Note: Descriptions are shown in the official language in which they were submitted.
103660~
- The present invention relates to new compounds,
the method for their manufacture, their use for stabilizing
organic material and the organic material stabilised with
their aid.
The new compounds correspond to the general
: formula I
- r ~ N - C~
N - ¦ R5 (I)
wherein Rl denotes alkyl with 1 to 8 carbon atoms; R2 denotes
hydrogen or alkyl with 1 to 8 carbon atoms; R3 denotes hy~
drogen or methyl; X denotes a direct bond, alkylene with
.~ 1 to 18 carbon atoms; R4 denotes hydrogen, alkyl with 1 to
: 17 carbon atoms, or a group . :
Rl
:i: CH~-CH2 ~ OH
,.,: )~
R3 R2
m denotes 1 to 3, R5 - if m is 1 - denotes hydrogen, alkyl
with 1 to 18 carbon atoms, hydroxybenzyl which is unsubstituted
or substituted by 1 to 3 alkyl groups each with 1 to 4 carbon
atoms, or one of the groups -CH2CH2CN or ~~CH2)q -COOR, ~ .
wherein R is alkyl with 1 to 18 carbon atoms and q is 1 or .~.
2, or a group
Rl ~.
CH -CH-CH ~ OH
R3 2
~ ~ '~ '' ' `
~ ~()36601
or - if m is 2 - denotes alkylene with 1 to 18 carbon atoms
or oxaalkylene with 4 to 21 carbon atoms, wherein the carbon
atom bonded to the nitrogen does not carry any further
heteroatoms; or - if m is 3 - denotes alkanetriyl with 1 .
to 18 carbon atoms or the group
2 2
N \ ~:
;': CIH2 ICH2
- N N
-CH2CH2CO CH2 COCH2CH2- ~,
and R6 if - m is 1 - is hydrogen, alkyl from 1 to 18 carbon
atoms or one of a group of the formula
~,.,: ~R "
,.,
H0 ~ ~ - CH2- or C6H5NHCO-
/~ '.
. R2 3
or - if m is 2 or 3 - is hydrogen,
i~, . . .
- It has been found that the compounds of the for-
. mula I are very suitable for stabilising organic material
against thermo-oxidative degradation. Herein, the new
hydantoins of the formula I show, surprisingly, better
activity than the ketones on which they are based.
Preferred compounds of the formula I are those
. wherein Rl denotes alkyl with 1 to 4 carbon atoms; R2
denotes hydrogen or alkyl with 1 to 5 carbon atoms, pre-
ferably butyl; R3 denotes hydrogen, X denotes a direct
20 bond or alkylene with 2 or 3 carbon atoms, preferably one
of the radicals -CH2CH2- or -CH23-CH-; R4 denotes alkyl with
~ 1 to 17 carbon a~oms, cyclohexyl or a group
:~ ~R
-CH2CH2~H
R3 R2
--3--
-' .
"~
1036601
R5 - if m is 1 -denotes hydrogen~ alkyl with 1 to 18, pre-
~ ferably 8 to 18, carbon atoms, hydroxybenzyl substituted by -
1 to 3, preferably 2, alkyl groups each having 1 to 4 car-
: bon atoms, or a group ~(CH2)q~COOR, wherein R is alkyl with
1 to 18, preferably 2 to 18, carbon atoms and q is 1 or 2,
or - if m is 2 - denotes alkylene with 1 to 18, preferably
1 to 6, carbon atoms or the group -CH2CH2-O-CH2CH2-, m de-
notes 1 or 2 and R6 denotes hydrogen.
Amongst the preferred compounds the following
classes should above all be mentioned: -
a) H ~O
H~ ~ /NH (la)
' R2 R3
wherein Rl and R2 independently of one another denote alkyl
with 1 to 4 carbon atoms, R3 denotes hydrogen, X denotes a
.: CIH3
:. direct bond, -CH2-CH2- or -CH2-CH- and R4 denotes alkyl with
1 to 17 carbon atoms, or a group .
,_~ Rl ;~
-CH2CH2 ~ OH
,. :
~ R3 R2
b)
` R~ I \ N-CH ~-- OH (Ib)
HO ~ R4 o R
~ R 3
.. rl T
. ~ 4 .
;
-.. , - . : .: -. ~.. .. .. : ~ - . . .
~036601
wherein Rl, R2, Rl' and R2' independently of one another
; denote alkyl with 1 to 4 carbon atoms, R3 and R3' indepen-
.~ dently of one another denote hydrogen or methyl, X denotes
CH3
a direct bond, -CH2-CH2- or -CH2-CH- and R4 denotes alkyl
with 1 to 17 carbon atoms, or a group
2 2~0H
~: R3 R2
' c )
~:` H ~ O
i: Rl~ N C
\ N-R5 (Ic)
` H0 ~ X - C--C~
R2 3
'
wherein Rl and R2 independently of one another denote alkyl
with 1 to 4 carbon atoms, R3 denotes hydrogen, X denotes a
~ .
i: r
~ -5-
- . - -: . . ~
.,. . . . . ~
10366l~1
~ ÇH3
: ~ir~ct bond, -CE12-CI12- or -C1l2-C~-, R4 denotes alkyl with
1 to 17 cc~rbon atoms or a group
.~ -Cfr2Cff2-~)-
R3 2
and R5 denotes alkyl with 1 to 18 carbon atoms.
~- d) R ~ \ N - C
¦ ~r-cEl2cf l COof~ ~
'.
wherein Rl and R2 independently o one another denote alkyl
with 1 to 4 carbon atoms, R3 denotes hydrogen, X denotes a
direct bond, -CH2-C~2- or -CH2-CH3-, R4 denotes alkyl with
. .
1 to 17 carbon atoms or a group ~~
:`, Rl ' ' .'
~l CI2C~2 ~ -OH
,.~, 10
~ R3 R2
j I :
and R denotes alkyl with 1 to 18 carbon atoms.
.: e)
i~ 7 /u-(cfr2)p-N\ ¦ 1
(Ie)
~ flO ~ X-C - C~ O Rl~ ~ R2
' ~ .
` ~C1
...... . . . . . ~ . ... ~ .
~0366~)1
wherein Rl and R2 independently of one another denote alkyl
with 1 to 4 carbon atoms, R3 denotes hydrogen, X denotes a
direct bond, -CH2-CH2- OT -CH2-CH-, R4 denotes alkyl with
~ 1 to 17 carbon atoms or the group
; R
~ -CH2CH2 ~ OH
R3 R2
and p denotes 1 to 18.
In the definition of the compounds of the formula
I, R, Rl, R2, R3, R5 and R6 can represent alkyl groups.
Within the indicated limits, these groups can be methyl,
ethyl, isopropyl, butyl, sec.-butyl, tert.-butyl, amyl,
sec.-amyl, tert.-amyl, hexyl, heptyl, octyl, tert.-octyl,
nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl or
octadecyl.
If the radicals X and R5 in the definition of
the formula I are alkylene, it can be, for example, methyl-
ene, ethylene, 1,2-propylene, 1,3-propylene, tetramethyl-
ene, hexamethylene or octamethylene.
When R5 is oxaalkylene it can denote, for example,
the divalent radical of 2-oxapropane, 2-oxabutane J 3-oxapen-
tane, 3-oxaheptane J 3-oxaundecane, 3-oxapentadecane or 3-
oxaheneicosane.
When R5 denotes alkanetriyl it can be, for example,
neopentanetriyl.
; Examples of compounds of the formula I are:
5-(3,5-diisopropyl-4-hydroxy-phenylethyl)-5-methyl-hydan-
toin, 5-t3,5-di-tert.-butyl-4-hydroxybenzyl)-5-heptadecyl-
hydantoin, 5-(3-tert.-butyl-4-hydroxy-5,6-dimethyl-phenyl-
ethyl)-5-methyl-hydantoin, and 3,3~-tetramethylene-bis-
~5-~3,5-di-tert.-butyl-4-hydroxy-phenylethyl)-5-methyl-hy-
,`'
~ 7 ~7~
.
` ~03660~
dantoin].
The compounds of the formula I in which R5 has : .
a different meaning from hydrogen and R6 is hydrogen may
-~ be prepared from compounds of the formula I in which m de- :
; notes 1, R5 and R6 denotes hydrogen (here described as ~:
compounds of the formula II).
. R H~N ~ `~ .
~\ I ~NH ~II)
HO~ R4 0
; 2 3 . ~ :
Such compounds may be prepared, in turn, by re- .
action of 1 mol of a compound of the formula III ~:
i. 1 .: :
HO--~ X - 1! R4 (111)
R2 R3 ::
'
,','~ , .
::
' ''
', '
~ .
:.' :
' ,. ~ i
''' ~~,-
10366l
with on~ mol o~ sodium cyanide or l)otas~sium c~anide and an
excess of an~nonium carbonate in a polar solvent at 40-50C.
Methanol, ethanol~ isopropanol~ dimethylformamide
or dioxane can be used as solvents, their mix~ures with
water being employed preferen~ially.
Compo~lnds of the formula I in which R5 denotes a
hydroxybenzyl group unsubstituted or substituted by 1-3 alkyl
groups each wi~h 1 to 4 carbon atoms and R6 denotes hydrogen
may be prepared by reaction o~ the compounds of the formula II
]o with compounds of the ~ormula IV
.: .
1 (IV)
Y CH2 ~
: . R3 R2
;
i wherein ~ denotes a halogen atom, the group
.'~ . .
:~ ~ / lkyl al~yl
-N or ~he group -~C-N
alkyl ~. alkyl
. ' .
The reaction is preferably carried out in the
presence o~ a basic catalyst such as sodium methylate,
sodium ~Iydride, calcium hydride, lithium amide or sodium
amide. Hydrocarbons, ethers, alcohols and, preferably,
. .; .
dimethylformamide or dimethylacetamide can be used as
~- solvents.
:.. ' q
r ~
.', ~ ' ~
~, ,~J ~ ' " '
1036601
Compounds of the formula I in which R5 denotes
alkyl, or -CH2-COOR and R6 denotes hydrogen may be pre-
. .,- .
ferably prepared by reaction of the compounds of the for- -
mula II with compounds of the formula V
Z-R5 (V)
wherein Z denotes a halogen atom.
The reaction is carried out in the presence of
a basic catalyst such as potassium carbonate, sodium hy-
droxide, sodium methylate or lithium amide. As solvents,
it is possible to use alcohols such as methanol, ethanol, - -~
isopropanol or butanol, ethers such as tetrahydrofurane or
dioxane, ketones such as acetone, methyl ethyl ketone or
cyclohexanone, as well as dimethylformamide or diemethyl-
acetamide.
: :.
; The compounds of the formula I, in which R5 -
denotes one of the groups -CH2CH2CN or -CH2CH2-COOR and
R6 denotes hydrogen, may be prepared by reaction of the
- compounds of the formula II with acrylonitrile or compounds
~; of the formula VI, respectively
CH2=CH-COOR ~VI)
The reaction takes place in the presence of a
basic catalyst such as sodium methylate, sodium hydride,
calcium hydride, lithium amide or sodium amide, Alcohols,
ethers, ketones, or dimethylformamide or dimethylacetamide
can be used as solvents.
The compounds of the formula I in which R5 denotes
the group
"' .:
.. -. : .
.
':, `
~.. 1; ;:
~ 1036601
. ~ . . .
-c~l2-cb~-c!2 ~ -Ol~
3 2
and R6 denotes hydrogen may be prepared by reaction of the
compounds of the formula II with compounds of the Eormula VII
OH (~II)
3 2
The reaction takes place in the presence of a
basic catalyst, preferably a tertiary amine such as tri-
ethylamine, tripropylamine or pyridine, in a polar solvent,
for example dioxane, tetrahydro~urane, isopropanol or di-
~ethyl~ormamide.
; 10 Compounds of the formula I in which m is 1 and R6
deno~es alkyl or the group
;,~ CH2-~ 0~1
R3 R2
may be prepared by the reaction of an hydantoin of the
-
formula I wherein R6 is hydrogen with a compound to the
formula
:... ~,4 . .
.
.; ~' . ,;,
., ~
: . ':
.
.. ., . . . .. . - :: . , . - , - - ~ . - ~
1036601
.
CH3 ~ 1
CH / 2 ~ OH or Y-alkyl
R3 2
wherein Y is halogen. ~ -
The reaction takes place as described for the re-
` action of compounds IV with compounds II.
Compounds of the formula I in which m is 1 and
i R6 denotes the group - CONHC6H5 may be prepared by the ~ `
reaction of an hydantoin of the formula I, wherein R6 is
hydrogen with phenylisocyanate.
The reaction takes place in a solvent such as
mixtures of toluol and dioxane.
Compounds of the formula I in which m is 2 and
R5 denotes alkylene or oxaalkylene, may be prepared by re-
action of compounds of formula II with dihalides of the
- formula VIII
. Z-R5-Z ~VIII)
wherein Z denotes a halogen atom. The reaction takes place
in the presence of a basic catalyst such as potassium car-
bonate, sodium hydroxide, sodium methylate or lithium amide.
As solvents it is possible to use alcohols such as methanol,
. 20 ethanol, isopropanol or butanol, ethers such as tetrahydro-
~.,
furane or dioxane, ketones such as acetone, methyl ethyl
ketone or cyclohexanone, as well as dimethylformamide or
dimethylacetamide.
The reaction takes place according to a method
customary for trans-esterification reactions, in the pre-
sence of an acid catalyst such as hydrochloric acid, sul-
phuric acid or p-toluenesulphonic acid or of a basic cata-
lyst such as lithium hydroxide, sodium hydride or potassium
-12-
` 1036601
amide.
Compounds of the formula I in which m is 3 and
R5 denotes a'kanetriyl may be prepared by reaction of the
compounds of the formula II with compounds of the formula
XI
Z-R5 (XI)
Z
.
" ;: .
.
: ~ .
~, . . . ..
,: '
:.'' ': . '
,
',. ' ~ ~
... , : .
`; ~'
' ~ ' ', ' ~ :
-' ~ .
1036601
wllereLn ~ d~liotes a llalogen atotn. Tllc react-ion takes place
under the conditions described for the reaction with the
compounds V alld VIII.
Compo~ ds oE the ~ormula I in which m is 3 and
R5 deno~.es the group
COC}I~C~
N
.'. C~ Cl{2
~ Cl~ CO ~ `~2~ ~ CoC}12C~2-- ~
' ' ' .
may be prepared by reacting the compounds of the formula II
with 1,3,~tris-acryloyl-hexahydro-s-triazine.
The reacting takes place under collditions as described
for the reaction of compounds of the formula VI with compounds
.: of the formula II.
~ The compounds of the formu].a I are used as stabi-
,
lisers for organic subs~ates. Examples of such substrates are:
s 1. Polymers which are derived ~rom singly or doubly
unsaturated hydrocarbons, such as polyoleines, such as,
~or example, polyethylene, ~hich can optionally be cross-
b,, linked, polypropylene, polyisobutylene, po].~nethylbutene-l,
.:
'; polymethylpentene 1, polybutene-l, polyisoprene, polybuta-
' diene, polystyrene, polyisobutylene, ~olymers of the mono-
-, 20 me~s on ~hich the homopolymers mentioned are based, such as
. .
ethylenepropylene copolymers, propylene-butene-l copolymers,
!""' propylene-isobutylene copolymers, and styrene-bu~adiene co-
- ` .
: ~ .
-, ~
lQ366¢~1
polymers, as well as terpolymers of ethylene and propylene
with a diene, such as, for example, hexadiene, dicyclopenta-
i diene or ethyliclerlenorbornene; mixtures o~ the abovemen-
tioned homopolyrners such as, for example, mixtures of poly-
propylene and polyethylene, polypropylene and polybutene-l,
polypropylene and polyisobutylene.
2. Vinyl polymers containing halogen, such as poly-
vinyl chloride, polyvinylidene chloride, and poly~inyl
fluoride, but also polychloroprene and chlorinated rubbers.
3. Polymers which are derived from a,~-unsaturated
acids and their derivatives,such as polyacrylates and poly-
methacrylates, polyacrylamides and polyacrylonitrile as well
-` as their copolymers with other vLnyl compounds, such as
acrylonitrile/butadiene/s~yrene, acrylonitrile/styrene and
acrylonitrile/styrene/acrylic ester copolymers.
.
4. Polymers which are derived from unsaturated alcohols
and amines or their acyl derivatives or acetals, such as
polyvinyl 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. Hvmopolymers and copolymers which are derived from
epoxidesj such as polye~hylene 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.
.', .
:; .
~036601
7~ Polyphenylene oxides.
8. Poly-lrethanes and polyureas.
g. 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,
polyamide 6l5, polyamide 6/10, polyamide 11 and polyamide 12.
12. Polyesters wl-ich are derived from dicarboxylic acids
and dialcohols and/or from hydroxycarboxylic acids or the
corresponding lactones, such as polyethy.ene glycol tere-
ph~halate and poly-l,4-dimethylol-cyclohexane terephthalate.
13. Crosslinked polymers which are derived from alde-
- hydes on the one hand and phenols, ureas and melamines on
the other, such as pheno]-formaldehyde, urea-formaldehyde
. and melamine-formaldehyde resins.
L,'~ 14. ~lkyd resins, such as glycerine-phthalic acid resins
and their mixtures with melamine-fonnaldehyde resins.
15. Unsaturated polyester resins which are derived
from copolyesters of sa~wrated and uns~turated cticarboxylic
~` acids with polyhydric alcohols, as well as 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,
.... . .
' ~ ' -.
.
.. ,~ ' . ~.
.. j.. . . . - . . . . - . . . . . ... . . . .. ..
.. . . . .. . . . . . . . .
1036601
such as cellulose acetates, cellulosc propionates and
cellulose butyrates, or the cellulose ethers, such as methyl-
cellulose.
17. High molecular monomeric substances, for example
mineral oils, animal and vegetable fats~ oils and waxes, or
oils, waxes and fats based on synthetic esters.
The compounds o~ the formula I are incorporated
into the subs~ates in a concentration of 0.01 to 5% by
weight calculated rela~i~e to the material to be stabilised.
Preferably, 0.05 to 2.0, especially preferentially
0.1 to 1.0% by weight of ~he compounds, calculated relative
to the material to be stabilised, are incorporated into the
latter. The incorporation can, ~or example~ be e~fected by
admixing at least one of the compounds of the ormula I and ;
optionally further addlt-ives according to the methods custo-
mary in the art, be~ore or during shaping, or by application
o~ the dissolved or dispersed compounds onto the polymer,
- .
`; i~ appropriate with subsequent evaporation of the solvent.
` In the case of crosslinked polyethylene, the com-
; 20 pounds are added before the crosslinking.
As furtller additives, together with which the
stabilisers can be employed, thcre should be mentioned:
A. Simple 2,6-dialkylphenols, such as, for example, 2,6-
di-~er~.-butyl-4-rnethylphenol, 2-~ert.-butyl-4,6-dimethyl-
phenol, 2,6-di-tert. bu-tyl-4-methoxyrnethylphenol and 2,6-
dioctadecyl-4-methylphenol.
. ' .
l7
_ ,;~ _
", ~ ' .
,~ :
.
1~366~1
R. Deriva~iv~s of alk~lated h~drocluinone~s, such as, for
example, 2,5-di-~ert.-butyl~hydroquinone, 2,5-di-tert.-amyl-
hydroquinone, 2,6-di-tert -bu~yl-hydroquinolle, 2,5-di-
~e~ -bu~yl-4-hydroxy-anisole, 3,5~di-tert.-butyl-4-hydroxy-
anisole,tris(3,5-di-tert.-butyl-4-hydroxyphenyl)-phosphite,
3,5-di-~ert-buty]-4-hydroxyphenyl-stearate and bis-(3,5-di-tert.
butyl-4-hydroxypherlyl)-adipate.
C. ~dro~ylated thiodiphenyl ethers, such as, for example,
2,21-~hiobis-(6-ter~.-butyl-4-methylphenol), 2,2'-thiobis-
~', 10 (4-octylpllenol), 4,4'-thiobis-(6-t~rt,-butyl-3-methylphenol),4,4'-thio~is-(3,6-di-sec.~amylphenol)~ 4,4'-thiobis-(6-
tert.-butyl-2^me~hylphenol)J and 1~,4'-bis'-(2,6-dimethyl-4-
hydroxyphenyl)-disulfid.
D. Alky]idene~bi _ henols, such as, or example, 2,2'-
methylene-bis~(6 tert.-bu~yl-4-methylph2nol), 2,2'-methylene-
bis-(6-tert -bu~yl-4-ethylphenol), 4,4'-m~thylene-bis-(6-
ter~.-bu~yl-2--methylphenol, 4,4'-me~hylene-bis-(2~6-di-tert.-
butylphenol), 2,6-di-(3-ter~.-butyl-S-methyl-2-hydroxybenzyl)-
~--methylphenol, 2,2i-methylene-bis-¦4-methy].-6-(~-methyl-
cyc]ohexyl)~henyl~, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl-
butane), l,l-bis-(5-t~rt.-butyl-4~hydroxy-2-me~hylphenyl)-
butane, 2,2-bis-(5-~ert,-butyl-4-hydroxy~2-methylphenyl)-
butane, 2,2-bis-(3,5-di-~ert.~bu~yl-4-hydroxyphenyl)-propane,
1,1,3-tris~(5-ter~ -bu~.yl-~-hydroxy-2-methylphenyl)-b~ane,
2,2-bis-(5-~r~.~bu~yl-4~hydroxy-2-methylphenyl)-4-n-dodecyl-
mercapto-butane, l,l,S,5-~e~ra-(S-tert.-bu~yl-4-hydroxy-2-
. ~. .. .
,
: , -
.. ~ - .
,. - : . .. :
10366~
me~hylphenyl)-pcni.~ne and ethylene glycol-bis-[3,3-bis-(3'-
tert.-butyl-4' hydroxyphcnyl)-butyrate~.
E._0-~ N- ~ntl , such as, for example,
3,5,3',5'-tetr~-~er~.-butyl-~,4'-dihydroxydibenzyl-ether,
~-hydroxy 3,5-dime~hylbenzyl-merca~toacetatic acid octadecyl
es~er, tri-(3,5-di~er~.-bu~yl~4-hydroxybenzyl)-amine, and
~he bis-(4-tert.~bu~yl-3-hydrox~r-2~6-dime~hylbenæyl)-dithiol-
terephthala~e.
~ , such as, ~or example
2,2-bis-(3,5-di-tert.-butyl-2-hydroxyben~yl)-~alonic acid
dioctadecyl es~er, 2-(3-tert.-butyl-~-hydroxy-5-methylbenzyl)-
malonic acid dioctydecyl ester, 2,2-bis-(3,5-di-tert.-butyl-
4-hydroxybenzyl)-malonic acid didodecylmercapto-ethyl ester,
and 2,2-bis-(3,5-dl-tert.-butyl 4-hydroxybenzyl)-malonic
scid di-(4-tert.-octylphenyl) ester.
G. Hydroxybenzyl-aromat-ics, such as, ~or example, 1,3,5-tri-
(3,5 di~tert.-butyl-4-hydroxybenzyl)~2,4,6-trin~ethylbenzene,
. ~ . . .
1,4-di-(3,5-di-tert.-butyl-4-hydroxybenzyl)-2,3,5,6-tetra-
methylbenzene and 2,4,6-tri-(3,5-di-tert.-butyl-~-hydroxy-
benæyl)-phenol.
I-l. s-Triazine compounds, such as, for example, 2,4-bis-octyl-
mercapto-6-(3,5-di-tert -butyl-4-hydroxyan;lino)-s-triazine,
2-octylmercapto-4,6-bis-(3,5-di-tert.-butyl-4 hydroxyanilino)-
s-triazine, 2-octylmercapto-4,6-bis-(3,5-di-tert.-butyl-4-
hydroxyphenoxy)-s-triazine, 2,4,6-tris-(3,5-di-tert.-butyl-4-
hydroxyphenoxy)-s-triazine, 2,4,6-tris-(3,5-di tert.-butyl-
:
;`,'' ~ ';
~' ', '
,
- . - . . . .- ~ . . .. .. . . . . . .
~()366~1 -
~-hydrox~ypllenyle~hyl)-s-triazine and 1,3,5-tris-(3,5-di-tert.-
butyl-4-hydro~ybenzyl)-isocyanurate.
~ I. Amicles of 3,5-di-tert.-butyl-4 hyclroxyphenyl~propionic acid,
such as, for example 1,3,3-tri-(3,5-di-tert.-butyl-4-hydroxy-
phenyl-propionyl)-hexahydro-s-triazine and N,N'-di-(3,5-di-
tert.-butyl-4-hydroxyphenyl-propionyl)-hexamethylenediamine.
K. Esters of 3,5-di-tert.-butyl-4-hydroxyphenyl-propionic
acid with monohydric or p lyhydric alcohols, such as, for
. example, methanol, ethanol octadecanol; 1,6-hexanediol;
l,9-nonanedi.ol, ethylene glycol; 1,2-propanediol, diethylene
glycol, thiodie~hylene glycol, neopentyl glycol, 3-thia-
undecanol, 3-thi.a-pentadecanol, trimethylhe~anediol, tri-
- methylolethane, trimethylolpropane, Fentaerythritol, tris- ~-
hydroxyethyl-isocyanurate and 4-hydroxymethyl-1-phospha-2,
r: 15 6,7-trioxabicyclo [2,2,2]-octane.
;: L. Esters of 5-tert.-butyl-4-hydroxy-3-me_lly-phenyl-~ropionic
: acid with monohydric or polyhydric alcohols, such as, for
example methanol, ethanol, octadecanol; ].,6-hexanediol; i,9-
nonanediol, ethylene glycol; 1,2-propanediol, diethylene
glycol, thiodiethylene glycol, neopentyl glycol, 3-thia-
~ undecanol, 3-thia pentadecanol, tri~ethylhexanediol, tri-
methylolethane,trimethylolpropane, pentaerythrital, tris-hy-
droxyethyl-isocyanurate and 4-hydroxymethyl-1-phospha-2,6, :
7-trioxabicyclo [2,2,2]-octane.
:,, .
. ,' ,;~o
- .:~F -
," ~ , .
. . .
~(~36601
M. ~sters o~ 3,5-di tert.-butyl-4--h~clroxyF)lleny~ce~ic acid
with monohyclric or polyhydric alcoho]s, such as, for example
methanol, e~hanol, octadecanol, 1,6-he~anediol; l,9-nonane-
diol, ethylene glyco], 1,2-propanediol, diethylene glycol,
thiodiethylene glycol, neopentyl glycol, 3-thia-undecanol,
3-thia-pentadecanol, trimethylhexanediol, trimethylolethane,
trilllethylolpropane, pentaerythritol, tris~hydroxyethyl-isocya-
nurate a~d 4-hydroxymethyl-1-phospha-2,6,7-~rioxabicyclo ;~
[2,2,2]-octane.
N. Acy~aminophenols, such as, for example, N-(3,5-di-tert.-
., .
butyl-4-hydroxyphenyl)-stearic acid amide and N,N'-di-(3,5-
di-tert.-butyl-4-hydroxyphenyl)-thio-bis-acetamide.
0. 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-hydro~ybenzyl-phosphonic acid diocta-
decyl ester and 5-tert.-butyl-4-hydroxy-3-methylbenzyl-
phosphonic acid dioctadecyl ester.
Amongst the aminoaryl derivatives there. should be
mentioned aniline and naphthy].amine derivatives as well as
thei.r heterocyclic deriva~ives, ~or example: phenyl-l-
na~thylamine, phenyl-2-naphthylamine, N,N'-diphenyl-p-
phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine,
N,N'-di-sec.-butyl-p-phenylenediamine, 6-etho~y-2,2,4-tri-
methyl-1~2-dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-],2-
dihydroquinoline, mono- and di.-octyliminodibenzyl and
polymerised 2,2,4-trimethyl-1,2-dihydroquinoline.
~`. .
a~
` !
.: :.
.,~..''
1036601
2. UV-absorbers and light protection agents such as:
a) 2-(2 7 -I-lydroxyphenyl)-benztriazoles, for example the
S'-methyl-, 3',5'-di-tert -butyl~-, 5~ tert.-butyl-, 5'-(1,1,3,3-
tetramethylbutyl);5-chloro-3'-, 5'-tert.-butyl~-' 5-chloro-3'-tert.-
butyl-5'-methyl-, 3'-sec.-butyl-5'-tert.-butyl-' 3'-[a-methyl-
benzyl]-5'-methyl-: 3'-[a-methylbenzyl~-5'-methyl-5-chloro-;
4'-hydroxy; 4'-metho~y; 4'-octoxy-, 3',5'-di-tert.-amyL-:
3'-methyl-5'-carbomethoxye~hyl-' and 5-chloro-3', 5'-di-ter~.-
amyl-derivative.
. .
b) 2,4-bis~(2'-~1ydroxyphenyl)-6-alkyl-s-triazines,
for example the 6-ethyl- or 6-undecyl-derivative.
~- cj 2-~lydroxy-benzophenones, for example the 4-hydroxy-, -
~. .
4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4,2',4'-
trihydroxy- or 2'-hydroxy-4,4'-dimethoxy-derivative. -
d) 1,3-bis-(2'-Hydroxy-benzoyl)-benzenes, for example
.... . . .
; 1,3-bis-(2'-hydroxy-4'-hexyloxy-benzoyl)-benzene, 1,3-bis-
(2'-hydroxy-4'-octoxy-benzoyl)-benzene, and 1,3-bis-(2'-
hydroxy-4'-dodecyloxy-benzoyl)-benzene.
e~ ~ryl esters of optionally substituted benzoic acids
such as, or example, phenyl sc~icylate, octylpherlyl sali-
cylate, di-benzcylresorcinol, bis-~4-tert.-butylbenzoyl)-
`; resorcinol, benzoxyl-resorcinol, 3,5-di-tert.-butyl-4-
- hydroxybenzoic acid 2,4-di-tert.-butyl-phenyl ester, octa-
decyl ester or 2-methyl-4,6-di-tert -butylphenyl ester.
f) Acrylates, for example, a-cyallo-~ dipllenylacrylic
acid ethyl ester or isooctyl ester, a-carbomethoxy-cinnamic
acid methyl ester, a-cyano-B-methyl-p-methoxy-clnnamic acid
. .
.~ ~
~r7 - ~ -
~J
....
- ~ ... . : - .
... .. .. ~ . . . ..
.. ~ ~ .. . .
~0366~)1
methyl est:er or butyl ester and ~-(e-carbomethoxy-vinyl)-
2-methyl-indoline.
g) Nickel compounds, for example nickel complexes o~
2,2'-thio-bis-(4-tert.-octylphenol), such as the 1:1 and 1:2
complex, optionally with other ligands such as n-butylamine,
ni~æl complexes of bis-(4-tert.-octylphenyl)-sulph~ne, such
as the 2:1 complex, optionally with o~her ligands such as
2-ethyl-caproic acid, nickel dibutyldithiocarbamate, nickel
salts o~ 4-hydroxy-3,5-di-tert.-butylbenzyl-phosphonic acid
monoalkyl esters, such as the methyl, ethyl or butyl ester,
the nickel complex of 2-hydro~y-4-methyl-phenyl-undecyl-
ketonoxime and nickel 3,5-di-tert.-butyl-4-hydroxy-benzoate.
h) Oxalic acid diam~s, for example 4,4'-cli-octyloxy-
anilide, 2,2'-di.-octyloxy-5,5'di-tert.-butyl-oxanilide, and
2,2'-di-dodecyloxy-5,5'-di-~ert.-butyl-oxanilide.
i) Sterically hindered amines, for example 4-benzoyl-
oxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-
tetramethylpiperidine, bis-(2,2,6,6-tetramethylpiperidyl)-
sebacate, 3-n-octyl-7,7~9,~-tetramethyl-1,3,8-triaza spiro
` 20 [4,5]-decan-2,4-ciione.
;~ 3. Metal deactivators, such as oxanilide, isophthalic
acid dihydrazide, sebacic acid bis-phellylhydrazide, bis-
benzylideneoxalic acid dihydrazide, N,N'-diacetyl-adipic
.. . . .
acid dihydrazi.de, N,N'-bis-salicyloyl~oxalic acid dihydrazide,
N,N'-bis-salicyloyl-hydrazine; and N,N'bis-(3,5-di-tert-butyl-
4-hydroxyphenyl)-hydrazine.
. ~3
_ ,~ _
, . .
~? ~
~ .
` 1036601
.
4. Phosphltes, such as triphenylphosphite, diphenyl-
alkyl-phosphites, phenyl~ialkylphosphites, trinonylphenyl~-
: phosphite, trilaurylphosphite, trioc~adecylphos~hite, and 3,9-
di-isodecyloxy-2,4,8,10-tetraoxa-3,9-diphospha-spiro-(5,5)-
undecane.
5. Compounds which destroy peroxide, such as esters of
. j ~ .
~; B-thiodipropionic acid, for example the lauryl) s~earyl,
: myrysityl or tridecyl ester, salts of 2-mercaptobenzimidazole,
. . .
~or example the zinc salt, and diphenylthiourea for poly- -
. 10 olefines.
. 6; Polyamide stabilisers such as copper salts in
combination wi~h iodides and/or ~urther phosphorus compounds
and salts of divalent manganese~
7. Basic co-stabilisers, such as polyvinylpyrrolidone,~ .
. - 15 melamine, benzoguanamine, triallyl cyanurate, dicyandiamide,
urea derivatives, hydrazine derivatives, amines, polyamides,
": .
. polyurethanes, and alkali metal salts and alkaline earth
metal salts of higher saturated or unsaturated fatty acids
such as, for example, Ca stearate.
.` 20 8. PVC stabilisers, such as organic tin compouncls,
organic lead compounds and Ba/Cd salts of fatty acids.
; ` 9. Nucleating agents, such as 4-tert.-butylbenzoic acid,
.~ adipic acid and diphenyl.aceti.c acid.
10. Other additives such as plasticisers, lubricants,
ior example glycerine monostearate, emulsiiers, antistatic
. .
~: "~ :
.
. .
. . .
`~ ~036601
agents, flameproofing agents, pigments, carbon bl~ck~ asbes~os,
glass ibres, kaolin and talc.
. lhe inverltion is explained in more detail in the
. examples which follow. Ilerein, per cent (%) denotes per
cent by weight and parts denote parts by weight.
., - .: ,
:
'
.. , , ':
,.' .
,~ , ' ''''''".
.. ~ , .
.~, ..
'; '
'''.;
. A~ . .
. ,
- ~ . . ... , . . ,. ., . . ,~ , .. . .,~ . . ..
.
~0366Ql :
Exam~le_l
ter~.Butyl
}10 ~
~e I' ~ . Butyl HI C=0
' C
' 0~ ' '."
27.6 g (~.1 mol) o (3,5-di tert.-butyl-4-hydroxy-
phenylethyl)-methyl-ketone, 4.9 g (0.1 mol) of sodium cyanide
S and 28.8 g (0.3 mol) of a~nonium carbonate are initially
introduced into 180 ml of 80% strength aqueous ethanol and
the mixture is heated to 45C for 6 hours whilst stirring.
Thereafter it is diluted with 60 ml of water and cooled to
room temperature over the course of 2 hours. The precipitate
: .
formed is filtered off, thoroughly washed first with water
and then with hexane and recrystallised from acetonitrile.
; 31.5 g oI 5-(3,5-di-tert.-butyl-4-hydroxy-phenylethyl)-5-
methyl-hydantoin (stabiliser No. 1) of melting point
, 207-2090C are thus obtained.
Example 2
If, in Example 1, (3~5-di-tert.-butyl-4-hydroxy-
phenylethyl)-methyl-ketone is replaced by an equivalent
amount o (3-tert.-butyl-4-hydroxy-5-methyl-phenyl-ethyl)-
methyl-ketone and otherwise the same procedure is followed,
5-(3-tert.-butyl-4-hydroxy-5-methyl-phenylethyl)~5-methyl-
b~...l
.; ` . .~
., .
~` 1036601
hydantoin of meltin~ point 210-211C is obtained (stabiliser
No. 2).
Example 3
If, in Example 1, (3,5-di-tert.-butyl-~-~-hydroxy-
; 5 phenylethyl)-methyl-ketone is replaced by an equivalent
- amount o 2-(3,5-di-tert.-butyl-4-hydroxy-phenyl)-isopropyl-
methyl-ketone,and otherwise the same proceclure is followed,
5-[2-(3,5-di-tert.-bu~yl-4-hydroxy-phenyl)-isopropyl]-5-
methyl-hydantoin of melting point 2400C is obtained
~ 10 (stabiliser No. 3).
Example 4
If, in Example 1, (3,5 di-tert.-butyl-4-hydroxy-
phenylethyl)-methyl-ketone is replaced by an equ-i~alent
amo~mt o, 3,5-di-tert.-butyl-4-hydroxy acetophenone, and
othe~wise the same procedure is followed, 5-(3,5-di-tert.
~ butyl-4-hydroxy-phenyl)-5-methyl-hydantoin o melting point
;;~ 2600C is o~ained (stabiliser No. 4).
- Example 5
IfJ in Example 1, (3,5-di-tert.-butyl-4-hydroxy-
phenylethyl)-methyl-ketone is replaced by an equivalent
~mount of 3-(3,5-di-tert.-butyl-4-hydroxy-phenyl)-propional-
dehyde, and other~ise the same procedure is followed, 5-(3,5-
di-tert.-butyl-4-hydroxy-phenylethyl)-hydantoin o~ melting
point 207-2080C is obtained (stabiliser No. 5).
Example 6
If~ in Example 1, (3,5-di-tert.-butyl-4--hydroxy-
: ~ ~L :
.,. ~ , ~ ,
. ~,~ :
: ' ' .~ -
. . . . . . . ,. . . . . . , . . .. , . . . . ~ , . . . ~ . - -. - . . . .~ .- . . .
~036601
~` .
phenylet-lyl)-metllyl-ke~one is rep~aced by an equival-~nt
amount o (3-ter~.-butyl-4-hydroxy-phenylethyl)-methyl-
ketolle, and othe~7ise the same procedure is followed,
5-(3-tert.-butyl-4-hydroxy-phenylethyl)-5-methyl-hydantoin
o~ melting point 2460C is obtained (stabiliser No. 6).
Example 7
tert.But-yl
H0 ~ C~l2CI~2 / C \ C17 35
HN C-0
; tert.Bu~yl I I
,~ C
0~ ' ` .
19.3 g (0.039 mol) of (3,5-di-tert.-butyl-4-hydroxy-
phenylethyl)-heptadecyl-ketone, 1.9 g (0.039 mol) o sodium
...... .
cyanide and 11.1 g (0.116 mol) of ammonium carbonate are
initially introduced into 150 ml o 90% strength ethanol and
the mixture is kept for 36 hours at 40-45C, whilst stirring.
Thereafter, 150 ml of water are added to the pasty reaction
mixture, which is stirred for a further hour at room temper-
` 15 ature. After filtration, washing with water and then with
hexane, and subse~uent recrystallisation from hexane, 5-(3,5-
di-tert,-butyl-4-hydroxy-phenylethyl)-5-heptadecyl-hydantoin
~stabiliser No. 7) melts at 890C.
.
Z Y
' Cl
~ . 1
'' ' .
. .
. . . ~ .
,
- . . ~ .
. . ~. ,
,. ~ . - . . ~
: ` :
10i 16601
.:
E~ample 8
If, in Example 7, (3,5-di~tert.-butyl-4-hydroxy-
phenylethyl)-hep~adecyl-ketone is replaced by an equivalent
amount of di-(3,5-di-tert.-butyl-4-hydroxy-phenylethyl)-
ketone of German Offenlegungsschrift 2,009,504 and other~ise
the same procedure is ~ollol~ed, 5,5-bis-(3,5-di-tert.-butyl-
4-lydroxy-phenyletllyl)-hydantoin (stabiliser No. 8) is
obtained. Melting point 218-220C.
Example 9
ter~.~utyl
10H ~ } CH2C~I2 / C \ CH3 :~
tert.~utyl I C=O O-
0~ ~ 22C C2H5
. ,~ ' .
. 30 g (0.087 mol) o~ 5-(3,5-di-tert.~butyl-4-hydroxy-
phenylethyl)-5-methyl-hydantoin and 13.1 g (0.131 mol) of
`: acrylic acid ethyl ester are dissolved in 100 ml of ethanol,
- 2 ml of a 40% strength solution of benzyl-trimethyl-am~lonium
I-ydroxide in methanol are added and the mi~ture is heated
under reflux for 12 hours, whilst stirring. Thereafter it is
~: neutralised with glacial acetic acid, diluted with 50 ml of
water and cooled wIilst stirring. The precipitate formed
is filtered off, washed with 50% strength ethanol and re-
,: ,,, -:
., ~ .
: 1036601
- crystallised from 70% stren~th alcohol. 29 g of 5-(3,5-di-
tert.-bu~yl-4-hydroxy-phenyletllyl)-5-methyl-3-e~hoxycar~onyl-
ethyl-hydalltoin o melting point 100C are thus obtained.
(Stablliser No. 9).
If in Example 9 the acrylic acid ethyl ester is
replaced by an equivalent amount ~crylic acid octadecyl ester,
; and otherwise the same procedure is followed, 5-~3,5-di-tert;-
butyl-4-hydroxy-phenylethyl)-5-methyl-3-octadecycloxycarbonyl-
ethyl-hydantoin of melting point 63C is thus obtained.
E,xample 10
I, in Example 9, the acrylic acid ethyl ester is
replaced by an equivalent amount o acrylonitrile and other-
wise the ~me procedure is followed, S-(3,5-di-tert.-butyl-4-
hydroxy-phenylethyl)-5-methyl-3-cyanoethyl-hydantoin is
.~ .
obtained in the form of a light-colored resin (stabiliser
No. 10).
Example 11
:.
....
.:. C~2
; ICII2
7
~N
}~2C C~l
I 1 2
R-CH CH -C ~ ~ C C~I CH R
.' ,
~: 30
. .
. . ~ ` i
, ~ `............................................................ .
.
... . . ...
1036601
-N - C=0
I I tert.Bu~yl
H~ C-CII2C~ ~ O~I
tert.Butyl
21 g (0.06 mol) o~ 5-(3,5-di-tert.-butyl-4 hydroxy-
phenylethyl)-5-methyl-hydantoin and 5 g (0.02 mol) of 1,3,5-
tris-acryloyl-hexahydro-s-triazine are dissolved in 100 ml
of dimethyl~orm~mide, a few drops of a concentrated Na
ethylate solution are added and the mixture is heated
to 100C over the course of 90 minutes, ~hilst stirring.
Thc mixture is stirred for a further 5 hours at this temper-
ature, the bro~nish solution is subsequently decolorised with
a little glacial acetïc acid, cooled and mixed first wi~h
toluene and then with 200 ml o water, and the organic phase
which separates out is separated off. After thorough washing
with water, the toluene phase is completely concentrated
under reduced pressure. 1,3,5-tris-[5-(3,5-Di-ter~.-butyl-4-
hydroxy-phenylethyl)-5-methyl hydantoin-3-yl]-propionyl-
; hexahydro-s-triazine, a light-colored brittle resin of
softening point > 100C is thus obtained. (Stabiliser No. 11)
.
'
.' . . ,' ' ~
,C~ - ~ - '
.'" . ,
.-~ . .
1~)366Ql
Example 12
tert Butyl
HO ~ 0 \) C~2CH~C;~H3
- ~- ~ HN C=O tert,Butyl
tert.Butyl
2 ~
C~I-
- 3
17.3 g (0.05 mol) of 5-~3,5-di-tert.-butyl-4-
,. :
hydroxy-phenylethyl)-5-methyl-hydantoin and 11 g (0.05 mol)
of 3-tert.-butyl-4-hydroxy-5-1~ethyl-benzyl)~ime~llylamine are
dissolved in 100 ml of dimethyl~ormamide~ a pinch of lithium
amide is added and the mixture is heated to 90C for 16
hours wllilst stirring and passing nitrogen ~hrough it, The
.. . .
bro~n solution is brightened with a little glacial acetic
acid and the solven~ is dis~illed off under reduced pressure.
. .
' On recrystallisation from acetonitrile, 20 g of 3-(3-tert.-
butyl-4-hydroxy-5-methyl-benzyl)-5-(3,5-di-tert.-butyl-4-
hydroxy-phenylethyl)-5-methyl-hydantoin o~ melt~g point 218C
(stabiliser No. 12) are obtained.
.. :. ,,
Example 13
If, in Example 12, 5-(3,5-di-tert.-butyl-4-hydroxy-
phenylethyl)-5-methyl-hydantoin is replaced by an equivalent
; amount o~ 5-(3-tert.-butyl-4-hydroxy-5-methyl-phenylethyl)-
5 methyl-hydantoin and otherwise the same procedure ;s ollo~.7ed,
3-(3-tert.-butyl-~-hydroxy-5-methyl-benzyl)-5-(3-tert.-butyl-
. .
_ ,~ _
' ~C 1
;, . .
:
. ~ ''. .
~.
1036601
4-hydroxy-S-r.lc~hyl-yhcnyletllyl)-5-methyl-hydantoin of melting
oint 110-120C (stabilisel No. 13) is ob~ained.
If, in Example 12, 5-(3,5-di-tert.-butyl-4~hydroxy-
phenylethyl)-5-methyl-hydantoin is replaced by an equivalent
- amount o 5,5-bis-(3,5-di-tert.-butyl 4-hydroxy-phenylethyl)-
hydantoin and othen~7ise the same procedure is ~ollowed, 5,5-
bis-(3,5-di-tert.-butyl-4-hydroxy-phenylethyl)-3-(3-tert.-
butyl-4-hydroxy-S-methylb-enzyl)-hyd~toin of m.elting point
125-130C is obtained (stabiliser No. 14).
,,; ,
Example 15
. , .
If, in Example 12, 5-(3,5-di-tert.-butyl-4-hydroxy-
phenylethyl)-5-methyl-hydantoin is replaced by an equivalent
am~unt o 5-[2-(3,5-di-tert.-butyl-4-llydroxyphenyl)-isopropyl~-
5-methyl-hydantoin and otlleL~ise the ~Ille proccdure is followed,
3-(3-tert.-butyl-4-hydroxy-5-methylbenzyl)-5-[2-(3,5-di-
~'. tert.-butyl-4-hydroxyphenyl)-isopropyl]-5-methyl-hydaIItoin '::
of melting point 193C is obtained (stabiliser No. 15).
EYample 16
tert.Butyl
,,~ > \
~ C~2CI~ C \ 17~35
~iN C=O tert.Butyl
tert.Butyl I I r~
; O=C N-CI-I2- ~ -OH
; ert.Butyi
~3
.: _ ~ _
... .
. .. . ; . . ,. ~.~ . .
~ .
1036601
5.7 g (0.01 mol) of 5-(3,5-di--tert.-butyl-4-hydroxy-
phenylethyl)-S-heptade~yl-hydan-toin and 2 6 g (0.01 mol) of
~3,5-di-tert.-butyl-4-hydroxyben~yl)-dimethylamine are
dissolved in 50 ml of dimethylformamide and the mixture is
stirred or 16 hours at 100C ~hilst passing nitrogen through
it. ~le brown solution i5 brightened with a little glaci~l
acetic acid and ~he solvent is distilled off under reduced
- pressure. On recrystallisation from acetonitrile, 3-(3~5-
di-tert.-butyl-4-hydroxybenzyl)~5-(3,5-di-ter~.-butyl-4-
hydroxy-phenylethyl)-5-heptadecyl-hydantoin melts at 48-500C
(stabi]iser No. 16).
Example 17
If, in Example 16, 5-(3,5-di-tert -butyl-4-hydroxy-
phenylethyl)-5-heptadecyl-hydantoin is replaced by an
; 15 equivalent amount of 5-(3,5-di-tert.-butyl-4-hydroxy-phenyl-
ethyl)-5-methyl-hydantoin and otlle~lise thesame procedure
is followed, 3-(3,5-di tert.-butyl-4-hydroxy-benzyl)-5-(3,5-
di-tert.-butyl-4-hydroxy-phenylethyl)-5-methyl-hydantoin of
melting point 217~C (stabiliser No. 17) is obtained.
:
Exainple 18
tert.~utyl
~ .
}~0 ~ C~2C~ C \}~3
~N C=O
~ert.Bu~yl I I
; O=C N C18~37
,~ 12.1 g (0.035 mol) of 5-(3,5-di-tert.-butyl-4-
hydroxy-phenylethyl)-5-methyl-hydantoin, 11.65 g (0.035 mol)
:., .
~ .
' , 103660~ ~
of l-bromooctadecane and 1.9 g (0.035 mol) of sodium methyl-
ate (dissolved in 10 ml of me~hanol) are initially introduced
into 100 ml of dimethyl~onnamide and the mixture is ~irred
or 14 hours at 80C. Thereafter it is cooled, first mixed
with 100 ml of toluene and ~hen with 100 ml of water, and
~; the organic phase is separated off. After thorough washing
with water, the toluene phase is completely concentrated
- under reduced pressure and taken up in acetoni~rile. Af~er
prolonged ~tanding, 15 g o~ 5-(3,5-di-tert.~butyl-4-hydroxy-
: l0 phenylethyl)-5-methyl-3-octadecyl-hydantoin of mel~ing point
620C (stabiliser No. 18) crys~allise.
`,~ - ' . Example 19
If, -ln Example ]8, the l-bromooctadecane is replaced
by an equivalent amount o l-~bromohexadecane and otherwise ~-
the same procedure is follo~.Ted, 5~(3,5-di-tert.-butyl-4-
hydroxy-phenylethyl)-5-methyl~3~hexadecyl-hydantoin of : -
; melting point 640C (stabiliser No. 19) is obtained.
~ample 20
'.';' ' -, .......... . . ~ ;''
/ tert.Bu~yl
~ \
~ C~C~I~C~I3
¦ tert.Butyl ¦ ¦ ~
\ 0=C - N l CH2
` ~ / 2
..
~` 35
,
~,; r
-
., ~ .
1036601
.:
3~.6 g (0.1 mol) of 5-(3,5-di-tert.-butyl-4-hydroxy-
pIIenylethy])-5-~etIlyl-hydantoin, 8.7 g (0.05 mol) of methy]-
ene bromide and 38 g (0.1 mol) of ~otassium hycIroxide are
initially introduced into 100 ml of dime~hylformamide and
the mixture is kept at 80C for 1~ hours, ~hilst stirring,
Ater cooling, insoluble matter is filtered o~, irst 100 ml
of toluene and then 100 ml of water are added and the tol~ene
~hase is separated off and repeatedly washed wi~h water.
Therea~ter, 50 ml of toluene are d;stilled of~ under reduced
pressure an~ the residual brown solution is left to ~nd for
24 hours at room temperature. The resulting precipitate is
filtered off and recrystallised from ~cetonitrile. 3-Methyl-
ene-bis-5-(3,5-di-tert.-butyl-4-hydro~y-phenyletllyl)-5-
methyl-hydantoin of melting point 2220C (stabiliser No. 20)
are tllus ~ tained.
Example 21
. . .
~ t~rt.Butyl
.'~ . ~
~10 ~ O ~-Cl~2c~fc\~3
~ ~IN C=0 OH t/ rt.Butyl
tert.Bu~yl I ¦ `
0=C - N-C~I2-CH CII2- ~ -~
~ert.Butyl
::'. .
'
-~ 17.3 g (0.05 mol) of 5-(3~5-di-tert.-butyl-4-
hydroxy-~lenylethyl)-5-methyl-hydantoin, 13 g (0.05 mol) of
~3~5-di-tert.-butyl-4-hyclroxybenzyl)~oxirane and 1 g of
;
G
: ` :
1036601
.: .~ripropylamine in 100 ml o~ dimethylformalllide are hea~e~l for
5 ~lours under ~e]ux, whils~c s~;rrillg. A~ter cooling, 5 ml
of glac~al acetic acid, ]00 ml of toluene allcl 100 ml of
water are a~ded. The toluenc ~nase is ~ashecl with water,
co~pletely concen-L-rated under reduced pressure and dissol~ed
in acetonitrile to give a concentrated solution. After
prolonged s~anding, a precipita~e forms and is fil~ered off. ~-
3-~3-(3,5-di-tert.-but~rl-4-hydroxyplenyl)-2-hy~roxy]-propyl-
5-(3,5-di-tert.-butyl-4-hydrov~y-phenyletllyl)-5-methy]~
- ]0 hydantoil~ of -,nel~ing poin. 193C ~stabiliser ~o. 21) is
` thus obtaiLled,
." :
Exa-nple 22
/ tert,butyl
:: > \
}30 ~ CH~C~I2 ~ C - H
N C-0
tert.b~lt~
C~ N-CH2C'~12C'H? ~
. 2
S g (0,015 mo]) of 5~(3,5-di-tert.-butyl-4-hydroxy-
phenylethyl)-l-ydantoin, 1.83 g (0,0075 mol) of 1,6-dibromohexane,
~` 0,9 g of sodium methylate and 0.1 g of potassium jodide are
,. . .
initially int~odllced into 50 ml of dimethylformamide and
the mixture is s~irred for 20 hours at 80C. After cooling,
' ' .''"-F, ~X
-- .
~03660~
~heLe ar~ a~ded 100 ml of toluene, the mi~ture is washed
- twice with 200 ml o water, and the organic phase is separated
off. A~ter drylllg, the toluene solu~ion is completely concen-
trated under reduced pressure and ~he residue is further
purified by column chromatography. Elution with a
tnixture of toluene and methanol there is obtained
3-hexamethylene-~is-5-(3,5-di-tert.-butyl-4-hydroxy-phenyl-
- ethyl)-hydantoin of melting point 199C (stabilizen No. 22).
.
E~ 23
.
` 100 parts of polypropylene (meltindex 3.2 g/10
minutes, 230C/2,160 g) are thoroughly mixed for 10 minutes,
` in a sl~aking apparatus, with 0.2 part of an additive listed
in Table 1 below.
The resulting mixture is kneaded for 10 minutes in
a Brabender plastograph at 200OC and the mass thus obtained
is subsequently pressed in a shOEt press at 260C platen
temperature to give 1 mm thick sheets, from which strips
. . .
1 cm wide and 17 cm long are punched.
The activity of the additives introduc~d into the
test sti~s is tested by heat aging in a circulating air oven
.
~t 149C, using~ for comparison7 an addi~ive-free test strip.
. .
3 test strips of each ormulation are cmployed. The inci-
; pient, easily visible decomposi~ion of the test strip is
~ deined as the end point. The results are quoted in days.
3~
. .raJ . ~
Table 1
l0366nl
. __ .. ...
Stabiliser I Days to incipient decol.nposltion
: ~o. 1~9C
. . . .. . _
No add tive 1/2 ~:~
8 23 :~
12 7
13 15
14 . 34 ::
.~ 16 17
17 6
. 18 10
;. 19 18
. 20 26
. 21 19 . .
- Example 24
.. . .
The test specimens describcd in Example23 were
adaitionally tested for their color stability, namely:
- a) after incorporation (Table 2, column 2).
,. 5 b) a~tcr 500 hours' e~posure in a Xenotest instrument of
Messrs. I~anau (Table 2, column 3)
c) ~ter l week's treatment with boiling ~7at:er (Table 2,
- column 4).
.
3q
.'' :"':
'' ' .
Q366al
An empirical color scale ~as used for Table 2, in
wllich S clenotes colorless,4 cienotes a just perceptible slight
discoloration and 3, 2, 1 and <]. denote progressively
stronger discoloration.
~. ~
'`:' .
,: .,
. .
;.' '
.
, .
.
.. ,. :
~.;. .
, . .
. ,.: . .
.
:;
,........................... . .
;. :'
4~ :
.,. ~.
..:
. ~. .
- i, .
~ . .
; . . . - . .. . . . . .. ~ . ....
.. . . . .. . . .... .. , . . ~.- -.. ,.. ~ . . . .- , ., . ~
Table 2 1036601
.: I ............................................. .... _
¦ Stabiliser Colour assessment accordin~ to scale 1 ~o 5
No, After Af~er exposure Boiling water, :
in(orpora~ion to ligh~ 1 week
_ _ .
No additive 4-5 5 5
' 8 4-5 5 4-5
12 4-5 5 4-5
. 13 4-5 4-5 4-5
: 14 5 5 4-5
` 15 4-5 5 4-5
.17 4-5 5 4-5
., 18 4-5 5 5
. 19 4-5 5 4-5
;. 20 5 5 5
. ~1 4-5 4-5 .
. .
Example 25
100 parts o~ polypropylene (melt index 3.2 g/10
`:-
minutes, 230C/2,160 g) are thorou~hly mixed ~or 10 minutes
in a shaking apparatus with 0.1 part of an additive listed
in Table 3 below and 0.3 part of d-llauryl thiodipro~ionate.
The resulti.ng mixture is lcneaded for 10 minutes in
;- a ~rabender plastograph a~ 200C and the mass thus obtained
is subsequently pressed in a sheet press at 2600C platen
- temperature to give 1 mm thick sheets rom which strips 1 cm
, wide and 17 cm long are punched.
:.............. a~. ~ 4~~
"~ - .
~ 10366~
T~l~ ac~ivity o~ the additives in~odueed in~o the
pressed strips is testc(l by heat aglllg in a circulating ~ir
ovèn at 14'9C,~ing for con~parisoTI a test strip ~hich only
contains 0.3 part o~ dilauryl thiodil~ropionate. Three
test strips of each formulation are employe~. The incipient,
easily visible decomposition o the test strip is defined
as the end point and the resul~s a~^e quote-l in days.
Table 3
~Stabiliser Days up to incipient decomposition
No - _ _ 149C _ _
No additive 5
7 24
8 33
12 19
~`~ 13 17
14 56
16 40
17 14
18 21
19 28
~0 33
21 32
.
'' ':
:. .f Z, ::
... ..
.
~'.,: . '
... ... . , . .~ , .. :.. . ,... . . . : . :
E~ O 1 ..
. .
The test speci.mens described in Example 25 ~ere
~dditionally tested fol their color stabili~y, namely: -
a) a~er i.ncorpora~ion (Table 4, column 2),
b) a~ter 500 hours' exposure in a Xenotes~ ins~rument of
Messrs. Hanau (Table 4, column 3)
c) after 1 week's treaL~nent with boiling water (Table 4,
column 4).
An empirical color scale ~as used for Table 4, in
which 5 denotes colorless, 4 denotes a just perceptible
slight discoloration and 3, 2, 1 and ~1 denote p~ogressively
stronger discoloration.
Table 4
. .
.. ~ .
. . S-tabiliser Colour assessment according -to scale l to 5
:~. No. _. --
.~ .. After ¦After exposure ¦Boiling ~rater,
_ _ _corporation t light I . l week
. No. 5 5 - 5
~ 7 ~ 4 5 ~ 5 ¦
.:~ 14 .5 . 5 5
.. ~ 16 4-5 5 5
7 4-5 5 4-5
~ 2U 4-5 5 4~5 ..
.. 21 4-5 _ 5 4-5
. , . _ .
. ~3
.. .
... . , , - .
`
lQ366C~1
Example 27
Sllavings (chips) o~ 25~ ~hi.ckness are cut by means
- o~ a micro~om~ from the 1 mm thick ~Lest sheets described in
Example 23. These chips are sandwiched bet~een stainless steel
grids and the sample carriers thus obtained are suspended in
a circ~llating ai.r oven and the sa~ples are aged at 135C and
147C, respectively. `
Table S
____ . .
Stabiliser hours to incipient dec^mposition
. No. 147 C 135C
`, .
No 10 20
; 7 40 1~0
i 8 60 1~0 :~
34 120 70
. ~ 16 70 220
~`' 18 `35 70 `
19 40 100
250 `
21 55 140 1 :
..,
`
.
:.
:.
' . ' .
. ,.,-~ j . .
`',' ~ ' '
.:
~03660~
,' The time af~er ~h;.ch, on gentle tc~pping on ~lle grid, degra-
- ded polypropylene falls ou~ in the foml of a po~d~,r is
de.ined as the end point (a clleck is made 1 - 2~ daily)~ The
results are quoted in hours. (Table 5).
'`-'
xample 28
Shavings (chips) of 25f~ thickness are cwt by means
'.' . of a m;crotome from the 1 mm thick test sheets described in
:. Example 25. These chips are cLamped bet~een stainless steel
. grids and the sample carriers thus obtained are suspended in
;' 10 a circulating air oven and the samples are aged at 135C or147C. The time after which, on gentle tapping on the gri.d,
degraded polypropylene falls out in the form of a p~7der is
-defined ~s the end point (a check is made 1 - 2x daily). The
,. results are quoted in hours. (Table 6).
. . .
`'' :
:~,, .
i,~'
.~" .
.~"......................................................................... :
~. .
:
.``'''' '
' .
' ~ '
. ~ .
. ~ .
:
,''" .
, ... - . ~ . : . : ; . . :,
l'ab]e 6
1~366~1
=. .~
. Stabiliser IIo~lrs -to illcipien~i; c~ecor~posi-tion
.- ~o. . ~
ll~7C 1~5C
:. . _~ ~ ~
No additive lO 20
7 70 220
8 90 215
13 70 190
14 160 380
~ 16 210 575
't 18 45 120
19 70 210
100 310
21 140 380
:. ;'
Example 29
. .. ~ .
0,05 mol of 5-[2-(3,5-di-tert.-butyl-4-hydroxyphenyl)-
isopropyll-5-methyl-hydantion and 0,05 mol of (3,5-di-tert-
~ .
butyl-4-hydroxybenzyl)-dimethylamine are dissolved in
100 ml of dimethylformamide, a pinch of lithium amide is
added and the mixture is heated to 90C for 16 hours whilst
stirring and passing nitrogen through it. The solution is
neutralized with a little ~acia] acetic acid and the solvent
is distilled off under reduced pressure. On rec~ystallisation
from acetonitrile, 3-(3,5-di-tert-butyl-4-hydroxybenzyl)-5-
; [2-(3,5-di-tert.-butyl-4-hydroxyphenyl)-isopropyl~-5-methyl-
` hydantoin is obtained.
,:, S~
~ _ ~ _
'
r~r~ l
- ~03660~
Example 30
.
If in example 18, i:he l-bromooctadecane is replaced
by an equivalent amount of l-bromooctane, and otherwise the
- same procedure is followed, 5-(3,5-di-tert.-butyl-4-hydroxy-
phenylethyl)-5-methyl-3-octyl-hydantoin oE melting point
94C is obtained.
. .
Example 31
If in example 18, the 5-(3,5-di-tert.-butyl-4-hy-
droxy-phenylethyl)-5-methyl-hydantoin is replaced by an
equivalent amount of 5-(3-tert.-butyl-4-hydroxy-5-methyl-
phenylethyl)-5-methyl-hydantoin, and otherwise the same
procedure is followed, 5-(3-tert.-butyl-4-hydroxy-5-methyl-
phenylethyl)-5-methyl-3-octadecyl-hydantoin is obtained which
is a viscous oil.
Example 32
. . .
If in example 18, the 5-(3,5-di-tert-butyl-4-
hydroxy-phenylethyl)-5-methyl-hydantoin is replaced by an
equivalent amount of 5-(3,5-di-tert.-butyl-4-hydroxyphenyl)-
5-methyl-hydantQin, and otherwise the same procedure is Eollowed,
5-(3,5-di-tert.-butyl-4-hydroxyphenyl)-5-methyl-3-octadecyl-
hydantoin of melting point 80C is obtained.
..
.. ' ' _ ~ :
~ ' ~
... .
: ,, - - .
.'*'h'.'~
, . ..
~366Ql
. Example 33
. . _
0,05 mol of 5J5-bis-(3,5-di-tert.-bulyl-4-hydroxy-phenyl-
. ethyl)-hydantoin, 0,05 mol of l-bromooctane and 0,05 mol
of sodium methylate (dissolved i.n 20 ml of methanol) are
- 5 initially introduced into 200 ml of dimethylformamide and
the mixture is stirred for 14 hours at 80C. Thereafter it is .
. cooled, mixed with each 200 ml of toluene and water and
. the organic phase is separated off. After washing with water
the toluene phase is e~aporated and the residue cri.stallized :
from acetonitrile. 5,5-bis-(3,5-di-tert.-butyl-4-hydroxy-
phenylethyl)-3-octyl-hydantoin of melting point 147C
` is thus obtained.
~:
''' , ~
.
.'''
::.
'. :
.: .
., :
. -::
., ~ ~ ~ ~ ' ,' .. :.
..."
'` ~C~
: 1()366(~1
Example 34
. ' .
ter~: Bu~yl l ~13
~} Cll 2CH 2 - C -- CO
NH NCH2CH2Cal2
I:ert Butyl CO ~
6.95 g. (0.02 nlol) of 5-(3,5-di-tert.-butyl-4-hydroxyphenylethyl)-
5-methyl-hydantoin, 1.38 g. (O,Ol mQl) of potassium carbonate,
and l.55 g. (0.01 mol) of 1,6-dichlorohexane in 30 ml of
dimethylformamide are stirred 20 hours at 100C under nitrogen.
;.; .
~ The reaction mixture is cooled to 25C, and added slowly to
,
120 ml of stirred water, and the white suspension obtained
; is stirred for an additional 1-3 hours. The precipitated
solid is collected on a filter and dried. The dried solid,
`~; 7.8 g., is taken up in 40 ml of ethanol and the solution treated
-~ with charcoal and filtered. The filtrate is added slowly to
400 ml of wat:er and the thick, white suspension stirred for
an additional 1-2 hours. The precipitated white solid is
. ~
- 15 filtered and dried to constant weight in vacuo. In this way
6.7 g. of 3-hexamethylene-bi.s-5-(3,5-di-tert-butyl-4-hydroxy-
~ phenylethyl)-5-methylhydantoin of melting point 100-112C
`.; are ob~ained.
Example 35
If, in Example 34, 1,6-dichlorohexane is replaced by an equi-
valent amount of bis(2-chloroethyl) ether and otherwise the
... .
.,'., ~q
, -- ~ _
.~ .
.,,~ `~
."" '
~` 1()366~1
same procedure is followed 3-oxydiethylene-bis-5-(3,5-di-tert-
butyl-4-hydroxyphenylethyl)-5-meth~lhydantoill of melting
- point 105-116C is obtained.
Example 36
.,
: tert~B~tyl ter~,Butyl
~CU,CII~ C~Iz~
tert Butyl N tert Butyl
,:
t
; OH
5.65 g (0.01 mol) of ~-(3,5-di-tert-butyl-4-hydroxybenzyl)-
~(3,5-di-tert-butyl-4-hydroxyphenylethyl)-5-methylhydantoin
and 4.35g (0,017 mol) of (3,5-di-tert-butyl-4~hydroxybenzyl)
dimethylamine are dissolved in 20 ml of dimethylformamide and
the mixture is stirred under nitrogen for 44 hours at 120C.
~ The reaction mixtures is cooled and poured slowly into 120ml
; of stirred water. The resulting mixture is extracted with
lOOml of benzene, the phases sep~rated and the aqueous phase
extracted twice more with 75ml portions of benzene. The benzene
extracts are combined and dried, and the solvent is removed
under reduced pressure. The residue is taken up in lOOml of
.:' . .
hot heptane and on cooling the insoluble crystals are separated
by filtration. The filtrate is evaporated to dryness in vacuo,
,.,, '~.. ;-.
;, S~
. _ .
; ~,
... .
.: - -- .. , - .. . . . . . . ..
"` 10366(~1 `
.
and t:Lle residue dissolved in ]OOml of fresh ben~enc. The
ben~ene solution is washed successively with two 40ml
portions of 3n hydrochloric acid and one 40ml portion oE
water, dried, and the benzene solvent is -removed in vacuo.
The residue is taken up in boiling hexane, and on cooling
a small amount of insoluble crystalline solid is separated
~ by filtration. The filtrate is evaporated to dryness in
` vacuo and the residue recrystallized at low temperature from
petroleum ether. In this manner l lg of 1,3-di(3,5 di-tert.-
butyl-4-hydroxy-benzyl)-5-(3,5-di-tert-butyl-4-hydroxyphenyl-
ethyl)-S-methylhydantoin of melting point 112-114C are ob-
-~ tained. -
Example 37
.' ''
~ert.butyl
HO-~-C112C1~2 - CjCH3 .
O=C ~ N- ~ -
tert.butyl ~ I=o ~- /
" , .
6.92g (0.02 mol) of 5-(3,5-di-tert.-butyl-4-hydroxyphenylethyl)-
5-methyl-hydantoin and 0.5 g of tributylamine are dissolved
with stirring in 50 ml of a mixture of 7.5 parts of absolute
; toluene and 2.5 parts of absolute dioxan at 95C. To this
solution are added dropwise over the course of 15 minutes
3.57g (0.03 mol) of a solution of 3.57g (0.03 ~ol) of phenyli-
socyanate in 10 ml of absolute toluene. Stirring is continued
; :
`
.~,............ ~1 '
:
;'' :
. . .
,
., . ~ .
:. . .
10366~1
for a Eurtller 4 hours at 95C ancl then under re~lux. The mix-
ture is subsequently cooled to room temperature, treated with
' 50 ml of ~ater, stirred for 30 m;,nutes, and the organic phase ~'
,; is then ,isolated. The so]vent is removed in a rotary evapora-
tor and the residue is then dissolved hot in cyclohexane and
the solution is filtered. The filtrate is cooled, whereupon
'- the 5-(3,5-di-tert.-butyl-4-hydroxy-phenylethyl)-5-methyl-1-(N-
phenylcarbamido)-hydantoi~ is prècipitated (m.p. 148C).
.
,
... . .
`:'i~ " '' "'
.: .
!
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,}. _ ,~ _
.,, ~ .
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