Note: Descriptions are shown in the official language in which they were submitted.
10485Z~
The invention relates to new phenolaldehydes, a process
for their manufacture, their useforthe protection of substrates
which are sensitive to oxidation and, as an industrial product, : :.
the substrates protected with their aid.
The new compounds correspond to the general formula I ~-
R3 ~ H2 ~ ~ ~ CH-O
~.
in which Rl and ~ independently of one another denote hydro-
gen or methyl, or Rl conjointly with R2 and/or R4 conjointly
with ~ denotes tetramethylene, R2 denotes alkyl, cycloalkyl -: -
or aralkyl, R3 denotes hydroxyl, R4 denotes hydrogen, alkyl,
cycloalkyl or aralkyl, R6 denotes alkyl, aralkyl, acyloxyalkyl,
oxaalkyl or phenyl, R7 denotes alkyl, phenyl or the group
R~
~3 - ~ - CH2
R
4 5
~ .
--1--
.
~)48529
in which Rl to ~ have the indicated meaning, or, conjointly
with R6, denotes alkylene, and n denotes O or 1.
Preferred compounds are those of the formula I in which
and R5 independently of one another denote hydrogen or methyl,
or R conJointly with R2 and/or R4 conjointly with R5 denotes -.
tetramethylene, R2 denotes alkyl with 1 to 8 carbon atoms, ~ -
cycloalkyl with 6-8 carbon atoms or aralkyl with 7-9 carbon
atoms, R3 denotes hydroxyl, R4 denotes hydrogen, alkyl with. -
1 to 8 carbon atoms, cycloalkyl with 6-8 carbon atoms or aralkyl :-~
with 7-9 carbon atoms, R6 denotes alkyl with 1 to 8 carbon
atoms, R7 denotes alkyl with 1 to 8 carbon atoms or the group
R2 Rl
R3--~--CH2
R4 5
:~ ,
in which Rl to R~ have the indicated meaning, or, conjointly
with R6, denotes alkylene with 2 to 11 carbon atoms, and n
denotes O or 1.
Particular preference attaches to compounds of the
formula I in which ~ and ~ independently of one another denote
hydrogen or methyl, ~ denotes particularly hydrogen, R2 denotes
alkyl with 1-4 carbon atoms or, conjointly with Rl, denote$
tetramethylene, R2 being preferably alkyl with 1 to 4 carbon
atoms, R3 denotes hydroxyl, R4 denotes alkyl with 1-4 carbon
atoms or, conjointly with ~ , denotes tetramethylene, R4 being
preferably alkyl with 1-4 carbon ato~s, R6 denotes alkyl with
1 to 4 carbon atoms or phenyl, R6 being preferably aIkyl with
--2--
la4ss2s ~ ~
1-4 carbon atoms, R7 denotes alkyl with 1-4, preferably 1-2,
carbon atoms or the group
R2 Rl . . ,
R~ CHz
R4 :- -
in which Rl to ~ have the indicated meanIng, or, conjointly ~ ~-
with R6, denotes alkylene with 4 or 5, pre~erably 5, carbon
atoms, and n denotes 0 or 1, preferably 1.
m ose compounds of the formula I in which n denotes
the number 1, are a special group, preferred because of their
easy accessibility.
If, in formula I, R2, R3 and R4 denote alkyl, it can
be methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec.-butyl,
tert. butyl, n-amyl, sec.-amyl, tert.-amyl, hexyl, octyl or
1,1,3,3-tetramethylbutyl.
R2, R3 and R4 can denote a cycloalkyl group, such as,
for example, cyclopentyl, cyclohexyl, a-methylcyclohexyl or
cyclooctyl.
R2, R3, R4 and R6 can denote an aralkyl group, such as,
for example, benzyl, a-phenylethyl or a,a-dLmethylbenzyl.
R6 meaning oxaalkyl, for example with 3 to 10 carbon
atoms, can be 3-oxabutyl, 3-oxapentyl or 3-oxaheptyl.
If R6 denotes acyloxyalkyl with, for example, 4 to 20
carbon atoms, then "acyl" is the radical of an aliphatic or
aromatic carboxylic acid with, for example, 2 to 18 carbon
-3-
. : . .
1~4~529
atoms, such as an alkanoic acid such as acetic acid, propionic
acid, caproic acid, lauric acid or stearic acid or an unsub-
stituted or substituted benzoic acid, such as benzoic acid, ;
p-tert.butylbenzoic acid or p-tert.octylbenzoic acid. Acyl-
oxy is, for example, 2-acetoxyethyl, 2-propionyloxyethyl,
2-capryloxyethyl, 2-lauryloxyethyl, 2-stearyloxyethyl,
3-acetoxypropyl, 3-propionyloxypropyl, 3-lauryloxypropyl,
3-capryloxypropyl, 3-stearyloxypropyl or 3-benzoyloxypropyl.
If R6 and R7 in formulaI denote an alkyl group, it can
be methyl, ethyl, n-propyl, n-butyl, isobutyl, n-hexyl or n-octyl.
If R6 and R7 conjointly denote an alkylene group, it
can be ethylene, propylene, trimethylene, tetramethylene,
pentamethylene, hexamethylene, heptamethylene, nonamethylene
or undecamethylene.
Examples of compounds of the ~ormula I are: 3-(3-
tert.butyl-4-hydroxy-5-methylphenyl)-2,2-dimethyi-propionaldehyde,
3-(3-tert.butyl-4-hydroxy-5,6-dimethylphenyl)-2,2-dimethyl-
propionaldehyde, 3-(3,5-di-cyclooctyl-4-hydroxyphenyl)-2,2-
dimethyl-propionaldehyde, 3-(4-hydroxy-3,5-di--methylcyclo-
hexylphenyl)-2,2- dimethyl-propionaldehyde, 3-(4-hydroxy-3,5-
di-~-phenylethyl-phenyl)-2,2-dimethyl-propionaldehyde, 2-ethyl-
2-(3,5-di-butyl-4-hydroxybenzyl)-caproaldehyde, 2-(3,5-di-tert.-
butyl-4-hydroxybenzyl)-2-octyl-capraldehyde, 1-(3,5-di-tert.butyl-
4-hydroxybenzyl)-hexahydro-benzaldehyde, 1-(3-tert.butyl-4-
hydroxy-5,6-di-methylbenzyl)-hexahydro-benzaldehyde, 1-(3-
tert.butyl-4-hydroxy-5-methylbenzyl)-cyclooctane-carboxaldehyde,
(3,5-di-tert.butyl-4-hydroxyphenyl)-acetaldehyde, (3-tert.butyl-
4-hydroxy 5-methylphenyl)-aGetaldehyde,
_4_
~485Z9 -
(3-tert.butyl-4-hydroxy-5,6-dimethylphenyl)-acetaldehyde,
2,2-bis-(3-tert butyl-4-hydroxy-5--a-methylbenzyl)-propionalde-
hyde, 2,2-bis-(3,5-di-tert.butyl-4-hydroxybenzyl)-caprylaldehyde
and 2,2-bis-(3,5-di-tert.butyl-4-hydroxybenzyl)oenanthaldehyde.
The compounds of the formula Ia according to the inven-
tion
2 Rl
R3 - ~ O ~ _ CH2-CH=O (Ia)
X /~R ' ' '
4 s
: . :
that is to say compounds of the formula I in which n denotes
0, can be obtained in a manner which is in itself known from
compounds of the formula II
R2~Rl .
R3 - ~ C~I2-CO-Cl (II)
4 5
by reduction with hydrogen gas in the presence of specific
catalyst systems (Rosenmund reduction).
The compounds of the formula Ib
HO - ~ H2- C - CH=O (Ib)
R4 R5 7
:. .
1~4~529
in which Rl denotes hydrogen, or, conjointly with R2, denotes
tetramethylene, Rl being preferably hydrogen, R5 denotes
hydrogen or methyl or, conjointly with R4, denotes tetramethyl-
ene, R5 being preferably hydrogen or methyl, R2 and R4
independently of one another denote alkyl, cycloalkyl or
aralkyl, and R6 and R7 independently of one another denote
alkyl or conjointly denote alkylene, can be obtained in a
further process which is in itself known by reacting compounds
of the formula III
R'
HO ~ CH2 _ X
. R
4 5
in which X denotes halogen such as chlorine or bromine, with.
compounds of the formula IV
H - C - CH=O (IV)
I
in the presence of concentrated aqueous sodium hydroxide solu-
tion and catalytic amounts of a tetraalkylammonium salt in a
so-called "phase transfer catalyséd" reaction.
It has further been found that the compounds, which
fall under formula I, of the formula Ic
1~)48S29
R2 Rl 6 :-
~ ,.
~10 ~ CH2 1 :- CH==O ~ - (Ic) - .
R'J ~R 7
in which Rl denotes hydrogen or, conjointly with R2, denotes
tetramethylene, Rl being preferably hydrogen, R5 denotes . -
hydrogen or methyl or, conjointly with R4, denotes tetramethy~
lene, R5 being preferably hydrogen or methyl, R2 and RL
independently of one another denote alkyl, cycloalkyl or - -
aralkyl, R6 denotes alkyl, and R7 denotes alkyl or the group
; ,
~10~C~2- ~.,.'
R4 ~5 m
in which Rl, R2, RL and R5 have the indicated meaning, or,
conjointly with R6, denotes alkylene, can be obtained,
surprisingly, in a new process by reacting a compound of the ~-
formuia V
HO - ~ CH2 -S - C- N R8 Rg (V)
4 R
-7-
.
.. . . .
1~48S29
wherein Rl, R2, RL and ~ have the meaning defined in formula
Ic and R8 and Rg independently of one another denote alkyl or
conjointly, with the inclusion of the nitrogen atom, denote a
saturated, heterocyclic 5- or 6-membered ring, with a compound
of the formula ~I
R~
H - C - CH=O (VI)
R~
wherein R6 denotes alkyl and R7 denotes hydrogen or alkyl or,
conjointly with R6, denotes alkylene,in a solvent in the
presence of a base.
In this reaction those compounds of the formula V are
preferably employed in which R8 and Rg independently of one
another denote alkyl with 1 to 5 carbon atoms or conjointly,
with the inclusion of the nitrogen atom, denote the radical
of morpholine or piperidine.
Compounds of the formula V in which R8 and Rg denote
methyl or ethyl are particularly preferentially employed.
The process according to the invention is carried out
in a solvent. Suitable solvents are alcohols such as methanol,
ethanol, iso-propanol, sec.-butanol, tert.-butanol or amyl
alcohol, aliphatic ethers such as dibutyl ether, tetrahydro-
furane or dioxane, hydrocarbons such as hexane, heptane, octane,
ligroin, decalin, cyclohexane, benzene, toluene or xylene, or
aprotic polar solvents such as dimethylformamide, dimethyl
acetamide or dimethylsulphoxide.
Examples of suitable bases in the process according to
-8-
~ . .. , ~ . . ~
i~485Z9 - ;
the invention are alkali metal hydroxides, such as sodium
hydroxide or potassium hydroxide, alcoholates, such as sodium ~ -
methylate, sodium ethylate, magnesium ethylate, potassium ~-
isopropylate or potassium tert.butylate, or hydrides, such as
lithium hydride, sodium hydride or potassium hydride
It has been shown that the process according to the
invention can be carried out particularly advantageously in a -
~ne-phase reaction mixture J for example in a solvent miscible
with water, such as lower alcohols, for example methanol,
ethanol or isopropanol, ethers, such as dioxane and tetrahydro-
furane, or aprotic polar solvents, such as dimethylformamide
or dimethylsulphoxide, using an aqueous or alcoholic or aqueous-
alcoholic solution of the base, an alkali metal hydroxide or
alkali metal alcoholate preferably being employed as the base.
Surprisingly, the aldehyde of the formula VI is not
destroyed as a result of side reactions, as would have been
expected on the basis of the literature. Instead, the com-
pounds of-the formula Ic are obtained under these reaction ;
conditions in substantially better purity and higher yield than ;
would be the case in known processes.
In order to prepare compounds of the formula Ic in
which R7 denotes alkyl or, conjointly with R6, denotes alkylene,
the aldehyde of the formula VI wherein R7 denotes alkyl or,
conjointly with R6, denotes alkylene, is advantageously used
in a 5 - 40% strength excess over the compound of the formula V,
the base being in an approximately molar ratio to this compound.
In order to prepare compounds of the formula Ic in
which R7 denotes the group
'" .
_g_ ~.
' ~ '
1~48S29
the aldehyde of the formula VI in which R7 denotes hydrogen,
is advantageously used in an approximately half-molar ratio
to the compound o~ the formula V, the base being in an
approximately molar ratio to the compound of the formula V.
The temperatures at which the process according to
the invention is carried out are not critical and are, for
example, between -10 and +120C. The reaction is preferably
carried out at elevated temperature, for example at 40 - 80C.
The process according to the invention is preferably
carried out under an atmosphere o~ nitrogen or rare gas. It
is possible initially to take the base in the solvent and to
add dropwise the compounds of the formulae V and VI, together
or separately, optionally in a dissolved form. In the particu- i
larly advantageous one-phase embodiment, it is advantageous
initially to take the two compounds of the formulae V and VI
in the solvent and to add the base slowly dropwise, preferably ~:
at elevated temperature and dissolved in water or in an organic :
solvent.
In a simplified embodiment of the inventive processS
a compound of the formula VII
--10--
-
i~4~529
~2 Rl
HO ~ (VII)
R4 ~5
is initially taken, together with carbon disulphide and a
formaldehyde donor, in the solvent, a secondary amine of
the formula VIII
/ R8 , ~:
HN ~ (VIII)
is added dropwise as such or in a solvent, and the reaction
mixture is then warmed. A compound of the formula VI is added
subsequently and the solution of a base is added dropwise. In
this embodiment the compound of the formula Ic is obtained in
a practically quantitative yield and high purity. One advan-
tage of this embodiment consists of the fact that the desired
compounds of the formula Ic are obtained starting directly
from cheap starting products and without isolation of the
intermediate product of the formula V.
In this simplified embodiment of the inventive process,
formaldehyde in -the form of an aqueous solution can be employed
as the formaldehyde donor. Preferably, however, paraformal-
dehyde is employed. One of the water-miscible, organic
solvents mentioned, preferably an alcohol such as isopropanol,
is used as the solvent. An alkali metal hydroxide, such as
sodium hydroxide or potassium hydroxide, or an alcoholate, such
:., ., ~
. .
104~3S29
as sod.ium methylate, sodium ethylate or sodium isopropylate,
is preferably employed as the base An aqueous alkali metal
hydroxide solution is used particularly preferentially.
In the formulae VII and VIII, the substituents Rl, R2,
R4, R5, R8 and Rg denote what is quoted under formula V. The
starting products of the formulae II, III, IV, V, VI, VII and
VIII are known or are easily accessible by generally known
methods.
The compounds of the formula I are used as stabilisers,
particul.arly processing stabilisers, for organic substrates.
They are also valuable intermediate products for the manufac-
ture of stabilisers for organic substrates.
For example, by reacting the compounds of the formula
I with alkali metal cyanide and ammonium carbonate, it is poss-
ible to obtain stabilisers of the formula IX
~ ~ 2 ~I ~ H C~ ~
in which q is 1 to 3, n, Rl, R2, R3, R4, R5t R6 and R7 ha~e ~.
the same meanings as indicated in the formula I and Rlo repre- ;
sents, if q = 1, hydrogen or a substituted or unsubstituted
alkyl, alkenyl or cycloalkyl group, if q = 2,.an alkylene group :~
which is optionally interrupted by ester functions, hetero-atoms :~.
and/or benzene rings, or, if q = 3, an alkanetriyl group or a ~ :
, , :: ,
- ~ . ~
~4~Z9
trifunctional group which contains a heterocyclic radical. -~
The following are examples of suitable substrates to ~ .
be stabilised by means of the compounds of the formula I
according to the invention or secondary products thereof of
the formula IX:
1. Polymers which are derived from hydrocarbons with
single or double unsaturation, such as polyolefines, such as,
for example, polyethylene, which can optionally be crosslinked,
polypropylene, polyisobutylene, polymethylbutene-l, poly- -
methylpentene-l, polybutene-l, polyisoprene, polybutadiene,
polystyrene, polyisobutylene, copolymers of the monomers on
which the homopolymers mentioned are based, such as ethylene-
propylene copolymers, propylene-butene-l copolymers,
propylene-isobutylene copolymers, styrene-butadiene copolymers
and terpolymers of ethylene and propylene with a diene, such
as, for example, hexadiene, dicyclopentadiene or ethylidene-
norbornene; mixtures of the abovementioned homopolymers,
such as, for example, mixtures of polypropylene and polyethy].-
ene, polypropylene and polybutene-l, or polypropylene and poly- -
isobutylene.
2. Vinyl polymers containing halogen, such as polyvinyl
chloride, polyvinylidene chloride, polyvinyl fluoride, but also
polychloroprene and chlorinated rubbers
3. Polymers ~hich are derived from ~,~-unsaturated
acids and their derivatives, such as polyacrylates and poly-
methacrylates, polyacrylamides and polyacrylonitrile, as well
as their copolymers with other vinyl compounds, such as acrylo-
nitrile/butadiene/styrene, acrylonitrile/styrene and ~ :
.
104~
acrylonitrile/styrene/acrvlic ester copolymers.
4. Polymer-s which are derived from unsaturated alcohols
and amines or their acyl derivatives or acetals, such as poly-
vinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl
benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl
phthalate, polyallyl melamine and their copolymers with other
vinyl compounds, such as ethylene/vinyl acetate copolymers.
5. Homopolymers and copolymers which are derived from
epoxides, such as polyethylene oxide or the polymers which are
derived from bis-glycidyl ethers.
6. Polyacetals, such as polyoxymethylene and polyoxy-
ethylene, as well as those polyoxymethylenes which contain
ethylene oxide as the comonomer.
7. Polyphenylene oxides.
8. Polyurethanes and polyureas.
9. Polycarbonates.
10. Polysulphones.
11. Polyamides and copolyamides which are derived from
diamines and dicarboxylic acids and/or from aminocarboxylic
acids or the corresponding lactams, such as polyamide 6, poly-
amide 6/6, polyamide 6/10, polyamide 11 and polyamide 12.
12. Polyesters which are derived from dicarboxylic acids
and dialcohols and/or from hydroxycarboxylic acids or the
corresponding lactones 9 such as polyethylene glycol terephtha-
late or poly-1,4-dimethylol-cyclohexane terephthalate.
13. Crosslinked polymers which are derived from
aldehydes on the one hand and phenols, ureas and melamines
on the other, such as phenol-formaldehyde~ urea-formaldehyde
-14-
. . . ~ . ~ , , . . ~ -
1~48S29 ~ ~
and melamine-formaldehyde resins ;
14. Alkyd resins, such as glycerine-phthalic acid resins
and their mixtures with melamine-formaldehyde resins.
Unsa-turated polyester resins which are derived from
copolyesters of saturated and unsaturated dicarboxylic acids
with polyhydric alcohols, with vinyl compounds as crosslinking
agents, and also their halogen-containing modifications of low
inflammability.
16. Natural polymers such as cellulose, rubber, proteins
and their polymer-homologously chemically modified derivatives,
such as cellulose acetates, cellulose propionates and cellulose
butyrates, or the celluIose ethers, such as methylcellulose.
17. Natural and synthetic organic substances which are
pure monomeric compounds or mixtures of such, for example
mineral oils, animal and vegetable fats, oils and waxes, or
oils, waxes and fats based on synthetic esters and mixtures of
synthetic esters with mineral oils in any desired weight ratios.
The compounds of the formula I are incorporated in the
substrates in a concentration of 0.005 to 5% by weight, rela-
tive to -the material to be s-tabilised.
Preferably, 0.01 to 1.0, particularly preferably 0.02
to 0.5, % by weight of the compounds, relative to the material
to be stabilised, are incorporated into the latter. The
incorporation can be carried out, for example, by mixing in at
least one of the compounds of the formula I and optionally
further additives by the methods customary in the art, before
or during shaping, or by applying the compounds, dissolved or
dispersed, to the polymer, where appropriate with subsequent
-15-
1048529
evaporation of the solvent.
In -the case o~ crosslinked polyethylene~ the compounds
are added before the crosslinking.
The compounds of the formula I can also be added before
or during the polymerisation, it being possible, by a potential
incorporation into the polymer chain, to obtain stabilised
substrates in which the stabilisèrs are not volatile or sucep-
tible to extraction.
me ~ollowing may be mentioned as examples of further
additives with which the stabilisers can be conjointly employed:
1 Antioxidants ~
1.1 SimPle 2.6-dialkylphenols, such as, ~or example, 2,6-di- ;
- ;.
tert.-butyl-4-methylphenol, 2-tert -butyl-4,6-dimethylphenol,
2,6-di-tert.-butyl-4-methoxymethylphenol and 2,6-dioctadecyl-
4-methylphenol.
1.2 Derivatives of alkylated hydroquinones, such as, for
example, 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-hydroxyphenylstearate and bis-(3,5-di-
tert.-butyl-4-hydroxyphenyl)adipate.
1.3 Hydroxylated thiodiphenyl ethers, such as, for example,
2,2'-thio-bis-(6~tert.-butyl-4-methylphenol), 2,2'-thio-bis-
(4-octylphenol), 4,4'-thio-bis-(6-tert.-butyl-3-methylphenol),
4,4'-thio-bis-(3,6-di sec.-amylphenol), 4,4'-thio-bis-(6-
tert.-butyl-2-methylphenol) and 4~4'-bis-(2,6-dimethyl-4-
hydroxyphenyl)-disulphide.
-16-
' . .' ''' :.. , . ~, . - -
1048~Z9
1.4 e_~Y _~L,~ LLDb~C~, such as, for example, 2,2'-methylene-
bis-(6-tert.butyl-4-methylphenol),2,2'-methylene-bis-(6-
tert.butyl-4-ethylphenol), 4,4'-methylene-bis-(6-tert.
butyl-2-methylphenol), 4,L~'-methylene-bis-(2,6-di-tert. ;
butyl-phenol), 2,6-di-(3-tert.butyl-5-methyl-2-hydroxybenzyl)- ~-
4-methylphenol, 2,2'-methylene-bis-[4-methyl-6-(~-methylcyclo-
hexyl)-phenol], l,l-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,
1,1-bis-(5-tert.butyl-4-hydroxy-2-methylphenyl)-butane,
2,2-bis-(3,5-di-tert.bu-tyl-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-dodecylmercapto-butane,
1,1,5,5-tetra-(5-tert.butyl-4-hydroxy-2-methylphenyl)-pentane
and ethylene-glycol-bis-C3,3-bis-(3'-tert.butyl-4'-hydroxy-
phenyl)-butyrate].
1.5 O-, N- and S-benzyl compounds, such as, for example,
3,5,3',5'-tetra-tert.butyl-4,4'-dihydroxydibenzyl ether,
4-hydroxy-3,5-dimethylbenzyl-mercaptoacetic acid octadecyl
ester, tris-(3,5-di-tert butyl-4-hydroxybenzyl)-amine and bis-
(4-tert.butyl-3-hydroxy-2,6-dimethylbenzyl)-dithioterephthal-
ate. ~-
1.6 HydroxYbenzylated malonic esters, such as, for example,
2,2-bis-(3,5-di-tert.butyl-2-hydroxybenzyl)-malonic acid
dioctadecyl ester, 2-(3-tert.butyl-4-hydroxy-5-methyl-
benzyl)-malonic acid dioctadecyl ester, 2,2-bis-(3,5-di-tert.
butyl-4-hydroxybenzyl)-malonic acid di-dodecylmercapto-ethyl-
ester and 2,2-bis-(3,5-di-ter-t.butyl-4-hydroxyphenyl)-
malonic acid di-[4-(1,1,3,3-tetramethylbutyl)-phenyl]-ester.
1.7 Hydroxybenzyl-aromatics, such as, for example, 1,3,5-
'~ '
17
1048529
.
tri-(3,5-di-tert.butyl-4-hydroxybenzyl~-~,4,6-trimethyl-
benzene, 1,4-di-(3,5-di-tert.butyl-4-hydroxybenzyl)-2,3,5,6-
te-tramethylbenzene and 2,4,6-tri-(3,5-di-tert.butyl-4-hydroxy-
benzyl)-phenol.
1.8 s-Triazine comPounds~ such as, ~or 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-
hydroxy-anilino)-s-triazi.ne, 2-octylmercapto-4,6-bis-(3,5-di-
tert.butyl-4-hydroxy-phenoxy)-s-triazine J 2,4,6-tris-(3,5-di-
tert.butyl-4-hydroxyphenoxy)-s-triazine, 2,4,6-tris-(3,5-di-
tert.butyl-4-hydr~xyphenylethyl)-s-triazine and 1,3,5-tris- ;
(3,5-di-tert.butyl-4-hydroxybenzyl)-isocyanurate.
1.9 Amides of ~-(3,5-di-tert.but~-4-hydroxyphenyl)-propionic
acid, such as, 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-propionyl)-hexamethylenediamine.
1 10 Esters of ~-(3,5-di-tert.butvl-4-hydroxyphenyl)-
.
propionic acid with monohydric or polyhydric alcohols, such as,
for example, methanol, ethanol, octadecanol, 1,6-hexanediol,
l,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene
glycol, thiodiethylene glycol, neopentyl glycol, pentaeryth-
ritol, 3-thia-undecanol, 3-thia-pentadecanol, trimethyl-
hexanediol, trime-thylolethane, trimethylolpropane, tris-
hydroxyethyl isocyanurate and 4-hydroxymethyl-1-phospha-2?6,7-
trioxabicyclo[2,2,2]octane.
1.11. _ters of ~-(5-tert.butyl-4-hydroxy-3-methy]~henyl
propionic acid wi-th monohydric or polyhydric alcohols, such as,
for example, methanol, ethanol, octadecanol, 1,6-hexanediol,
-18-
:. ' . . ~ : . :
1~)48529
l,9-nonanediol, ethylene glycol, 1,2-propanediol, diethylene
glycol, thiodie-thylene glycol, neopentyl glycol, pentaerythritol,
3-thia-undecanol, 3-thia-pentadecanol, -trimethylhexanediol,
trimethylolethane, trimethylolpropane, tris-hydroxyethyl
isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo
[2,2,2]octane.
1.12. Esters o~ 3,5-di-tert.butyl-4-hy~drox~phenylacetic acid
with monohydric or polyhydric alcohols, such as, for example,
with methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-
nonanediol, ethylene glycol, l,2-propanediol, diethylene glycol,
thio-diethylene glycol, neopentyl glycol, pentaerythritol, 3-thia-
undecanol, 3-thia-pentadecanol, trimethylhexanediol,
trime-thylolethane, trimethylolpropane, tris-hydroxyethyl
isocyanurate and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo
[2,2,2]octane.
1.13. Acylaminophenols, such as, for example, N-(3,5-di--tert.
butyl-4-hydroxyphenyl)-stearic acid amide and N,Nt-di-(3,5-
di-tert.butyl-4-hydroxyphenyl)-thiobis-acetamide.
1.14. 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 dioctadecyl
ester and 5-tert.butyl-4-hydroxy-3-methylbenzyl-phosphonic
acid dioctadecyl ester.
1.15. Aminoaryl derivatives, such as, ~or example, phenyl-l-
naphthylamine, phenyl-2-naphthylamine, N,N'-diphenyl-p phenyl-
enediamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-di-sec.
butyl-p-phenylenediamine~ 6-ethoxy-2,2,4--trimethyl~1,2-dihydro-
--19-- ,
,
~)4~S29
qulnoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline,
monooc-tyllminodibenzyl and dioc-tyliminodibenzyl and polymerised
2,2,4-trimethyl-1,2-dihydroquinoline. Octylated diphenyl-
amine, nonylated diphenylamine, N-phenyl-N'-cyclohexyl-p-phenyl-
enediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N,N'-di-
sec.octyl-p-phenylenediamine, N-phenyl-N-sec.oc-tyl-p-phenylene-
diamine, N,N'-di-(1,4-dimethylpentyl)~p phenylenediamine, 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 li~ ~
2.1.2-(2'-Hydroxy~henyl~benztriazoles, such as, for example,
-the 5'-methyl-, 3',5'-di-tert.butyl-, 5'-tert.butyl-, 5'-(1,1,
3,3-tetramethylbutyl)-, 5-chloro-3',5'-di-tert.butyl-, 5-chloro-
3'-tert.butyl-5'-methyl-, 3'-sec.butyl-5'-tert.butyl-, 3'-a-
methylbenzyl-5'-methyl-, 3'-~-me-thylbenzyl-5'-methyl-5-chloro-,
4'-hydrox~y-, 4'-methoxy-, 4'-octox~y-, 3',5'-di-tert.amyl-, 3'-
methyl-5'-carbomethoxyethyl- and 5-chloro-3',5'-di-tert.-amyl-
derivative.
2.2. 2,4-Bis-(2'-hydrox~phenyl)-6-alk~l-s-triazines, such as,
for example, the 6-ethyl-, 6-heptadecyl or 6-undecyl-derivative.
2.3. 2-H~droxy-benzophenones, such as, for exarnple, the 4-
hydroxy-, 4-methoxy-, 4-octox~y-, 4-decyloxy-, 4-dodecyloxy-,
4-benzyloxy, 4,2',4'-trihydroxy- or 2'-hydroxy-4,4'-dimethoxy-
derivative.
2.4. 1~3-Bis-(2'-hydroxY=be~zoyl~-benzenes, such as, for example,
1,3-bis-(2'-hydroxy-4'-hexyloxy-benzoyl)-benzene, 1,3-bis-(2'-
hydroxy-4'-octyloxy-benzoyl)-benzene and 1~3-bis-(2'-hydroxy-4'-
-20-
~ 48SZ9
dodccyloxy-benzoyl)-benzene.
2 5 Esters of o~ y____st 1' _ b~ = , 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-4,6-
di-tert.butyl-phenyl ester.
2.6. Acrylates, such as, for example, ~-cyano-~,~-diphenyl- -
acrylic acid ethyl ester or isooctyl ester, ~-carbomethoxy-
cinnamic acid methyl ester, ~-cyano-~-methyl-p-methoxy-cinnamic
acid methyl ester or butyl es-ter and N-(~-carbomethoxy-vinyl)-
2-methyl-indoline.
2.7. Nickel com~ounds, such as,-for example, 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-cyclohexyl-di-
e-thanolamine, nickel cornplexes of bis-[2-hydroxy-4-(1,1,3,3-
tetramethylbutyl)-phenyl]-sulphone, such as the 2:1 complex,
optionally with addi-tional li~ands such as 2-ethyl-caproic acid,
nickel dibutyldithiocarbama-te, 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 ket-
oximes such as of 2-hydroxy-4-methyl-phenyl-undecylke-tonoxime,
nickel 3,5-di-tert.butyl-4-hydroxy-benzoa-te and nickel iso-
propylxanthate.
2.8. Stericall~ hindered amines, such as 9 for example, 4-
benzoyloxy-2,2,6 7 6-tetramethylpiperidine, 4-stearoyloxy-
2,2,6,6-tetramethylpiperidine, bis-(2,2,6,6-te-trame-thylpiperi-
-21-
1~48529
dyl) sebacate, and 3-n--octyl-7~7,9,9-tetramethyl-1,3,8-
triaza-spiroC4,5]decane-2,4-dione.
2.9. Oxalic acid.diamides, such as, for example, 4,4'-di-oc-tyl-
oxy-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-dime-thylaminopropyl)-oxalamide,
2-ethoxy-5-tert.butyl-2'-ethyl-oxanilide and its mixture with
2-ethoxy-2'-ethyl-5,4'-di-tert.butyl-oxanilide and mixtures
of ortho- and para-methoxy- as well as ot o- and p-ethoxy-
disubstituted oxanilides,
3. Metal d_activators, such as, for example, oxanilide,
isophthalic 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-N-salicylidenehydrazine and 3-salicyloyl~nino-
1,2,4-triazole.
4. Phosphites, such as, for example, triphenyl phosphite,
diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonyl-
phenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite,
3,9-di-isodecyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro~5,5
undecane and tri-(4-hydroxy-3,5-di-tert.butylphenyl) phosphite.
Compounds which destroy Peroxides~ such as, for example,
.
esters of ~-thiodipropionic acid, for example the lauryl,
stearyl, myristyl or tridecyl esters, mercapto-benzimidazole
and the zinc salt of 2-Mercapto-benzimidazole.
6. Polyamide stabilisers, such as, for example, copper salts in
1~48529 ~ ::
:
combina-tion with iodides and/or phosphorus compounds and salts ~-
of divalent manganese.
7. Basic co-stabilisers, such as, for example, melamine,
benzoguanamine, polyvinylpyrrolidone, dicyandiamide,
triallyl cyanurate, urea derivatives, hydrazine derivatives,
amines, polyamides, polyurethanes, and alkali metal salts and
alkaline earth metal salts of higher fa-tty acids, for example
Ca stearate, Zn stearate, Mg stearate, Na ricinoleate, K
palmitate, antimony pyrocatecholate or zinc pyrocatecholate,
8, PVC stabilisers, such as, for example, OrganiG tin compounds,
,
organic lead compounds and barium-cadmium salts of fatty acids, ~-
9, Nucleating a~ents, such as, for example, 4-tert,butyl-benzoie
acid, adipic acid and diphenylacetic aeid.
10, Urea derivatives, such as, for example, N-cyclohexyl-N'~
:: .
naphthylurea, N-phenyl-N,N'-dicyclohexylurea, N-phenyl-N'-2
naphthylurea, N-phenylthiourea and N,N'-dibutylthiourea.
11, 0-ther additives, such as, for example, plasticisers,
lubricants, emulsifiers, fillers, carbon black, asbestos,
kaolin, talc, glass fibres, plgments, optical brighteners~
flameproofing agents and antistatic agents,
The preparation and use of the compounds according to
the invention are described in greater detail in the examples
which follow, In these, parts denote parts by weight and %
denotes percentages by weight,
1C~485Z9 ~
Example 1
46 g (0.64 mol) of isobu-tyraldehyde and 184 g (0.5
mol) of N,N-diethyl-dithiocarbamic acid (3,5-di-tert butyl-
4-hydroxybenzyl) ester are dissolved in 600 ml of isopropanol
at 60C. A solution of 20 g (0.5 mol) of sodium hydroxide in
50 ml of wa-ter is added dropwise at this temperature, with
stirring, over the course of one hour. The mix-ture is -then
heated for 2 hours un1er r~luxand ~x~d-to 50~ and 600ml~of 1% s~eng~
acetic acid are added and the whole is cooled to 0C, whereupon
the product crystallises. After being filtered off with suction,
133 g (92% of -theory) of 3-(3,5-di-tert.butyl-4-hydroxyphenyl)-
2,2-dime-thyL~propionaldehyde are obtained. Af-ter recrystallis-
ation from 66% strength isopropanol, the product melts at 78C.
If, in this example, the isobutyraldehyde is replaced
by an equimolecular quan-tity of one of the aldehydes in Table
I which follows, an otherwise identical procedure gives the
2-(3,5-di-tert.-butyl-4-hydroxybenzyl)-substituted aldehydes with
the melting points shown: -
-24-
1q)48SZ9
T a b l e
Melting point of the
Aldehyde benzylatlon product
2~5 .
. . liquid ~)
- C~lO :-
4 9
C2H5
Cl~O 66C
2H5
., .
H /CIIQ
\/
/C\ 92C
f~2 ` Ic~l2
C~2 ~C 12
Cli2 .
fH3 90C
ll- C ~ CHO
_
~) Analysls Calculated C 79.71 H 11.05 0 9.2
Found 79.7 11.1 9.1
__ .
-25-
:
1~48SZ9
Exan?ple 2
206 g (1 mol) of 2,6-di-ter-t.butylphenol~ 30 g (1
mol) of paraformaldehyde and 76.1 g (1 mol) of carbon disul-
phide are su-pended in 350 ml of isopropanol. 7~.15 g (1
mol) of diethylarnine, dissolved in 125 ml of isopropanol, are then
a~d~x~se with stirring over the course of or.e hour. The
reaction is exothermic and the reaction mix-ture heats up from
room tempera-ture to approx. 40C. It is then heated under
reflux and stirred for a further 3 hours at this -temperature.
It is then cooled to 50C~ 92 g (approx. 1.3 mols) of isobuty-
raldehyde are added and a solution of 40 g of sodium hydroxide
in 100 ml of water is added dropwise over the course of one
hour. Further working up is carried ou-t according to Example
1. 3-(3,5-Ditert.butyl-4-hydroxyphenyl)-2,2-dimethyl-
propionaldehyde, melting point 76~78C, is thus obtained in an
almost quantitative yield.
If, in this exarnple, the 2,6-d~tert.-butylphenol is
replaced by an equimolecular quantity of one of the phenols
in Table II which follows, an otherwise identical procedure
gives the 3-(3,5-dialkyl-4-hydroxyphenyl)-2,2-dimethyl-
propionaldehydes with the melting points shown:
-26-~
. .,
~1)485Z9
T a b 1 e II
. , ~
Melting point of the -:
Phenol
reaction product
_. ,
iso-Propyl
U ~ 1 71C
o-Propyl . ~.
C~3 `
. ~ .
HO ~ ~ 7~ C
/~~
CH3
.
,
~27-
.
,
lV4~S;i~9
E~cam~le ~
- 14 g (0.35 mol) o~ sodi~ml hydroxide are dissolved in
14 ml of water and are run in-to a suspension of 1.5 g of
tetrabutylammonium iodide in 20 ml of benzene. The mixture is
hea-ted to 70C with stirring and a solution of 76.5 g (0 3
mol) of 3,5-di~tert.butyl-4-hydroxy-benzyl chloride and 28.8 g
(0.4 mol) of isobutyraldehyde in 100 ml of ligroin is added
dropwise a-t this temperature over the course of 2 hours. The
mixture is stirred for a further 2 hours at 70Cand is then
cooled, 10 ml of glacial acetic acid are added and the mix-
ture is diluted with 100 ml of toluene. The organic phase is
thoroughly washed with water and is completely evaporated under
reduced pressure. A red-brown oil is thus obtained, which,
according to thin-layer chromatography (migrating agen-t toluene),
contains 3-(3,5-di tert.butyl-4-hydroxyphenyl)-2,2-dime-thyl-
propionaldehyde.
Example 4
23.2 g (0.08 mol) of 3-(3,5-di-tert.butyl-4-hydroxy-
phenyl)-2,2-dimethyl-propionaldehyde, 3.92 g (0.08 mol) of
sodium cyanide and 23 g (0.24 mol) of ammonium carbonate are
suspended in 100 ml of 90% strength ethanol and are s-tirred
for 2 hours at 45 C. The mix-ture is then cooled -to room
temperature, treated with 200 ml of water and stirred Yor a
further hour. The precipitate which has formed is then
filtered off with suction,washed with a ~e ar~ount of water and
recrystallised from acetonitrile. The 5-Cl,l-dirnethyl-2
(3,5-di-tert.butyl-4-hydrox~phenyl)-ethyl]-hydantoin thus
..
--28-
, : .
10~
ob-tained sinters from 150C 7 becomes solid again and then
mel-ts from 220C.
Example 5
Stabilisation of polypropylene against degradation during
~__ces.sin _ _
O.1 pa-rt of 3-(395-di-tert.butyl-4-hydro~yphenyl)-
2,2-dime-th~Jl-propionaldehyde are homogeneously mixed wi-th
100 parts of polypropylene powder ("Propathene HF 20" of
Messrs. ICI) and are regranulated 5 times in succession in
a single~screw extruder at a maximum of 260C and 100 rpm.
The melt index (MI) of the material is measured in each case
after the lst-, 3rd and 5th extrusion (2,160 g through-
put at 230C; data in grams every 10 minutes). A degradation
of -the polymer manifes-ts itself in a rapid increase in the
melt index. A parallel experiment is carried out in the
same manner with no stabiliser added.
T a b 1 e III
. _ .
Melt index
Ini-tial 1st 3rd 5-th
state Extrusion Extrusion Ex-trusion
. _ __ . _
Unstabilised
sample 2.50 12.0 34.7 73.3
Stabilised
sample 2.50 3.5 5.8 6.1
-29-
i~48S29
Exam
36.7 g (0.1 mol) of N9N-dlethyl~di-thiocarbamic acid
(3,5-di-tert.butyl-4-hydroxybenzyl) ester and 3.5 g (0.6 mol)
of propionaldehyde in 120 mi of isopropanol are initially --
taken and are warmed to 40C. A solution of sodium hydroxide
in 10 ml of water is added dropwise with s-tirring over the
course of one hour. S-tirring is continued for a further 2
hours at the same temperature. The mixture is -then cooled
to room temperature and 30 ml of 10% streng-th acetic acid are
added. The precipitate which has formed is filtered off with
suction and thoroughly washed, first with 70% streng-th iso-
propanol and then with 1~ strength acetic acid. After
recrystallisa-tion from acetonitrile, the 2,2-bis-(3,5-di-
tert.bu-tyl-4-hydroxybenzyl)-propionaldehyde melts at 173C.
Example 7
46 g (0.64 mol) of isobu-tyraldehyde and 161.5 g (0.5
mol) of N,N-diethyl-dithiocarbamic acid (~-tert.-butyl-4-
hydroxy-5-methyl-benzyl) ester are dissolved in 600 ml of
isopropanol at 60C.-A solution of 20 g (0.5 mol) of sodium
hydroxide in 50 ml of wa-ter is added dropwise at this tempera-
tureJ with stirring, o~er the course of o~ hour. The mixture
is then heated under reflux for 2 hours. After distilling off
approx. 200 ml of isopropanol, the mixture is treated with 2
ml of g~acial acetic acid and 400 ml of water are then added,
whereupon the product crystallises. After filtering off with
suction, it is recrystallised from a 5:2 mixture of isopropanol/
water. 3-(3-Tert.-bu-tyl-4-hydroxy-5-methylphenyl)-2,2-dimethyl-
-30-
, . " . ' ,:
... . .
1~348S29
propionaldehyde, mel-ting poin~t 93C, ls thus obtained
If 7 in -this example, -the N,N-di.ethyl-di-thiocarbamic acid
(3-tert.butyl-4-hydro.xy-5-methylbenzyl) ester is replaced by
one of the nuclear-substituted die-thyldithiocar~amic acid
(4-hydroxybenzyl) esters in Table IV which follows, an o-ther-
wise identical procedure gives -the nuclear-substituted-3-(4
hydroxyphenyl)-2,2-dimethyl-propionaldehydes with the melting
points shown:
. T a b l e _ IV
Dithiocarbamic acid ester product
_ _ _ . . . .
tert.Butyl
H0 ~ ~ -Cll2S-C-N / ¦ 102C
C~3 CU3
,' ' . .~
H2C _cu~
H~G CH2 S
N \ 92C
--~ C 2H5
C 2
H2C CH2 .
