N-(SUBSTITUTED CYCLIC ALKYLENEIMINE)-.alpha.-(3,5-DI- ALKYL-4-HYDROXYPHENYL)-.alpha.',.alpha."-DIALKYL ACETAMIDES

N-(ALCOYLENEIMINE CYCLIQUE SUBSTITUEE)-.alpha.-(3,5-DI- ALCOYL-4-HYDROXYPHENYL)-.alpha.',.alpha."-DIALCOYL- ACETAMIDES

English Abstract

ABSTRACT OF THE DISCLOSURE
N-(2,2,6,6-tetraalkyl-4-piperidinyl)-?-(3,5-
di-alkyl-4-hydroxyphenyl)-?',?'' dialkylacetamides and
N-alkyl-N'-(3,3,5,5-tetraalkyl-2-keto-1-piperazinyl)-?-
(3,5-di-alkyl-4-hydroxyphenyl)?'.?''-dialkylacetamides
prepared by a new process are novel stabilizers for or-
ganic materials subject to attack and degradation, and
form useful combinations for this purpose with other
stabilizers against attack of polymer materials by
heat, oxygen and light.

Claims

-15-
The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as follows:
1. N-(substituted cyclic alkyleneimine)-?-
(3,5-di-alkyl-4-hydroxyphenyl)-?',?''-dialkyl acetami-
des having the general formula
<IMG>
wherein R1 and R2 are hydrogen or alkyl and cycloalkyl
groups containing 1 to 12 carbon atoms, alkylcycloalkyl
and aryl or alkaryl groups wherein the alkyl groups con-
tain 1 to 8 carbon atoms; R5, R6, R7, R8 and R9 are hy-
drogen, alkyl and cycloalkyl groups containing 1 to 12
carbon atoms, alkylcycloalkyl and aryl or alkaryl
groups wherein the alkyl groups contain 1 to 8 carbon
atoms, A is (1) an alkylidene group of the formula
<IMG> wherein R3 and R4 are alkyl groups containing
1 to 18 carbon atoms, C1-C18, or (2) cycloalkyl groups
containing 5 to 12 carbon atoms, and alkaryl groups
wherein the alkyl groups contain 1 to 8 carbon atoms; B
is a bond or alkylene group -(CH2)n- wherein n is 1 to

-16-
8; R10 is hydrogen or alkyl radicals containing 1 to 18
carbon atoms, O or OH; X is N or CH; and Y is H2 or O.
2. N-(2,2,6,6-tetraalkyl-4-piperidinyl)-?-
(3,5-di-alkyl-4-hydroxyphenyl)-?',?''-dialkylacetamides
and N-alkyl-N'-(3,3,5,5-tetraalkyl-2-keto-1-piperazin-
yl)-?-(3,5~-di-alkyl-4-hydroxyphenyl-?',?''-dialkylace-
tamides of Claim 1 wherein R1 contains 1 to 8 carbon
atoms; R2 contains 1 to 5 carbon atoms; R3 and R4 con-
tain 1 to 8 carbon atoms, the aryl groups are phenyl or
naphthyl; (2) is cyclohexyl, methylcyclohexyl, cyclohe-
ptyl, or dicyclohexyl, and R1, R2, R5, R6, R7, R8 and
R9 are alkyl groups containing l to 8 carbon atoms, and
R10 is hydrogen or an alkyl group containing 1 to
carbon atoms; in B n is 2 to 4; and X is CH.
3. The acetamides Gf Claim 2 wherein at
least one of R1 and R2 is t-butyl or t-amyl and R3 and
R4 are alkyl radicals containing 1 to 4 carbon atoms.
4, N-methyl-N'-(2,2,6,6-tetramethyl-4-piper-
-dinyl)-2-(3,5-di-t-butyl-4-hydroxyphenyl)-2-methylpro-
pionamide of Claim 3.
5. N-isopropyl-N'-[2-(3,3,5,5-tetramethyl-1-
piperazin-2-onyl)ethyl]-2-(3,5-di-t-butyl-4-hydroxyphe-
nyl)-2-methylpropionamide of Claim 3.
6. N-(2,2,6,6-tetramethyl-4-piperidinyl)-N'-
[2-(3,5-di-t-butyl-4-hydroxyphenyl)-2-methylpropanecar-
boxy-1]-1,6-hexanediamine of Claim 3.
7. A composition comprising (1) organic ma-
terials subject to degradation and stabilizing amounts
of (2) N-(substituted cyclic alkyleneimine)-?-(3,5-di-
alkyl-4-hydroxyphenyl)-?',?''-dialkyl acetamides hav-
ing the general formula

-17-
<IMG>
wherein R1 and R2 are hydrogen or alkyl and cycloalkyl
groups containing 1 to 12 carbon atoms, alkylcycloalkyl
and aryl or alkaryl groups wherein the alkyl groups con-
tain 1 to 8 carbon atoms; R5, R6, R7, R8 and R9 are hy-
drogen, alkyl and cycloalkyl groups containing 1 to 12
carbon atoms, alkylcycloalkyl and aryl or alkaryl
groups wherein the alkyl groups contain 1 to 8 carbon
atoms; A is (1) an alkyidene group of the formula
<IMG> wherein R3 and R4 are alkyl groups containing
1 to 18 carbon atoms, C1-C18, or (2) a cycloalkyl group
containing 5 to 12 carbon atoms, and alkaryl groups
wherein the alkyl groups contain 1 to 8 carbon atoms;
R10 is hydrogen or alkyl radicals containing 1 to 18
carbon atoms, O or OH; X is.N or CH; Y is H2 or O; and
B is a bond or alkylene group -(CH2)n- wherein n is 1
to 8.
8 Compositions of Claim 7 wherein R1 con-
tains 1 to 8 carbon atoms; R2 contains 1 to 5 carbon

-18-
atoms; R3 and R4 contain 1 to 8 carbon atoms; (2) is
cyclohexyl, methylcyclohexyl, cycloheptyl, or dicyclo-
hexyl, the aryl groups are phenyl or naphthyl; and R1,
R2, R5, R6, R7 and R8 are alkyl groups containing 1 to
8 carbon atoms; and R10 is hydrogen or an alkyl group
containing 1 to 8 carbon atoms; in B n is 2 to 4; and
X is CH.
9. Compositions of Claim 8 wherein at least
one of R1 and R2 is t-butyl or t-amyl and R3 and R4
are alkyl radicals containing 1 to 4 carbon atoms.
10, Compositions of Claim 9 wherein in (1)
said organic material is a polymer and (2) is N-methyl-
N'-(2,2,6,6-tetramethyl-4-piperidinyl)-2-(3,5-di-t-but-
yl-4-hydroxyphenyl)-2-methylpropionamide.
11. Compositions of Claim 9 wherein in (1)
said organic material is a polymer and (2) is N-isopro-
pyl-N'-[2-(3,3,5,5-tetramethyl-1-piperazin-2-onyl)eth-
yl]-2-(3,5-di-t-butyl-4-hydroxyphenyl)-2-methylpropion-
amide.
12. Compositions of Claim 9 wherein in (1)
said organic material is a polymer and (2) is N-(2,2,6,
6-tetramethyl-4-piperidinyl)-N-2-[(3,5-di-t-butyl-4-hy-
droxyphenyl)-2-methylpropanecarboxyl]-1,6-hexanediamine.
13. A process for preparing N-(substituted
cyclic alkyleneimine)-?-(3,5-di-alkyl-4-hydroxyphen-
yl)?,?'-dialkyl acetamides having the general for-
mula

-19-
<IMG>
wherein R1 and R2 are hydrogen or alkyl and cycloalkyl
groups containing 1 to 12 carbon atoms, alkylcycloalkyl
and aryl or alkaryl groups wherein the alkyl groups con-
tain 1 to 8 carbon atoms; R5, R6, R7, R8 and R9 are hy-
drogen, alkyl and cycloalkyl groups containing 1 to 12
carbon atoms, alkylcycloalkyl and aryl or alkaryl
groups wherein the alkyl groups containing 1 to 8 car-
bon atoms; A is (1) an alkyidene group of the formula
<IMG> wherein R3 and R4 are alkyl groups containing 1
to 18 carbon atoms, C1-C18, or (2) a cycloalkyl group
containing 5 to 12 carbon atoms, and alkaryl groups
wherein the alkyl groups contain 1 to 8 carbon atoms;
R10 is hydrogen or alkyl radicals containing 1 to 18
carbon atoms, O or OH; X is N or CH, B is a bond or al-
kylene group -(CH2)n- wherein n is 1 to 8; and Y is H2
or O; comprising reacting together a 2,6-dialkylphenol
having the formula
<IMG>

-20-
wherein R1 and R2 have the meanings above, a ketone se-
lected from the group consisting of dialkyl ketones,
cycloalakanones, alkcycloalkanones, and alkaryl ketones
wherein the alkyl groups contain 1 to 18 carbon atoms,
a haloform selected from the group consisting of chloro-
form and bromoform, and an alkali metal hydroxide and
piperidines and the piperazines, having the general
formula
<IMG>
wherein R5, R6, R7, R8 and R9 are hydrogen, alkyl, cy-
cloalkyl or alkaryl radicals containing 1 to 12 carbon
atoms; R10 is hydrogen, alkyl or alkaryl as defined
herein, oxygen radical or hydroxyl; X is N or CH; in B
n is 2 to 4; and Y is H2 or O.
14. A process of Claim 13 wherein R1 con-
tains 1 to 8 carbon atoms and R2 contains 1 to 5 carbon
atoms, the ketone is a dialkyl ketone of the formula
<IMG>
wherein R3 and R4 are alkyl radicals containing 1 to 8
carbon atoms, cyclopentanone, cyclohexanone, cyclohep-
tanone and alkyl derivatives thereof wherein the alkyl
groups contain 1 to 4 carbon atoms, R1, R2, R3, R4, R5,
R6, R7, R8 and R9 are alkyl groups containing 1 to 8
carbon atoms, and X is CH.

Description

N-(SUBSTITUTED CYCLIC ALKYLENEIMINE)-~ -
-(3,5-DI-ALKYL-4-HYDROXYPHENYL)-~',~''-
-
DIALKYL ACETAMIDES
.
SUMMARY OF THE INVENTION
.
: Novel N-(substituted cyclic alkyleneimi.ne)-~
-(3,5-di-alkyl-4-hydroxyphenyl)-~' ~''-dialkyl acetami-
des prepared by a new process are novel stabilizers for
organic materials subject to attack and degradation by
heat, oxygen and light, and form useful combinations
for this purpose with other hindered phenol stabllizers.
DETAILED DESCRIPTION
The novel N-(substituted cyclic alkyleneimi-
ne)-d-~3,5-di-alkyl-4-hydroxyphenyl~-~',~''-dialkyl ace-
tamides of this invention have the general formula
,OH
~r
A
C=O
R5 ~ $
.. I/x~f~y
R ~ ~ R9
R7 R8
1 10
~ .

~ ;'f~
wherein Rl and R2 are hydrogen or alkyl and cycloalkyl
groups containing 1 to 12 carbon atoms, alkylcycloalkyl
and aryl or alkaryl groups wherein the alkyl groups con-
tain 1 to 8 carbon atoms, and the aryl groups are nor-
mally phenyl or naphthyl; R5, R6, R7, R8 and R9 are hy-
drogen, alkyl and cycloalkyl groups containing 1 to 12
carbon atoms, alkylcycloalkyl and aryl or alkaryl
groups wherein the alkyl groups contain 1 to 8 carbon
atoms, and the aryl groups are normally phenyl or naph-
thyl; A is (1) an alkylidene group of the formulaR3-C-R4 wherein R3 and R4 are alkyl groups containing
1 to 18 carbon atoms, Cl-C18, or (2) a cycloalkyl group
containing 5 to 12 carbon atoms, and alkaryl groups
wherein the alkyl groups contain 1 to 8 carbon atoms,
including for example those groups derived from cyclo-
hexanone, cycloheptanone, alkyl aryl ketones wherein
: ~ the alkyl groups contain 1 to 8 carbon atoms and the
: ~ ~ aryl preferably is phenyl or naphthyl, and the like;
`~ B is a bond or an alkylene group oE the formula -(CH2)n-
wherein n is 1 to 8, preferably n is 2 to 4; R10 iS
hydrogen or alkyl radicals containing 1 to 18 carbon
atoms, O or OH; ~ is N or CH; and Y is H2 or o. Prefer-
ably, Rl is an alkyl group containing 1 to 8 carbon
atoms, Cl-C8, and R2 is an alkyl group containing 1
to 5 carbon atoms, and more pre~erably at least one of
Rl or R2 is a t-alkyl group including t-butyl and t-am-
yl; R3 and R4 are alkyl groups containing 1 to 8 carbon
atoms, Cl-C8, and more pre~erably 1 to 4 carbon atoms;
R5 is an alkyl group containing 1 to 6 carbon atoms;
R6 and R7 are methyl; R8 is an alkyl group containing 1
to 3 carbon atoms; R~ is an alkyl group containing 1 to
~ carbon atoms; R10 is hydrogen; in B n is 2 to 4; and
X is C~.

~J~
These N-(substituted cyclic alkyleneimines)-
~-~3,5-di-alkyl-4-hydroxyphenyl)-~', ~''-dialkyl aceta-
mides, more speei~lcally the N-(2,2,6,6-tetraalkyl-4-
pipereidinyl~ (3,5-di-alkyl-4-hydroxyphenyl)-~',~
di-alkylacetamides and N~alkyl-N'-(3,3,5,5-tetraalkyl-2-
keto-l-piperazinealkyl)-~-(3,5-di-alkyl-4-hydroxyphenyl)
-~',~''-dialkylacetamides, are prepared by a new process
by reacting a 2,6-di-alkylphenol with an aliphatic, cy-
cloaliphatic or alkaryl ketone, a haloform and a piper-
idine or piperazine compound in the presence of alkalimetal hydroxide. An organic solvent may be used, or
large amounts of the ketone reactant may be employed.
The amide is isolated in excellent yields by crystalli-
zing the filtered reaction product.
Typical 2,6-dialkyl phenols used have the
formula
OH
Rl--~R2
wherein Rl and R2 have the meanings set forth above,
including 2-methyl-6-t-butylphenol, 2-ethyl-6-t-but-
: 20 ylphenol~ 2-propyl-6-t-butylphenol, 2-isopropyl-6-t-
butylphenol, 2-n-butyl-6-t-butylphenolt 2,6-di-t-bu-
tylphenol, 2-n-amyl-6-t-butylphenoll 2-isoamyl-6-t-
butylphenol, 2-hexyl-6-t-butylphenol, 2~heptyl-6-t-
butylphenol, 2-isooctyl-6-t-butylphenol, 2-isopropyl-
6-methylphenol, 2-n-butyl-6-isopropylphenol, 2-isoamyl-
-6-ethylphenol, 2-isoamyl-6-methylphenol, 2-isooctyl-6-
methylphenol, 2-isooctyl-6-ethylphenol, 2-isooctyl-6-
n-propylphenol, 2-isooctyl-6-n-hexylphenol, and the
like.
The ketones used include dialkyl ketones,

3~3
Cycloalkanones r alkylcycloalkanones, and alkyl aryl ke-
tones. Typical ketones that may be used in the novel
process to make the new 3,5-dialkyl-4-hydroxyphenyl-
substituted acetic acids of the invention are alkyl
ketones of the formula
o
R3 - C - R4
wherein R3 and R~ are alkyl radicals containing 1 to
18 carbon atoms, preferably 1 to 8 carbon atoms, Cl-
C8, including for example acetone, methyl ethyl ke-
tone, methyl n-propyl ketone, diethyl ketone, 2-hexa-
none, 3,hexanone, di-n-propyl ketone~ 2-octanone,
methyl isopropyl ketone, and the like~ Also useful
are the cycloalkane ketones containing S to 12 car-
bon atoms in the cyclic ring such as cyclobutanone,
cyclopentanonel cyclohexanone, cycloheptanone, cyclo-
octanone, cyclodecanone, methylcyclopentanone, methyl-
cyclohexanone, dicyclohexyl ketone, alkyl aryl ketones
when the alkyl group contains 1 to ~ carbon atoms such
as acetophenone, o-methoxyacetophenone, p-chloroaceto-
phenone, and the like; in amounts from at least about1 mole of ketone per mole o~ 2,6-dialkylphenol, up to
amounts sufficient for the ketones to be the solvent
of the reaction, 10 moles or more, No more than about
two moles is preferred when the ketone is a reactant
only. Use of less than 1 mole reduces the product
yield, and more than about 2 moles is unnecessary un-
less the ketone is the solvent.
The haloform, such as chloroform, is also
used in a molar ratio of at least about one mole per
mole of 2,6-dialkylphenol used, but preferabl~ a
slight molar excess is used up to about a 50 percent
molar excess, i.e., 1.5 mole per mole of 2,6-dialkyl-

2.~
phenol. While larger amounts may be used, there isno advantage realized, and lesser amounts will decrease
the ultimate yield of the desired product~ Bromoform
may be substituted for the chloroform and excellent
results will be obtained.
The alkali metal hydroxide is used in pow-
der form, or in solution, and includes sodium hydro-
xide and potassium hydroxide. Preferablyr a molar
excess of the alkali metal hydroxide is used in re-
lation to the amount of 2,6-dialkylphenol present.
Normally from about 4 moles of alkali metal hydroxide
per mole of 2,6-dialkylphenol up to 10 or more moles
may be used, but the amount used preferably is about
4 to about 8 moles of hydroxide per mole of 2,6-di-
alkylphenol. Use of less than about 4 moles willreduce the yield of desired product.
The N-substituted cyclic alkyleneimines used
in the process of this invention to make the novel
acetamides, the piperidines and the piperazines, have
the general formula
R5 - N -H
B
~X~Y
R6 ~ ~ R9
R N R8
R10
wherein R5, R6, R7, R8 and R9 are hydrogen, alkyl, cy-
cloalkyl or alkaryl radicals containing 1 to 18 carbon
atoms, more preferably wherein the alkyl groups contain
1 to 8 carbon atoms, R10 is hydrogen, alkyl or alkaryl
as defined above, oxygen or hydroxyl; X is N or CH; Y

is H2 or O, more preferably X is CH; B is a bond or an
alkylene group of the formula -(CH2)n- wherein n is
1 to 8, preferably n is 2 to 4. Typical compounds are
substituted piperidine and piperizine derivatives such
as 4-amino-Z,2,6,6-tetramethy] piperidine, N'-(2-iso-
propylaminoethyl)-3,3,5,5-tetramethyl-2-piperazinone,
N'-(2-cyclohexylamino ethyl)-3,3,5,5-tetramethyl-2-pip-
erazinone, 4-methylamino-2,2,6,6-tetramethyl piperidi-
ne, Nl-(20-isobutylaminoethyl)-3,5,5-trimethyl-3-iso-
butyl-2-piperazinone, N,N'-(2,2,6,6-tetramethyl-4-pip-
eridyl)-1,6-hexanediamine, and the like.
The amount of substituted piperidine or pipe-
razine used in the reaction is based on one mole of the
2,6-dialkylphenol, While the amount may vary from less
than a stoichiometric amount, resulting in low product
yield, to larger excesses that are not required and
have to be separated from the reaction mixture, normal-
~ly about 1 to 4 moles to about 1 mole is used~
; The solvent used may be any polar organic
solvent, including an excess of the ketone used in
place of an added solvent. Typical solvents that may
be used include methylene chloridel tetrahydrofuran,
diethyl ether, dibutyl ether, dimethyl sulfoxide, 1,4-
dioxane, carbon tetrachloride, toluene, xylene, and the
like. The amounts of solvent used will vary from about
-5 moles to 100 moles per mole of 2,6-dialkylphenol
used. As has been stated, the solvent may be elimina-
ted if an excess of the reactant ketone is used. In
this case, the amount of ketone used, based on the
moles of 2,6-dialkylphenol used may be from about 5 to
about 20, preferably about 7.5 to 15 moles per mole
of 2,6-dialkylphenol.

3~i
While the reactants may be added in any
order, it is preferred that the alkali metal hydrox-
ide be added last, over a period of time to control
the exothermic reaction and preferably maintain the
S reaction below 30C, preferably below about 10C. The
reaction temperature may be varied from about 0C to
about 30C, but preferably is conducted from about 0C
to 10C. The reaction time normally will vary from
about 5 to about 15 hours.
The amides are readily isolated from the re-
action mixture by filtration, washing the filtrate
with aqueous inorganic acid, including hydrochloric or
sulfuric acid, to the reaction mixture to isolate the
amide, most of which is in the organic layer that
forms~ The aqueous layer may be extracted with solvent
to remove all traces of the amide, and this is added to
the other organic layer and this mixture is dried with
a desiccant such as anhydrous sodium sulfate, and heat-
ed to dryness. This product may be recrystallized if
desired.
The practice of the invention is demonstra-
ted in the following Examples. The structures of the
amides of the following Examples were confirmed by in-
frared and nuclear magnetic resonance spectra. Mole-
cular weights were determined and confirmed by field
desorption mass spectra ~FD/M~). Elemental analysis
of carbon and hydrogen was done and the amounts found
- were consistent with the Eormulas oE the materials.
.

~XAMPLE 1
N-methyl-N'-(2,2,6,6~tetramethyl-4-
piperidinyl)-2-(3,5-di-t-butyl-4-hydroxyphenyl)-
2-methyl propionamide
0.1 Mole of 2,6-di-t-butylphenol, 1.0 mole
of acetone, 0.15 mole of chloroform and 0.1 mole of 4-
methylamino-2,2,6,6~tetramethylpiperidine were added to
a reactor and mixed by stirring while being cooled to
5C by a circulating cold bath. 0.5 mole of powdered
sodium hydroxide was slowly added in small portions
over a period of 1 hour. The reaction mixture was
stirred at 10C overnight. The reaction mix from the
reactor was filtered. The solid residue was washed
with methylene chloride and the wash added to the fil-
trate. The filtrate was washed with 50 ml 4N hydro-
chloric acid, 50 ml of 5% sodium carbonate, and wasthen dried over sodium sulfate. The filtrate was eva-
porated to dryness and the dried product wa~ washed
with hexane. The resulting amide was a white solid
that had a melting point of 168-173C and a molecular
~; 20 weight of 44~. By elemental analysis it was determined
that the amide contained 75.38~ carbon (75O67~ calcula-
ted), 10.76% hydrogen (calculated 10.88%) and 6.20
nitrogen (calculated 6.30%).
EXAMPLE 2
- N-Isopropyl-N'-[2-(3,3,5,5-tetramethyl-1-
piperazinyl)]ethyl-2-(3,5-di-t-butyl-4-
hydroxyphenyl)-2~methylpropionamide
0.1 Mole of 2,6-di-t-butylphenol, 1.0 mole

3~,
of acetone, 0.15 mole of chloroform, 0.1 mole of N'-(2-
isopropylaminoethyl-3,3,5,5-tetramethyl-2-piperizinone
were added to a reactor and mixed by stirring while
being cooled by a circulating cold bath. 0.5 mole of
powdered sodium hydroxide was slowly added over a peri-
od of 1 hour. The reaction mixture was stirred at 10C
overnight. The reaction mix from the reactor was fil-
tered. The solid residue was washed with methylene
chloride and the wash added to the filtrate. The
filtrate was washed with 50 ml of 4N hydrochloric acid,
50 ml of 5~ sodium carbonate and was then dried over
sodium sulfate. The filtrate was evaporated to dryness
and the dried product was washed with hexane. The re-
sulting amide was a white solid that had a melting
15 point of 165-169C and a molecular weight of 515. By
elemental analysis it was determined that the amide
contained 72.~3~ carbon (72.19% calculated), 10.26~ hy-
drogen (calculated 10.36~) and 8.02% nitrogen (calcu-
lated 8.15%).
EXAMPLE 3
N-(2,2,6,6-tetramethyl-~-piperidinyl)-N'-
[2-(3,5-di-t-butyl-4-hydroxyphenyl)-2-methyl
propanecarboxyl]-1,6-hexanediamine
0,2 mole of 2,6-di-t-butylphenol, 1.0 mole of
acetone, 0.15 mole of chloroform, 0.1 mole of 4-hexami-
- 25 no-2,2,6,6-tetramethyl piperidine were added to a reac-
tor and mixed by stirring while being cooled by a cir-
culating cold bath. O.S mole of powdered sodium hydro-
xide was slowly added in small portions over a period
of 1 hour. The reaction mixture was stirred at 10C

--10--
overnight. The reaction mix from the reactor was fil-
tered, The solid residue was washed with methylene
chloride and the wash added to the filtrate. The fil-
trate was washed with 50 ml 4N hydrochloric acid, 50
ml of 5% sodium carbonate and was then dried over so-
dium sulfate. The Eiltrate was evaporated to dryness
and the dried product was washed with hexane. The
resulting amide was a white solid that had a melting
point of 255-260C and a molecular weight o~ 983.5.
By elemental analysis it was determined that the amide
contained 76.40% carbon (76.38% calculated), 10.71%
hydrogen (calculated 10.90%) and 5.79% nitrogen (cal-
culated 5.~4~).
To demonstrate the stabilizing activity of
the amides of this invention, test samples of the
amides in polypropylene were prepared by mixing the
stabilizer compounds with polypropylene in a Brabender
Plasticorder fitted with a Cam-Head (mixing chamber)~
The polypropylene is first masticated ~or 1 1~2 minu-
~es at 190C. Then the stabili2er is added, followedby 3 minutes additional mixing. The mass is removed
and pressed into 20 mil thick sheets. From these
sheets are cut 1" x 1" plaques for oven aging. Type
C (3`' x 1/8") tensil bars are cut for UV stability
tests.
Thermal/oxidative stability (oven aging) tes-
- ting consisted of aging the samples in triplicate in
an air-circulating oven at 125C. The time to catas-
trophic crumbling ~ailure) of the plaque was measured
and reported as days to failure. Each sample contained
0.1 weight part of the named amide per 100 weight parts

~6~
of polypropylene (pHr). The following results, in days
to failure, were obtained:
125C
Control 2
N-methyl-N'-(2,2,6,6-tetramethyl-4-piperidinyl)-
2-(3,5-di-t-butyl-4-hydroxyphenyl)-2-methyl-
propionamide 7
N-Isopropyl-N'-[2-(3,3,5,5-tetramethyl-1-piper-
azinyl))ethyl-2-(3,5-di-t-butyl-4-hydroxy-
phenyl)-2-methylpropionamide 9
Samples containing 0.1 weight part of the a-
mide listed below was tested for ultraviolet light sta-
bility, i.e., resistance to degradation by UV radiation.
The samples were tested in an Atlas Xenon Weatherometer,
Model No. 65-WR, equipped with a 6500 watt Xenon burn-
er tube in accordance with ASTM #D2565-79-A. The black
panel temperature was 60C. The samples were subjected
to an 18~minute water cycle ev~ry 2 hours. The time
in hours to a 50% loss in tensile strength was deter-
mined. For comparison purposes a samples with no amidewas tested. The following results, in hours, were ob-
tained:
Hours
Blank (Control) 220
N-Isopropyl-N'-[2-(3,3,5/5-tetramethyl-1-piper-
aæin 2-onyl)ethyl]-2-(3,5-di-t-butyl-4-hydroxy-
- phenyl)-2-methylpropionamide (0.1 phr) 1280
The N-(2,2,6,6-tetraalkyl-4-piperidinyl)-
3,5-di-alkyl-4 hydroxyphenyl)-~',c~ dialkylacetamides
and N-alkyl-N'-(3,3,5,5-tetraalkyl-2-keto-1-piperazin-

Jl3~:~
-12-
ealkyl)_~-(3,5-di-alkyl-4-hydroxyphenyl)~',~''-dialkyl-
acetamides as defined herein provide exceptional heat
stabiity and resistance to ultraviolet degradaticn to
polyolefin polymers. They are especially useful for
the stabilization of ~-monoolefin homopolymers and co-
polymers, wherein the ~-monoolefin contains 2 to about
8 carbon atoms. High and low-density polyethylene,
isotactic and atactic polypropylene, polyisobutylene,
and poly(4-methyl-l-pentene) have excellent resistance
to heat and oxygen when stabilized with the combina-
tions of the present invention. Ethylene-propylene co-
polymers and ethylene-propylene terpolymers, generally
containing less than about lO percent by weight of one
or more monomers containing multiple unsaturatation
provided, phenols; ring opened olefin polymers and the
like. Polymer blends, that is, physical admixture of
two or more polymers may also be stabilized in accord-
ance with the present invention.
In addition to polymeric materials, the pre-
sent compounds may stabilize a wide variety of other
organic materials. Such compounds include: waxes,
synthetic and petroleum-derived lubricating oîls and
greases; animal oils such as, for example, ~at, tal-
low, lard, codliver oil, sperm oil; vegetable oils
such as castor, linseed, peanut, palm, cotton seed,
and the like; fuel oil, diesel oil, gasoline and the
like.
- The (3,5-dialkyl-4-hydroxyphenyl~-substituted
amides may be used with other stabilizers including
hindered or partially hindered phenols, hindered amine
light stabilizers, phosphites, o-hydroxybenzophenones,
and the like. Typical hindered phenols are the hydrox-

3~
-13-
yphenylalkyleneyl isocyanurates such as the symmetrical
tris(3,5-di-t-alkyl-4-hydroxybenzyl) isocyanurates; te-
trakislmethylene 3-(3',5'-dialkyl-4'-hydroxyphenyl)pro-
panoate] methanes wherein the alkyl groups contain 1 to
8 carbon atoms, such as tetrakis[methylene 3-(3',5'-di-
t-butyl-4'-hydroxyphenyl)propanoate]methane; alkyl (3-
3~,5'-di-t-butyl-4'-hydroxyphenyl)propionates wherein
the alkyl groups contain 1 to 18 carbon atoms, such as
octadecyl 3~(3',5'-di-t-butyl-4-hydroxyphenyl)propion-
ate; 1,3,5-trimethyl-2,4,6-tris[3,5-dialkyl-4-hydroxy-
benæyl)benzene; 1,3,5-tris(3,5-di-t-butyl-4-hydroxy-
hydrocinnamoylethyl)-s-triazine-2,4,6-(lH,3H,5H)-trione;
2,2'-alkylidene bis (4,6-dialkylphenol)-s wherein the
alkyl group contains 1 to 8 carbon atoms, such as 2,2'-
methylene bis(4,6-di-t-butylphenol), 2,2'-ethylidene
bis(4,6-di-t-butylphenol), and 2,2'-methylene bis(4-
methyl-6-t-butylphenol), and the like.
For example, the following combinations pro-
vided excellent ageing in polypropylene as shown in
the Weatherometer: 0.05 phr of N-isopropyl-N'-[2-(3,3,
5,5-tetramethyl-1-piperazin-2-onyl)ethyl]~2-~3,5-di-t-
butyl 4-hydroxyphenyl)-2-methylpropionamide, 0.05 phr
o~ 1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetramethyl pipera-
zinone, and 0.05 phr of 2,2',2''-tris[3(3,5-di-t-butyl-
4-hydroxyphenyl)propionyloxy]ethyl isocyanurate - more
than 2,000 hours; 0~125 phr of N-isopropyl-N'-[2-(3,3,
5,5-te~ramethyl-1-piperazin-2-onyl)ethyl]-2-(3,5-di-t-
- butyl-4-hydroxyphenyl)-2-methyl propionamide, 0.05 phr
of 2,2',2 "-tris[3(3,5-di-t-butyl-4-hydroxyphenyl)pro-
pionyloxy]ethyl isocyanurate, and 0.125 phr of 3,9-bis
(octadecyloxy)-2,4,8,10-tetraoxa-3 r 9-diphosphaspiro[S,
5]-undecane - more than 2,000 hours.

-14-
The compounds are readily incorporated into
materialS to be patented by dis~olving or dispersing
them with the materials, in liquids, dispersions, so-
luations, and solid forms. If the material is a so-
lid, especially a polymeric solid such as rubber or aplastic, the compounds can be admixed using mixers
such as Banburys, extruders, two-roll mills, and the
like, following conventional techniques. One way to
disperse the compounds in plastic materials is to
dissolve or suspend the compounds in a solvent or di-
luent, mix the mixture with a plastic in powder or
solution form, and then ~vaporate the solvent.
Compositions containing the novel combina-
tion of compounds can also contain other known com-
pounding ingredients such as fillers like carbon black,silicar metal carbonates, talc, and the like; pigments
and colorants; curative ingredients like sulfur and
peroxides, and vulcanization accelerators; fungicides;
processing aids, reinforcing agents and standard ingre-
dients known to the art. Other ingredients ~nown inthe art as ultraviolet light, thermal and/or oxidative
stabilizers can also be used.

Representative Drawing