CA1036601A - Hydroxyphenylated hydantoins - Google Patents

Abstract

ABSTRACT
New 3-substituted for 3-unsubstituted hydroxyphenyl-ated hydantoins are useful as stabilizers for organic materials.
The 3-substituted hydroxyphenylated hydantoins are prepared by reacting 3-unsubstituted hydroxyphenylated hydan-toins with corresponding halogen derivatives. The 3-unsubs-tituted hydroxyphenylated hydantoins in their turn are pre-pared by reacting hydroxyphenylated carboxylic acid esters with alkalicyanid and ammonium carbonate.

Description

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
,.,: )~

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

~ ~ '~ '' ' `

~ ~()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 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

-' .

"~

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 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~

' 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-~)-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

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 ~ ' " ' 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) 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 may be prepared by the reaction of an hydantoin of the -formula I wherein R6 is hydrogen with a compound to the formula :... ~,4 . .
.
.; ~' . ,;, ., ~

: . ':
.

.. ., . . . .. . - :: . , . - , - - ~ . - ~

.

CH3 ~ 1 CH / 2 ~ OH or Y-alkyl 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 ` 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
.

" ;: .

.
: ~ .
~, . . . ..
,: ' :.'' ': . ' , ',. ' ~ ~
... , : .
`; ~' ' ~ ' ', ' ~ :

-' ~ .

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.. . . . - . . . . - . . . . . ... . . . .. ..

.. . . . .. . . . . . . . .

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~
` !
.: :.
.,~..'' 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 ; 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 ~N
}~2C C~l R-CH CH -C ~ ~ C C~I CH R

.' , ~: 30 . .
. . ~ ` i , ~ `............................................................ .

.

... . . ...

-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-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 ;, . .
:
. ~ ''. .

~.

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 .: _ ~ _ ... .

. .. . ; . . ,. ~.~ . .

~ .

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 -., ~ .

.:
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

: ` :

.: .~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

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 :~

14 . 34 ::
.~ 16 17 . 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~ :
.,. ~.
..:
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- 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 . 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 ~`~ 13 17 ~0 33 .

'' ':
:. .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 ~ 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 :~

. ~ 16 70 220 ~`' 18 `35 70 `

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 ~ 16 210 575 't 18 45 120 :. ;' 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~ " '' "' .: .
!
''" ' :' ' ' S.2~
,}. _ ,~ _ .,, ~ .

' :'

Claims (26)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Compounds of the general formula I
(I) wherein R1 denotes alkyl with 1 to 8 carbon atoms; R2 denotes hydrogen or alkyl with 1 to 8 carbon atoms; R3 denotes hydrogen 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 m denotes 1 to 3, R5 - if m is 1 - denotes hydrogen, alkyl with 1 to 18 car-bon 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 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 and R6 - if m is 1 - is hydrogen, alkyl from 1 to 18 carbon atoms or one of a group of the formula or - if m is 2 or 3 - is hydrogen.

2. Compounds according to claim 1 of the general formula I, wherein R1 denotes alkyl with 1 to 8 carbon atoms; R2 denotes hydrogen or alkyl with 1 to 8 carbon atoms; R3 denotes hydrogen or methyl; X denotes a direct bond, alkylene with 1 to 18 carbon atoms; R4 denotes hydrogen, alkyl with 1 to 17 car-bon atoms, or a group 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 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 and R6 denotes hydrogen.

3. Compounds according to claim 1 of the formula I wherein R1 denotes alkyl with 1 to 4 carbon atoms, R2 denotes hydrogen, methyl or butyl; R3 de-notes hydrogen; X denotes a direct bond, or alkylene with 2 or 3 carbon atoms, R4 denotes hydrogen, alkyl with 1 to 17 carbon atoms, or a group m denotes 1 to 3, R5 - if m is 1 - denotes hydrogen, alkyl with 8 to 18 carbon atoms, hydroxybenzyl substituted by 2 alkyl groups each with 1 to 4 carbon atoms, or one of the groups -CH2CH2CN or -(CH2)2-COOR, wherein R is alkyl with 2 to 18 carbon atoms or a group or - if m is 2 - denotes alkylene with 1 to 6 carbon atoms or -CH2CH2OCH2CH2O-, or - if m is 3 - the group and R6 - if m is 1 - is hydrogen or one of a group of the formula or C6H5NHCO

or - if m is 2 or 3 - is hydrogen.

4. Compounds according to claim 2, of the formula I wherein R1 denotes alkyl with 1 to 4 carbon atoms; R2 denotes hydrogen or alkyl with 1 to 4 car-bon atoms; R3 denotes hydrogen; X denotes a direct bond or one of the radicals -CH2CH2- or ; R4 denotes alkyl with 1 to 17 carbon atoms, or a group m denotes 1 or 2, R5 - if m is 1 - denotes hydrogen, alkyl with 1 to 18 carbon atoms, hydroxybenzyl substituted by 1 to 3 alkyl groups each having 1 to 4 carbon atoms, or a group -(CH2) -COOR, wherein R is alkyl with 1 to 18 carbon atoms and q is 1 or 2, or - if m is 2 - denotes alkylene with 1 to 18 carbon atoms or the group -CH2CH2-O-CH2CH2- and R6 denotes hydrogen.

5. Compounds according to claim 21 of the formula Ia (Ia) wherein R1 and R2 independently of one another denote alkyl with 1 to 4 carbon atoms, R3 denotes hydrogen, X denotes a direct bond, -CH2-CH2- or and R4 denotes alkyl with 1 to 17 carbon atoms or a group

6. Compounds according to claim 2, of the formula Ib (Ib) wherein R1, R2, R1' and R2' independently of one another denote alkyl with 1 to 4 carbon atoms; R3 and R3' independently of one another denote hydrogen or methyl, X denotes a direct bond, -CH2-CH2- or and R4 denotes alkyl with 1 to 17 carbon atoms or a group

7. Compounds according to claim 2, of the formula Ic wherein R1 and R2 independently of one another denote alkyl with 1 to 4 carbon atoms, R3 denotes hydrogen, X denotes a direct bond, -CH2-CH2- or R4 denotes alkyl with 1 to 17 carbon atoms or a group ~'~

and R5 denotes alkyl with 1 to 18 carbon atoms.

8. Compounds according to claim 2, of the formula Id wherein R1 and R2 independently of one another denote alkyl with 1 to 4 carbon atoms; R3 denotes hydrogen; X denotes a direct bond, -CH2-CH2- or -CH2-CH-;
R4 denotes alkyl with 1 to 17 carbon atoms or a group and R denotes alkyl with 1 to 18 carbon atoms.

9. Compounds according to claim 2, of the formula Ie (Ie) wherein R1 and R2 independently of one another denote alkyl, with 1 to 4 carbon atoms; R3 denotes hydrogen; X denotes a direct bond, -CH2-CH2- or ;
R4 denotes alkyl with 1 to 17 carbon atoms or the group and p denotes 1 to 18.

10. A compound according to claim 2 which is

11. A compound according to claim 2 which is

12. A compound according to claim 2 which is

13. A compound according to claim 2 which is

14. A compound according to claim 2 which is

15. Composition comprising an organic substrate and a compound of the general formula I

(I) wherein R1 denotes alkyl with 1 to 8 carbon atoms; R2 denotes hydrogen or alkyl with 1 to 8 carbon atoms; R3 denotes hydrogen 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 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 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 and R6 - if m is 1 - is hydrogen, alkyl from 1 to 18 carbon atoms or one of a group of the formula or C6H5NHCO-or - if m is 2 or 3 - is hydrogen.

16. Composition according to claim 15 comprising a compound of the gen-eral formula I, wherein R1 denotes alkyl with 1 to 8 carbon atoms; R2 denotes hydrogen or alkyl with 1 to 8 carbon atoms; R3 denotes hydrogen 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 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 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 and R6 denotes hydrogen.

17. Composition according to claim 15, comprising a compound of the for-mula I wherein R1 denotes alkyl with 1 to 4 carbon atoms; R2 denotes hydrogen, methyl or butyl; R3 denotes hydrogen; X denotes a direct bond, or alkylene with 2 or 3 carbon atoms; R4 denotes hydrogen, alkyl with 1 to 17 carbon atoms, or a group m denotes 1 to 3, R5 - if m is 1 - denotes hydrogen, alkyl with 8 to 18 carbon atoms, hydroxybenzyl substituted by 2 alkyl groups each with 1 to 4 carbon atoms, or one of the groups -CH2CH2CN or -(CH2)2-COOR, wherein R is alkyl with 2 to 18 carbon atoms or a group or - if m is 2 - denotes alkylene with 1 to 6 carbon atoms or -CH2CH2-O-CH2CH2 O-, or - if m is 3 - the group and R6 - if m is 1 - is hydrogen or one of a group of the formula or C6H5NHCO

or - if m is 2 or 3 - is hydrogen.

18. Composition according to claim 16, comprising a compound of the for-mula I wherein R1 denotes alkyl with 1 to 4 carbon atoms; R2 denotes hydrogen or alkyl with 1 to 4 carbon atoms; R3 denotes hydrogen; X denotes a direct bond or one of the radicals -CH2CH2- or ; R4 denotes alkyl with 1 to 17 carbon atoms, or a group m denotes 1 or 2, R5 - if m is 1 - denotes hydrogen, alkyl with 1 to 18 carbon atoms, hydroxybenzyl substituted by 1 to 3 alkyl groups each having 1 to 4 carbon atoms, or a group -(CH2)q-COOR, wherein R is alkyl with 1 to 18 carbon atoms and q is 1 or 2, or - if m is 2 - denotes alkylene with 1 to 18 carbon atoms or the group -CH2CH2-O-CH2CH2- and R6 denotes hydrogen.

19. Composition according to claim 16, comprising a compound of the for-mula Ia (Ia) wherein R1 and R2 independently of one another denote alkyl with 1 to 4 carbon atoms, R3 denotes hydrogen, X denotes a direct bond, -CH2-CH2- or and R4 denotes alkyl with 1 to 17 carbon atoms or a group

20. Composition according to claim 16, comprising a compound of the formula Ib (Ib) wherein R1, R2, R1' and R2' independently of one another denote alkyl with 1 to 4 carbon atoms; R3 and R3' independently of one another denote hydrogen or methyl, X denotes a direct bond, -CH2-CH2- or -CH2-CH- and R4 denotes alkyl with 1 to 17 carbon atoms or a group

21. Composition according to claim 16, comprising a compound of the for-mula Ic wherein R1 and R2 independently of one another denote alkyl with 1 to 4 carbon atoms, R3 denotes hydrogen, X denotes a direct bond, -CH2-CH2- or , R4 denotes alkyl with 1 to 17 carbon atoms or a group and R5 denotes alkyl with 1 to 18 carbon atoms.

22. Composition according to claim 16, comprising a compound of the for-mula Id wherein R1 and R2 independently of one another denote alkyl with 1 to 4 carbon atoms; R3 denotes hydrogen; X denotes a direct bond, -CH2-CH2- or ;
R4 denotes alkyl with 1 to 17 carbon atoms or a group and R denotes alkyl with 1 to 18 carbon atoms.

23. Composition according to claim 16, comprising a compound of the for-mula Ie (Ie) wherein R1 and R2 independently of one another denote alkyl with 1 to 4 carbon atoms; R3 denotes hydrogen; X denotes a direct bond, -CH2-CH2- or ;
R4 denotes alkyl with 1 to 17 carbon atoms or the group and p denotes 1 to 18.

24. Composition according to claim 15, 16 or 17, wherein the organic sub-strate is a polymer.

25. Composition according to claim 15, 16 or 17, wherein the organic sub-strate is a polyolefin.

26. Composition according to claim 15, 16 or 17, wherein the organic sub-strate is polypropylene.