Note: Descriptions are shown in the official language in which they were submitted.
~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)
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)
-- 3 --
. ~ .
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)
R5 R3
~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.
.
-- 4 --
:- : ~ . - - .
.. . . -: -
- .
: ~ :
.
1072122
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-
- 5 -
.
107212Z
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
~ . ~
. ~ .
:
107212Z
~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),
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-
., .
7 -
' ' ' .
-
.
10721ZZ
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-
-- 8 --
.. , . ~ , . ..
.
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
- 10 -
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.
-- 11 --
" 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-
. .
- 12 -
,:
''." ' '
.^ '- ' . . . ..
. . .
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
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.
-- 14 --
- . .
.. . .
- ... . .. . .
.. . .. . . .
' . .
107Z12Z
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 --
... . . . ~ .
- ~ . . . .
. : - . . -
.
. .
. . ` - . .
. - ` ~
.
.
1072122
'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 ~)
. .
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-4~
F~ N ~ ~ U~ ~D
1~3
- 16 -
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107212Z
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.
: .- - . . : -
:. .: .: .
.
. .
.
. ~ ' .
.:
10721Z2
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;
- 18 -
,~ . .
.. ~ .
- . . .
-- .
: . -
'~ :
~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
- 19 -
.
- - . : -
- .. . . . .
.
: . . ~ - . :
- .
.
~ . . - . ` `
1072122
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~ -
.
.... . . .. . . . .
: ,~ . . . . .
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