-dodecylthio)-butanal-]. in the previous example is replaced by one of t.he thia-aldehydes in Table 1 which follcws.
~ -- 15 --... . . . ~ .
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O ~0~ 0 ~ 0~ 0 h 4h ::5 h 4 h ::1 h I
O~ Q ~ O ~
h~ I :~ h ~ I:~ I
4.C S~ 4 O I II I I I I II O
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~: ~ Q~ ~ ~ O ~ O
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. X ll ll ll ll ll o m ~m ~ m ~ m ~ m ~ ~
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S~ N I ~ N ~ ~, I N
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-- . , When isolating the compo-mds of Examples 2 - 5 abore, consideration must be given under certain circumstances to the fact tha-t the tendency of the su~stances to c~ystallise varies greatly. If appropriate, ice water must be added to the reaction mixture and the organic phase must be washed until it is neutral and must be dried, after which it can be converted into the crystalline products either 'D-y evaporation and treatment ~nth methanol or by purification by colunLn chromatograpny.
Example 7 1,1-Bis-(3-methyl-5~tert.-butyl~2-hydroxyphenyl)-3-(ri-octyl-thio)-n-butane.
If, in Example 1, the 2,4-~me'~hylphenol is replaced by 2-methyl-4-tert.-butylphenol, ~n identical procedllre gives 1,1-bis-(3-methyl-5-tert.butyl-2-hydroxyphenyl)~3-n-octyl-thio)-n-butane (stabiliser No. 6) in the form of a viscGlls oil, which is freed from by-prodllc-ts by column chromatography.
The elementary analysis agrees with the formula indi-cated.
Example & 1,1-Bis-(3-ethyl-5-tert.-butyl-2-hydroxyphenyl)-3 (n-dodecylthio~~n-butane.
If, in Example 1, the 274-dimethylphenol is re~laced by 2-ethyl-L~tert.-butylpherlol, an identical procedure gives 1,1-bis-(3-ethyl-5-tert.-butyl-2-nydroxyphenyl)-3-(n~
dodecyl-thio)-n-butane (stabiliser No. 8) in the form of a ViSCGUS oil, which is freed from by-produGts by colu~
chromatograpny.
: .- - . . : -:. .: .: .
.
. .
.
. ~ ' .
.:
B) Technolo~ical examples ExamPles 9-13 Stabilisation of polybutadiene rubber.
100 parts of polybutadiene ("Solprene 250" of Messrs.
Phillips), which is pre-stabilised with 0.36% of 2,6-ditert.-butyl-p-cresol, are kneaded for 30 minutes in a Brabender plastograph at 150C and 60 revolutions/minute with an addi-tional 0.1 part of each of the stabilisers shown in Table 2. The resistance to kneading is continuously registered in the form of the torque during this time. A maximum occurs in the torque owing to crosslinking which sets in initially, and subsequent degradation. The effectiveness of the stabi-lisers is expressed by a reduction in the torque maximum.
The gel content which can be determined aft~r the Brabender treatment is considered a further criterion of the protective action of the stabilisers incorporated. For this purpose, 1 g of the sa~ple is dissolved overnight at room temperature in 100 ml of toluene. These solutions are filtered through glass wool, the gel particles which are retained are rinsed with a little toluene and the filtered solutions are evaporated to dryness and are dried to a con-stant weight. The gel content of a sample is obtained from the following calculation:
Gel content in % = T x loo E = total weight of the sample tested A = weight of the dissolved fraction;
In Examples 9-11 known stabilisers ha~e been used for comparison;
,~ . .
.. ~ .
- . . .
-- .
: . -'~ :
~072122 Table 2 Example Stabiliser Torque Gel maximum content . __ .
9 Without stabiliser 3,625 44 , 1 1,980 0 _ .
11 2,6-Di-tert.-butyl-4- 3,350 35 methyl-l-hydroxyphenol . . . _ 12 2,2'-Methylene-bis-(6- 3 550 33 tert.-butyl-4-methyl phenol) -. . _ 13 1,1-Bis-(2-methyl-5-tert.- 3,250 35 butyl-4-hydroxyphenyl)-3-(n-octadecylthio)-n-butane Exam~les 14-16 Stabilisation of polvbutadiene rubber . 100 parts of polybutadiene ("Solprene 250" of Messrs.
Phillips), which is pre-stabilised with 0.36% of 2,6-ditert.-butyl-p-cresol, are homogenised in a Brabender plastograph for 10 minutes at 150C and 60 revolutions/minute with an additional 0.1 part of one of the stabilisers shown in Table 3, The mixtures stabilised in this way are pressed into test pieces 10 mm thick for 5 minutes in a press at 120C.
The test piece of non-stabilised rubber which serves for comparison is prepared in the same manner;
The Mooney value which is determined after storage $n the atmosphere at elevated temperatures, is considered a .
- - . : -- .. . . . .
.
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- .
.
~ . . - . ` `
criterion o~ the protective action of the s-tabilisers incor-porated. For this purpose, the test samples arekep-t at 150C on aluminium suppor-ts in a circulating air oven and their Mooney value is determined after 20 hours. (DIN
53523,ASTM D ~27-57 T). The Mooney value is understood as the torque which has to be applied to turn a cylind~ical disc (rotor) at a speed of revolution of 2 revolutions/minute in chamber filled with the sample. The value is read off at a temperat-ure of 100C after the rotor has been rur~ing for a period of 4 minutes. Higher Mooney values denote cross-link7ng of the plastic and hence damage caused by the aging in the oven.
Table 3 Stabiliser Mooney value Torque , ___ - __ None 128 1.08 kp x m 1 48 0.40 kp x m _ _ ___. ~, / O K} :c n - 2~ -.
.... . . .. . . . .
: ,~ . . . . .
. ~ :
~- ', - ' - ' ' - ' :
. : . .
.
The preparation and use of the compounds which can be used in accordance with the invention are described in greater detail in the examples which follow. In these, parts denote parts by weight and percentagesdenote percentages by weight.
A) Preparation of the compounds Examples 1-6: 1,1-Bis-(3,5-dimethyl-2-hydroxyphen-yl)-3-(n-dodecylthio)-n-butane.
27.2 g of 3-~n-dodecylthio)-butanal-1 are added, over the course of 10 hours at 0-5C, to 24.4 g of 2,4-dimethylphenol and 46.9 g of boron trifluoride ethyl-etherate and the reaction mixture is stirred for a fur'her 24 hours at room temperature. A white paste of crystals is formed, which is treated with 70 ml of methanol while stirring a~d cooling. The suspension is warmed to 50C for half an hour and cooled once more and the crystals are filtered off.
The product is purified by washing successively with methanol, water and again methanol and is dried at 40C.
This gives 1,1-bis-(3,5-dimethyl-2-hydro~Jphenyl)-3-(n-dodecylthio)-n-butane (stabiliser No. 1) in the form of white crystals of melting point 106-108C.
- . .
.. . .
- ... . .. . .
.. . .. . . .
' . .
The corresponding thia-alkyl.idene-bisphenols are obtained if the 3-(n-dodecylthio)-butanal-]. in the previous example is replaced by one of t.he thia-aldehydes in Table 1 which follcws.
~ -- 15 --... . . . ~ .
- ~ . . . .
. : - . . -.
. .
. . ` - . .
. - ` ~
.
.
'o ~
C~ ~ C.) C) O -rl O O 4 ~ o o o o h C~ h ~1 O ~ D 4 o J~ ~ O O _14 0 4 .4 0 ~J
a) I ~ a) I I a)I
~ a~
X ~X ~ X ~ X tOX
O ~0~ 0 ~ 0~ 0 h 4h ::5 h 4 h ::1 h I
O~ Q ~ O ~
h~ I :~ h ~ I:~ I
4.C S~ 4 O I II I I I I II O
~ ~ _~ ~ ~ ~ ~ ~~ ,1 O I OI O I O I OI ~:
~I~ 1 . 4 ~1 J~ 1~ t) . ~ ~ ~ O
~: ~ Q~ ~ ~ O ~ O
~O U~
,1 ~ _~ _ _I ~ I~ I ~ I ~ I~ I
:~ _ "~
. X ll ll ll ll ll o m ~m ~ m ~ m ~ m ~ ~
_, ,~ x S~ ~ 4 ~ 1 ~4 . _ .~
~ _I _1 N
~ a~ C -Y C~
S~ N I ~ N ~ ~, I N
. ~ ~ m y~
N N N N
N
. t~ y y y y . :r: .
E~ O = V O = ~ = ~ = m = v h _ _~ N ~) . .
~Z
-4~
F~ N ~ ~ U~ ~D
1~3 :.
. . . - :. .
,' ' ~.
-- . , When isolating the compo-mds of Examples 2 - 5 abore, consideration must be given under certain circumstances to the fact tha-t the tendency of the su~stances to c~ystallise varies greatly. If appropriate, ice water must be added to the reaction mixture and the organic phase must be washed until it is neutral and must be dried, after which it can be converted into the crystalline products either 'D-y evaporation and treatment ~nth methanol or by purification by colunLn chromatograpny.
Example 7 1,1-Bis-(3-methyl-5~tert.-butyl~2-hydroxyphenyl)-3-(ri-octyl-thio)-n-butane.
If, in Example 1, the 2,4-~me'~hylphenol is replaced by 2-methyl-4-tert.-butylphenol, ~n identical procedllre gives 1,1-bis-(3-methyl-5-tert.butyl-2-hydroxyphenyl)~3-n-octyl-thio)-n-butane (stabiliser No. 6) in the form of a viscGlls oil, which is freed from by-prodllc-ts by column chromatography.
The elementary analysis agrees with the formula indi-cated.
Example & 1,1-Bis-(3-ethyl-5-tert.-butyl-2-hydroxyphenyl)-3 (n-dodecylthio~~n-butane.
If, in Example 1, the 274-dimethylphenol is re~laced by 2-ethyl-L~tert.-butylpherlol, an identical procedure gives 1,1-bis-(3-ethyl-5-tert.-butyl-2-nydroxyphenyl)-3-(n~
dodecyl-thio)-n-butane (stabiliser No. 8) in the form of a ViSCGUS oil, which is freed from by-produGts by colu~
chromatograpny.
: .- - . . : -:. .: .: .
.
. .
.
. ~ ' .
.:
B) Technolo~ical examples ExamPles 9-13 Stabilisation of polybutadiene rubber.
100 parts of polybutadiene ("Solprene 250" of Messrs.
Phillips), which is pre-stabilised with 0.36% of 2,6-ditert.-butyl-p-cresol, are kneaded for 30 minutes in a Brabender plastograph at 150C and 60 revolutions/minute with an addi-tional 0.1 part of each of the stabilisers shown in Table 2. The resistance to kneading is continuously registered in the form of the torque during this time. A maximum occurs in the torque owing to crosslinking which sets in initially, and subsequent degradation. The effectiveness of the stabi-lisers is expressed by a reduction in the torque maximum.
The gel content which can be determined aft~r the Brabender treatment is considered a further criterion of the protective action of the stabilisers incorporated. For this purpose, 1 g of the sa~ple is dissolved overnight at room temperature in 100 ml of toluene. These solutions are filtered through glass wool, the gel particles which are retained are rinsed with a little toluene and the filtered solutions are evaporated to dryness and are dried to a con-stant weight. The gel content of a sample is obtained from the following calculation:
Gel content in % = T x loo E = total weight of the sample tested A = weight of the dissolved fraction;
In Examples 9-11 known stabilisers ha~e been used for comparison;
,~ . .
.. ~ .
- . . .
-- .
: . -'~ :
~072122 Table 2 Example Stabiliser Torque Gel maximum content . __ .
9 Without stabiliser 3,625 44 , 1 1,980 0 _ .
11 2,6-Di-tert.-butyl-4- 3,350 35 methyl-l-hydroxyphenol . . . _ 12 2,2'-Methylene-bis-(6- 3 550 33 tert.-butyl-4-methyl phenol) -. . _ 13 1,1-Bis-(2-methyl-5-tert.- 3,250 35 butyl-4-hydroxyphenyl)-3-(n-octadecylthio)-n-butane Exam~les 14-16 Stabilisation of polvbutadiene rubber . 100 parts of polybutadiene ("Solprene 250" of Messrs.
Phillips), which is pre-stabilised with 0.36% of 2,6-ditert.-butyl-p-cresol, are homogenised in a Brabender plastograph for 10 minutes at 150C and 60 revolutions/minute with an additional 0.1 part of one of the stabilisers shown in Table 3, The mixtures stabilised in this way are pressed into test pieces 10 mm thick for 5 minutes in a press at 120C.
The test piece of non-stabilised rubber which serves for comparison is prepared in the same manner;
The Mooney value which is determined after storage $n the atmosphere at elevated temperatures, is considered a .
- - . : -- .. . . . .
.
: . . ~ - . :
- .
.
~ . . - . ` `
criterion o~ the protective action of the s-tabilisers incor-porated. For this purpose, the test samples arekep-t at 150C on aluminium suppor-ts in a circulating air oven and their Mooney value is determined after 20 hours. (DIN
53523,ASTM D ~27-57 T). The Mooney value is understood as the torque which has to be applied to turn a cylind~ical disc (rotor) at a speed of revolution of 2 revolutions/minute in chamber filled with the sample. The value is read off at a temperat-ure of 100C after the rotor has been rur~ing for a period of 4 minutes. Higher Mooney values denote cross-link7ng of the plastic and hence damage caused by the aging in the oven.
Table 3 Stabiliser Mooney value Torque , ___ - __ None 128 1.08 kp x m 1 48 0.40 kp x m _ _ ___. ~, / O K} :c n - 2~ -.
.... . . .. . . . .
: ,~ . . . . .
. ~ :
~- ', - ' - ' ' - ' :
. : . .
.
Claims (11)
1. Compounds of the general formula I
(I) wherein R1 is an alkyl group which has 1 to 18 carbon atoms and which is not branched in the .alpha.-position, R2 denotes a linear or branched alkyl group having 1 to 8 carbon atoms, or a hydrogen atom, R3 and R5 independently of one another each denote a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R4 denotes a linear or branched alkyl group having 1 to 20 carbon atoms wherein the carbon chain can be interrupted by sulphur atoms.
(I) wherein R1 is an alkyl group which has 1 to 18 carbon atoms and which is not branched in the .alpha.-position, R2 denotes a linear or branched alkyl group having 1 to 8 carbon atoms, or a hydrogen atom, R3 and R5 independently of one another each denote a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R4 denotes a linear or branched alkyl group having 1 to 20 carbon atoms wherein the carbon chain can be interrupted by sulphur atoms.
2. Compounds according to Claim 1, characterised in that R4 is an alkyl radical having 4 to 16 carbon atoms.
3. Compounds according to Claims 1 to 2, characterised in that R1 is a methyl or ethyl group.
4. Compounds according to Claim 1, characterised in that R3 and R5 independently of one another denote a hydrogen atom or a methyl group.
5. Compounds according to Claim 1, 2 or 4 characterised in that R1 and R2 represent the methyl group.
6. Process for the manufacture of compounds of the general formula I
(I) wherein R1 is an alkyl group which has 1 to 18 carbon atoms and which is not branched in the .alpha.-position, R2 denotes a linear or branched alkyl group having 1 to 8 carbon atoms, or a hydrogen atom, R3 and R5 independently of one another denote a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R4 denotes a linear or branched alkyl group having 1 to 20 carbon atoms, wherein the carbon chain can be interrupted by sulphur atoms, characterised in that a phenol of the formula II
(II) wherein R1 and R2 have the meaning indicated above, is reacted, in the presence of an acid catalyst, with a thia-aldehyde of the formula III
(III) wherein R3, R4 and R5 have the meaning indicated above.
(I) wherein R1 is an alkyl group which has 1 to 18 carbon atoms and which is not branched in the .alpha.-position, R2 denotes a linear or branched alkyl group having 1 to 8 carbon atoms, or a hydrogen atom, R3 and R5 independently of one another denote a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R4 denotes a linear or branched alkyl group having 1 to 20 carbon atoms, wherein the carbon chain can be interrupted by sulphur atoms, characterised in that a phenol of the formula II
(II) wherein R1 and R2 have the meaning indicated above, is reacted, in the presence of an acid catalyst, with a thia-aldehyde of the formula III
(III) wherein R3, R4 and R5 have the meaning indicated above.
7. Process according to claim 6, characterised in that the catalyst is a liquid Lewis acid etherate-adduct which is used at the same time as the re-action medium.
8. Process according to claim 7, characterised in that boron trifluoride etherate is used as the catalyst.
9. Process according to claim 7, characterised in that at least 3 mols of catalyst are employed per mol of reaction product.
10. A stabilised mixture consisting of a) an elastomer and b) 0.005 to 5%
by weight, based on the elastomer, of at least one of the compounds of the for-mula I as defined in claim 1.
by weight, based on the elastomer, of at least one of the compounds of the for-mula I as defined in claim 1.
11. Mixture according to claim 10, characterised in that it contains 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)-3-(n-dodecylthio)-n-butane as the compound of the formula I.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1257374 | 1974-09-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1072122A true CA1072122A (en) | 1980-02-19 |
Family
ID=4384289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA235,337A Expired CA1072122A (en) | 1974-09-16 | 1975-09-12 | Alkylidene-bisphenols containing sulphur, and their use as stabilisers |
Country Status (10)
| Country | Link |
|---|---|
| JP (2) | JPS5946262B2 (en) |
| AU (1) | AU8479575A (en) |
| BE (1) | BE833406A (en) |
| BR (1) | BR7505912A (en) |
| CA (1) | CA1072122A (en) |
| DE (1) | DE2540432C2 (en) |
| ES (1) | ES440962A1 (en) |
| FR (1) | FR2284593A1 (en) |
| GB (1) | GB1457089A (en) |
| NL (1) | NL7510346A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4721814A (en) * | 1986-01-23 | 1988-01-26 | Ciba-Geigy Corporation | Mercaptan-containing polyphenols |
| JPH0434316A (en) * | 1990-05-30 | 1992-02-05 | Osaka Gas Co Ltd | Flowmeter |
| EP3533786A1 (en) | 2018-03-02 | 2019-09-04 | Givaudan SA | Thioether precursors for fragrant ketones and aldehydes |
| GB201803410D0 (en) * | 2018-03-02 | 2018-04-18 | Givaudan Sa | Improvements in or relating to organic compounds |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3699152A (en) * | 1969-12-10 | 1972-10-17 | Carlisle Chemical Works | Sulfur containing esters of substituted hydroxyphenyl-alkanoic acids |
-
1975
- 1975-09-02 NL NL7510346A patent/NL7510346A/en not_active Application Discontinuation
- 1975-09-11 DE DE2540432A patent/DE2540432C2/en not_active Expired
- 1975-09-12 AU AU84795/75A patent/AU8479575A/en not_active Expired
- 1975-09-12 CA CA235,337A patent/CA1072122A/en not_active Expired
- 1975-09-15 BE BE160031A patent/BE833406A/en not_active IP Right Cessation
- 1975-09-15 GB GB3777475A patent/GB1457089A/en not_active Expired
- 1975-09-15 ES ES75440962A patent/ES440962A1/en not_active Expired
- 1975-09-15 FR FR7528185A patent/FR2284593A1/en active Granted
- 1975-09-15 BR BR7505912*A patent/BR7505912A/en unknown
- 1975-09-16 JP JP50112032A patent/JPS5946262B2/en not_active Expired
-
1984
- 1984-02-18 JP JP59029453A patent/JPS6011027B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2284593A1 (en) | 1976-04-09 |
| ES440962A1 (en) | 1977-03-16 |
| AU8479575A (en) | 1977-03-17 |
| DE2540432A1 (en) | 1976-04-01 |
| JPS59172462A (en) | 1984-09-29 |
| JPS6011027B2 (en) | 1985-03-22 |
| BE833406A (en) | 1976-03-15 |
| FR2284593B1 (en) | 1978-04-07 |
| GB1457089A (en) | 1976-12-01 |
| BR7505912A (en) | 1976-08-03 |
| JPS5155345A (en) | 1976-05-15 |
| NL7510346A (en) | 1976-03-18 |
| DE2540432C2 (en) | 1986-07-03 |
| JPS5946262B2 (en) | 1984-11-12 |
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