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Патент USA US3072617

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United States Patent 0 MICC
3,072,603
Patented Jan. 8, 1963
1
2
3,072,603
picnic acid as illustrated by those phenyl-substituted
amines having the formulas:
POLY - a - OLEFIN COMPOSITIONS CONTAINING
DIALKYL - 3,3’ - THIODIPROPIONATES AND A
(Ii
NITROGEN CONTAINING COMPOUND
Clarence E. Tholstrup, Kingsport, Tenn., assignor to East
man Kodak Company, Rochester, N.Y., a corporation
of New Jersey
No Drawing. Filed Mar. 23, 1960, Ser. No. 16,968
14 Claims. (Cl. 260-4535)
This invention relates to new poly-m-ole?n composi
tions. Preferred embodiments of the invention relate to
RIC OQNH c R1
Q“
10
polyethylene and polypropylene compositions having im
proved stability at elevated temperatures to oxidative deg
radation.
15
Poly-a-ole?ns such as polyethylene, polypropylene and
the like are commonly subjected to elevated temperatures
and
in the course of their processing into useful items of
commerce. Such processing methods as rolling, injec
tion molding, extrusion and the like at elevated tempera 20
tures usually result in oxidative degradation of the poly
wherein R1 and R2 are alkyl radicals having 1 to 18
mer. In addition, many uses of poly-u-ole?ns, such as
carbon atoms; wherein R3, R‘, R‘, and R10 are hydrogen
in electrical insulation and the like, often times expose
atoms, alkyl radicals having 1 to 18 carbon atoms, phenyl
the poly-a-ole?n to elevated temperatures. To minimize
radicals, naphthyl radicals or cyclohexyl radicals; and
oxidative deterioration in poly-a-ole?ns, antioxidants or
wherein R5, R‘, R", R‘, R", and R12 are hydrogen atoms
stabilizers are often times incorporated therein.
or alkyl radicals having 1 to 18 carbon atoms. The sub
It is an object of this invention to provide new poly-a
stituents R1 and R2 are preferably alkyl radicals having
ole?n compositions having improved resistance to thermal
8 to 18 carbon atoms. When the substituents R3, R4, R5,
degradation.
“a
R‘, R", R", R', R"), R", and Ru are alkyl radicals, these
It is another object of this invention to provide new 30 substituents preferably have 1 to 12 carbon atoms.
synergistic combinations of stabilizers for poly-u-ole?n
Typical phenyl-substituted amines that can be suitably
compositions. ‘
employed in combination with dialkyl-3,3'-thiodipropi
It is also an object of this invention to provide novel
onates include:
polyethylene and polypropylene compositions containing
synergistic combinations of compounds that improve the 35 p-lauramidophenyl laurate,
phenyl-Z-naphthylamine,
stability of the polyethylene and polypropylene composi
durenediamine,
tions against deterioration resulting from exposure to ele
isopropyltrimethyl-p-phenylenediamine,
vated temperatures.
Other objects of the invention will be apparent from
the description and claims that follow.
40
The present invention comprises poly-a-ole?n composi
tions having incorporated therein a stabilizer combina
N,N'-di( l-methyl heptyl)-p-phenylenediamine,
N,N'-dimethyl-p-phenylenediamine,
N-phenyl-N'-cyclohexyl-p-phenylenediamine,
N-phenyl~N'-isopropyl-p-phenylenediamine,
N,N'-dim'ethyl-N,N'-di-sec.-butyl-p-phenylenediamine,
N,N'-dilanryl-N,N’-distearyl-p-phenylenediamine,
tion of a diester of 3,3'-thiodipropionic acid and a phenyl
substituted amine.
The diesters of 3,3'-thiodipropionic acid comprising 45 4,4'-dimethyldiphenylamine,
4,4'-di(n-octyl)diphenylamine,
the present stabilizer combinations have the following
diphenylamine,
formula
4,4’-dimyristyldiphenylamine,
4,4'-distearyldiphenylamine,
50
v wherein R is an alkyl radical generally having 4 to 20
carbon atoms, with 8 to 18 carbon atoms being preferred.
A particularly effective ester has twelve carbon atoms for
the R substituent, namely, dilauryl-3,3’-thiodipropionate.
However, any diester of 3,3'-thiodipropionic acid as de
scribed above can be employed in the present stabilizer
combination including the butyl, amyl, hexyl, heptyl,
octyl, nonyl, decyl, tridecyl, myristyl, pentadecyl, cetyl,
heptadecyl, stearyl, and eicosyl diesters of 3,3'-thiodi
propionic acid, or mixtures thereof.
_
A wide variety of phenyl-substituted amines or nitro
gen-containing compounds can be e?ectively utilized in
combination with the described esters of 3p,3'-thiodipro
N,N'-diphenyl-p-phenylenediamine,
N,N'-di(2-naphthyl)-p-phenylenediamine,
N,N’-di( l-ethyl-3-methyl pentyl)-p-phenylenediamine,
and related phenyl-substituted amines.
The combination of the described diesters of 3,3'-thio
55 dipropionic acid and phenyl-substituted amines can be
used to stabilize a wide variety of solid poly-a-ole?n
compositions against deterioration. resulting from expo
sure to elevated temperatures.
Any of the normally
solid polymers of a-l'l'lOllOOlC?lliC aliphatic hydrocarbons
60 containing 2 to 10 carbon atoms can be stabilized in ac
cordance with the invention. The subject stabilizer com
binations are preferably used in polyethylene and poly
propylene, particularly polypropylene, although such
poly-a-ole?ns as poly(3-methylbutene-l), poly(4-methyl- ‘
3,072,603
pentene-l ) , poly (pentene-l ) , poly(3,3-dimethylbutene-1),
poly(4,4-dimethylbutene-l ), polywctene-l ). polytdecene
l) and the like can also be stabilized with the subject
stabilizer combinations. Both the so-called?low density”
and “high density” or high crystallinity poly-a-ole?n com
positions can be stabilized in accordance with the inven
tion. Reference is made to Fawcett et al. U.S. Patent
No. 2,153,553 granted April 11, 1939, and to copending
applications Coover U.S. Serial No. 559,536 ?led January
4
gation is compression molded into a smooth sheet or
plate. The plate is then cut into pieces weighing about
0.25 g. each. The 0.25 g. samples of the molded poly
mer are then placed in an air oven at 160° C.
Samples
are removed at intervals and each sample analyzed for
peroxides. The oven storage life is the time required
for initial peroxide formation in a sample of the polymer.
To determine peroxide formation in the oven exposed
samples, each 0.25 g. sample in question is dissolved or
17, 1956, now abandoned, and Coover et al. U.S. Serial 10 suspended in 20 ml. of carbon tetrachloride and allowed
to digest for 25 minutes. To this is added 20 ml. of a
No. 724, 904 ?led March 31, 1958, now abandoned, with
mixture consisting of 60% glacial acetic acid and 40%
regard to the preparation of various poly-u-ole?n com
chloroform, and then 1.0 ml. of a saturated aqueous
positions that can be stabilized against thermal degrada
solution of potassium iodide. The resulting mixture is
tion in accordance with the invention. The additive sta
allowed to react for two minutes, 100 ml. of water is
bilizer combinations of the invention are especially use
added to dilute the mixture, and then a starch indicator
ful for stabilizing the solid resinous poly-a-ole?ns having
is added. The resulting mixture is then back-titrated
average molecular weights of at least 15,000 and more
with 0.002 N sodium thiosulfate. The peroxide concen
usually at least 20,000, although the stabilizer combina~
tration, P, in milliequivalents per kilogram of polymer
tions of the invention can also be utilized to stabilize the
so-called poly-a-ole?n waxes having lower average mo 20 is given by the expression, P=8S, where S is the number
of milliliters of 0.002 N sodium thiosulfate used.
lecular weights of usually 3,000 to 12,000.
The amount of the combination of the diester of 3,3’
EXAMPLE 1
thiodipropionic acid and the phenyl-substituted amine em
ployed in poly-a-ole?n compositions in accordance with
the invention can be widely varied, the stabilizing amount 25
of this combination usually varying with the particular
use to which the poly-a-ole?n compositions are to be put.
Concentrations of at least about 001% of each stabilizer
component are suitable, although about .00l% to 5% for
Several samples of powdered polypropylene were mixed
with dilauryl-3,3'-thiodipropionate and typical phenyl
substituted amines of the invention, compression molded
into plates M6 inch in thickness, and the resulting molded
samples evaluated with respect to stability by the 160°
C. oven storage test described above. The polypropyl—
each stabilizer component are generally used, with about 30 ene was a plastic grade solid polypropylene having an
average molecular weight greater than 15,000, a density
.0l% to 3% of the diester of 3,3’-thiodipropionic acid
of about .91 and an inherent viscosity of about 1.6 as
and about .0l% to 1% of the phenyl-substituted amine
determined in tetralin at 145° C. The results of the sta
being preferred, the concentration being based on the
bility tests are summarized by the data set out in Table
weight of the poly-a-ole?n. We generally utilize the
A below. Samples of the individual components of the
combination of the subject stabilizers at a weight ratio
various stabilizer combinations in the polypropylene, as
of the diester of 3,3'-thiodipropionic acid to the phenyl
well
as the polypropylene with no additive, were included
substituted amine in the range of 1/100 to 100/1, and
in the stability test for purposes of comparison. In
preferably 1/50 to 50/1.
Table A, dilauryl-3,3'-thiodipropionate is indicated as
The stabilizer combinations of the invention can be in
corporated or blended into poly-a-ole?n compositions by 40 “DLTDP.” The concentrations in Table A are based on
the weight of the polypropylene.
the conventional methods utilized for blending such ma
terials into resins or plastics. Typical of such methods
Table A
that can be suitably employed include milling on heated
Additive:
Oven life at
rolls, deposition from solvents, and dry blending. The
160° C., hours
stabilizers of the invention can be incorporated separately
None
0.2
or together into the poly-a-ole?n compositions.
0.05% DLTDP __________________________ __ 0.5
The stabilizer combinations of the present invention
lend to poly-a-ole?n compositions improved stability, and
more particularly, improved stability against oxidative
0.05% diphenylamine ____________________ _..
0.05% diphenylamine-l-0.0S% DLTDP _____ __
0.05% N,N'~diphenyl-p-phenylenediamine_.____ 15
deterioration resulting from exposure to elevated tem 50
0.05% N,N' - diphenyl - p - phenylenediamine
peratures. In addition, poly-a-ole?n compositions con
taining the stabilizer combinations of the invention have
enhanced stability against deterioration resulting from
exposure to sunlight or ultraviolet light. Thus, poly-a
0.05% N,N’ - di(2 - naphthyl) - p -phenylene
ole?ns stabilized in accordance with the invention have
an extended life expectancy and can be used more e?ec
tively than unstabilized poly-a-ole?ns for a wide diversity
of uses.
Poly-a-ole?ns stabilized as described can be
12
20
+0.05% DLTDP ______________________ .._
diamine
_____________________________ __
25
65
0.05% N,N’-di(2-naphthyl)-p-phenylenediamine
+0.05% DLTDP ______________________ __
95
As can be observed from the data set out in Table A
above, combinations of certain phenyl-substituted amines
and dilauryl-3,3’-thiodipropionate are synergistic com
cast, extruded, rolled, or molded into sheets, rods, tubes,
pipes, ?laments and other shaped articles, including the 60 binations with respect to the stabilization of polypropyl
widely used ?lms of the polymers about .5 to 100 mils
in thickness. The present compositions can be used for
coating paper, wire, metal foil, glass ?ber fabrics, syn
thetic and natural textiles or fabrics, and other such mate
rials.
The subject stabilizer combinations of dialkyl esters of
3,3'-thiodipropionic acid and phenyl-substituted amines
are synergistic combinations, namely, the stabilizing effect
of such combinations in poly-a-ole?ns is substantially
greater than the additive elfect of the individual compo 70
nents of the combination.
ene, the stabilizing effect of such combinations being sub
stantially more than the additive stabilizing effect of the
components thereof. Similar synergism is demonstrated
if solid plastic grade polyethylene having an average
molecular weight greater than 15,000, a melt index of
about 7.59 and a density of about .91 is substituted for
the polypropylene, or if distearyl-3,3'-thiodipropionate or
di-n-octyl-3,3'-thiodipropionate is substituted for the di
lauryl-3,3’-thiodipropionate.
EXAMPLE 2
The invention is illustrated by the following examples
evaluated by the method described in Example 1 in the
of preferred embodiments thereof. In the following ex
stabilization of solid plastic gradetpolypropylene having
amples the stability of the poly-a-ole?ns was determined
by an oven storage test. The poly-a-ole?n under investi 75 an average molecular weight greater than 15,000, a density
Several stabilizer combinations of the invention were
3,072,603
6
ofabout .91 and an inherent viscosity of about 1.25 as
determined in tetralin at 145° C. The results of the
test are summarized by the data set out in Table B be
0.05% N’ - phenyl = N’ - cyclohexyl - p - phen
ylenediamine _________________________ __ 10
0.05% N’ - phenyl - N’ - cyclohexyl - p - phen
ylenediamine+0.l% DLTDP ___________ _... 25
0.05% N - phenyl - N’ - isopropyl - p - phenyl—
low._ In Table B, dilauryl-3,3'-thiodipropionate is indi
cated as “DLTDP.” The concentrations in Table B are
'based on the weight of the polypropylene.
I
enediamine
Additive:
Oven life at 160° C., hours
None
0.3% DLTDP
2
3 10
0.05% N,N’-diphenyl-p-phenylenediamine-____ 12
+03% DLTDP _____________________ ....
0.05 %
100
enediamine +0.1% DSTDP _____________ __ 21
0.05% durenediamine
0.05% - phenyl
15
4
-
2
-
naphthylamine+0.1%
DLTDP
18
0.05% p-lauramidophenyl laurate _________ __
N,N' - di(Z-naphthyl) -p-phenylenedia
0.05%
mine+0.3% DLTDP __________________ __ 190
0.05% N - cyclohexyl - N’ - phenyl - p - phenyl
'
enediamine
12
0.05% N - cyclohexyl - N' - phenyl - p - phen
ylenediamine+0.3% DLTDP __________ __ 160
0.05% 4,4’—di-n-octyldiphenylamine ________ __ 12
0.05 % 4,4’ - di - n - octyldiphenylamine+0.3%
0.05% N - phenyl - N’ - isopropyl - p - phenyl~
0.05% durenediamine+0.1% DLTDP ______ __ 20
0.05% phenyl-Z-naphthylamine ____________ __
4
0.05% N.N' - diphenyl - p - phenylenediamine
0.05% N,N' - di(2 - naphthyl) - p - phenylenedi
amine
' 30
6
0.05% N - phenyl - N’ - isopropyl - p - phenyl
enediamine+0.1% DLTDP ____________ _.. 20
Table B
20
2
p - lauramidophenyl laurate+0.l%
DLTDP
20
As illustrated by the data set out in Table C, a wide
variety of phenyl-substituted amines and dialkyl-3,3’
thiodipropionates have a synergistic stabilizing effect in
polypropylene. Similar synergism is demonstrated if
solid plastic grade polyethylene having an average molecu
DLTDP
25 25 lar weight greater than 15,000, a density of about .91 and
a melt index of about 7.59 is substituted for the poly
As observed from the data in Table 13, dilauryl-3,3'
. propylene.
thiodipropionate synergizes with a wide variety of phen
As used herein, inherent viscosity (1“) is calculated
yl-substituted amines in polypropylene. Similar syner
from the formula
gism is demonstrated if di-n-octyl-3,3’-thiodipropionate or
distearyl-3,3'-thiodipropionate is substituted for the di 30
In":
lauryl-3,3’-thiodipropionate. Such stabilizer combina
tions are likewise synergistic stabilizer combinations in
wherein C is the concentration of the polymer in grams
per 100 cc. of tetralin and n, is the ratio of the viscosity
of the solution of the polymer and tetralin to that of tetra
lin. The viscosities are determined at 145° C.
polyethylene as demonstrated if solid plastic grade poly
ethylene having an average molecular weight greater than
15,000, a density of about .91 and a melt index of about
7.59 is substituted for the polypropylene.
The present invention thus provides novel poly-u-ole
?n compositions having improved stability against de
EXAMPLE 3
terioration resulting from exposure to elevated tempera
Several stabilizer combinations of the invention were 40 tures, and particularly, it provides novel synergistic sta
evaluated by the method described in Example 1 in the
bilizer combinations for poly-a-ole?n compositions.
stabilization of solid plastic grade polypropylene having
Although the invention has been described in detail
an average molecular weight greater than 15,000, a density
with reference to preferred embodiments thereof, it will
of about .91 and an inherent viscosity of about 1.48
be understood that variations and modi?cations can be
as determined in tetralin at 145° C. The results of test
effected within the spirit and scope of the invention as
are summarized by the data set out in Table C below. 45 described hereinafter and as de?ned by the appended
claims.
In Table C, dilauryl-3,3'-thiodipropionate is indicated
I claim:
as “DLTDP,” di-n-octyl-3,3'-thiodipropionate is indicated
as “DOTDP” and distearyl-3,3’-thiodipropionate is indi
1. A solid poly-a-ole?n composition comprising a solid
poly-a-ole?n prepared from an a-monoole?nic aliphatic
cated as “DSTDP." The concentrations in Table C are
50 hydrocarbon having 2 to 10 carbon atoms containing a sta
based on the weight of the polypropylene.
bilizer combination comprising at least about .001% by
Table C
weight based on said poly-a-ole?n of a diester of 3,3’
thiodipropionic acid having the formula
Additive:
Oven life at 160° 0., hours
None
0.2 55
0
0.1% DOTDP
1
0.1% DLTDP
1
0.1% DSTDP
1
wherein R is an alkyl radical having 8 to 18 carbon atoms,
0.05% N,N’-di~sec.-butyl-p-phenylenediamine__ 5
and at least about .001% by weight based on said poly
0.05% N,N' - di(sec. - butyl) - p - phenylene
60 a-ole?n of a nitrogen-containing compound selected from
swmomiion),
diamine+0.1% DOTDP ________________ __ 10
0.05% N,N' - di(sec. - butyl) - p - phenylene
diamine+0.l% DLTDP ________________ .... 11
0.05% N,N’ - di(sec. - butyl) - p - phenylene
diamine+0.l% DSTDP ________________ .._ 12
0.05% N,N' - di(l - methyl hcptyl) - p - phenyl
enediamine'
the group consisting of compounds having the formulas
65
14
p-phenylenediamine ___________________ __
4
70
0.05% N,N' - dimethyl - N,N' - di(sec. - butyl)-'
p-phenylenediamine-i-0.l% DLTDP ______ __ 30
0.05% N,N' - dimethyl - N,N’ - di(sec.-butyl)
p-phenylenediamine-l-0.l% DSTDP ______ __ 32
0
II
II
RIC 0-QNHC RI
QM
6
0.05% N,N' - di(l - methyl heptyl) - p - phenyl
enediamine+0.1% DLTDP ____________ ....
0.05% N,N' - dimethyl - N,N' - di(sec. - butyl)
O
75
8,072,603
7
8
and
and
RIQNHQR"
wherein R1 and R2 are alkyl radicals having 8 to 18 5 wherein R1 and R2 are alkyl radicals having 8 to 18 car
bon atoms, wherein R3, R‘, R9 and R10 are selected from
carbon atoms, wherein R3, R‘, R9 and R10 are selected
the group consisting of hydrogen atoms, alkyl radicals
from the group consisting of hydrogen atoms, alkyl radi
having 1 to 12 carbon atoms, phenyl radicals, naphthyl
cals having 1 to 12 carbon atoms, phenyl radicals, naph
radicals and cyclohexyl radicals, and wherein R5, R',
thyl radicals and cyclohexyl radicals, and wherein R5,
R", R‘, R11 and R1’ are selected from the group con
R‘, R", R“, R11 and R12 are selected from the group con 10 sisting
of hydrogen atoms and alkyl radicals having 1
sisting of hydrogen atoms and alkyl radicals having 1
to 12 carbon atoms.
to 12 carbon atoms.
_
4. A solid poly-a-ole?n composition comprising solid
2. A solid poly-a-ole?n composition comprising a solid
polypropylene
containing a stabilizer combination com
poly-a-ole?n selected from the group consisting of poly
ethylene and polypropylene containing a stabilizer com 15 prising about .001% to 5% by weight based on said poly
propylene of a diester of 3,3'-thiodipropionic acid having
bination comprising about .001% to 5% by weight based
the formula
on said poly-a-ole?n of a diester of 3,3'-thiodipropionic
acid having the formula
0
_
II
SCHCHCOR
(
a
a
)1
20
wherein R is an alkyl radical having 8 to 18 carbon atoms,
and about .00l% to 5% by weight based on said poly
S(CH2CH1(% 0 R);
wherein R is an alkyl radical having 8 to 18 carbon atoms,
and about .001% to 5% by weight based on said poly-a
ole?n of a nitrogen-containing compound selected from
the group consisting of compounds having the formulas
propylene of a nitrogen-containing compound selected
from the group consisting of compounds having the
25 formulas
ii
RIC OQ-NHCR'
0
ll
Q“
31
30
o
NHCR!
@e
Ba
R:
R1
RI
35
R0
BKN
R|/
Rn
31
o
RICO
RI
/R'
—-N
R1
Ra
\Ru
and
wherein R1 and R2 are alkyl radicals having 8 to 18 car
bon atoms, wherein R3, R‘, R9 and R“ are selected from
wherein R1 and R2 are alkyl radicals having 8 to 18 car
bon atoms, wherein R3, R‘, R9 and R" are selected from
the group consisting of hydrogen atoms, alkyl radicals 45 the group consisting of hydrogen atoms, alkyl radicals
having 1 to 12 carbon atoms, phenyl radicals, naphthyl
having 1 to 12 carbon atoms, phenyl radicals, naphthyl
radicals and cyclohexyl radicals, and wherein R5, R‘,
radicals and cyclohexyl radicals, and wherein R5, R5,
R", R”, R11 and R12 are selected from the group consist
R7, R“, R11 and R12 are selected from the group consist
ing of hydrogen atoms and alkyl radicals having 1 to 12
ing of hydrogen atoms and alkyl radicals having 1 to 12
50
carbon atoms.
3. A solid poly-a-ole?n composition comprising solid
carbon atoms.
5. A solid poly-a-ole?n composition comprising solid
polyethylene containing a stabilizer combination compris
polypropylene containing a stabilizer combination com
ing about 001% to 5% by weight based on said polyeth
prising about .00l% to 5% by weight based on said poly
ylene of a diester of 3,3’-thiodipropionic acid having the
propylene of dilauryl-3,3’-thiodipropionate and about
55
formula
.001% to 5% by weight based on said polypropylene of
a nitrogen’containing compound selected from the group
consisting of compounds having the formulas
S(CH:CH:(% 0 R):
wherein R is an alkyl radical having 8 to 18 carbon atoms,
and about .001% to 5% by weight based on said poly
ethylene of a nitrogen-containing amine selected from the
group consisting of compounds having the formulas
i!)
i)
RIC OQ-NHC RI
75
- 8,072,608
wherein R1 and R2 are alkly radicals having 8 to 18 car
bon atoms, wherein R3, R‘, R’ and R1° are selected from
the group consisting of hydrogen atoms, alkyl radicals
having 1 to 12 carbon atoms, phenyl radicals, naphthyl
to 12 carbon atoms, and wherein R‘, R‘, R’ and R" are
selected from the group consisting of hydrogen atoms,
alkyl radicals having 1 to 12 carbon atoms, phenyl rad
radicals and cyclohexyl radicals, and wherein R‘, R‘, R",
9. A solid poly-a-ole?n composition comprising solid
icals, naphthyl radicals and cyclohexyl radicals.
R‘, R11 and R12 are selected from the group consisting of
hydrogen atoms and alkyl radicals having 1 to 12 carbon
I
polypropylene containing a stabilizer combination com
prising about .001% to 5% by weight based on said poly
propylene of a diester of 3,3'-thiodipropionic acid having
the formula
atoms.
6. A solid poly-a»ole?n composition comprising solid
polypropylene containing a stabilizer combination com 10
prising about .001% to 5% by weight based on said poly
propylene of a diester of 3,3’-thiodipropionic acid having
the formula
wherein R is an alkyl radical having 8 to 18 carbon atoms
and about .001% to 5% by weight based on said polypro
15 pylene of a nitrogen-containing compound having the for
mula
wherein R is an alkyl radical having 8 to 18 carbon atoms
and about .001% to 5% by weight based on said poly
propylene of a nitrogen-containing compound having the
formula
‘
f’
i’
aid o-Q-mac 12:
20 wherein R11 and R12 are selected from the group consist
ing of hydrogen atoms and alkyl radicals having 1 to 12
carbon atoms.
10. A solid poly-a-ole?n composition comprising solid
polypropylene containing a stabilizer combination com
wherein R1 and R2 are alkyl radicals having 8 to 18 car 25 prising .0l% to 3% by weight of dilauryl-3,3'-thiodipro
bon atoms.
pionate and .01% to 1% by weight based on said poly
7. A solid poly-a-ole?n composition comprising solid
propylene of. N,N'-di(2-naphthyl)-p-phenylenediamine.
polyproplyene containing a stabilizer combination com
11. A solid poly-u-ole?n composition comprising solid
prising about .00l% to 5% by weight based on said poly
polypropylene containing a stabilizer combination com
propylene of a diester of 3,3'-thiodipropionic acid having 30 prising .01% to 3% by weight of dilauryl-3,3'-thiodipro
the formula
pionate and .01% to 1% by weight based on said poly
propylene of N,N’-diphenyl-p-phenylenediamine.
12. A solid poly-a-ole?n composition comprising solid
wherein R is an alkyl radical having 8 to 18 carbon atoms
_ polypropylene containing a stabilizer combination com
and about .001% to 5% by weight based on said poly 35 ,prising .01% to 3% by weight of dilauryl-3,3'~thiodipro
’ pionateand .01% to 1% by weight pased on said poly
propylene of phenyI-Z-naphthylamine.
propylene of N-cyclohexyl-N'-phenyl-p-phenylenediamine.
8. A solid poly-a-ole?n composition comprising 'solid
13. A solid poly-d-ole?n composition comprising solid
polypropylene containing a stabilizer combination com
polypropylene
containing a stabilizer combination com
prising about .00l% to 5% by weight based on said poly
propylene of a diester of 3,3'-thiodipropionic acid having 40 prising .0l% to 3% by weight of dilauryl-3,3'-thiodipro
pionate and .01% to 1% by weight based on said poly
the formula
propylene of N,N'-dimethyl-N,N’-di(sec.-butyl)-p-phenyl- '
enediamine.
14. A solid poly-a-ole?n composition comprising solid
wherein R is an alkyl radical having 8 to 18 carbon atoms 45 polypropylene containing a stabilizer combination com
prising .01% to 3% by weight of dilauryl-3,3’-thiodipro
and about .001% to 5% by weight based on said poly
pionate and .0l% to 1% by weight based on said poly
propylene of a nitrogen-containing compound har'ing the
propylene of N,N'-dimethyl-N,N’-di(l-methyl heptyl)-p
formula
phenylenediamine.
'
References Cited in the ?le of this patent
34/
1
I
\mo
UNITED STATES PATENTS
2,448,799
Happoldt et'al. _______ .. Sept. 7, 1948
2,519,755
2,543,329
Gribbins _____________ .._ Aug. 22, 1950
Myers .............. -- Feb. 27, 1951
Thompson et al. ...... .... Sept. 25,1951
wherein R", R‘, R7 and R' are selected from the group 55
consisting of hydrogen atoms and alkyl radicals having 1
2,568,902
' UNITED STATES PATENT OFFICE
‘CERTIFICATE’ OF CORRECTION
Patent No», 3,072,603
“
v
-
i '
'
1
January 8t 1963
‘v ‘‘C11?whoev E‘, ‘Tholstrup
It is hereby certified the't error appears in the above numbered pat
ent requiring correction and that the said Letters Patent should read as
3 corrected below.
Column 7', line 61-, ‘7 ;€=orf5”"'amine'Vread- —~— compound N;
column ‘9, line 1, for ,-"al'kly""~ read -,=-1 alkyl -—~; column 10, line ’
36,
for "pasedn read
_-- "based
~70
.
'
'
'
Signed and sealed this 27th day of August 1963,
(SEAL)
Attest:
ERNEST w.
SWIDER
Attesting Office!‘
I
‘
4
~
iv
‘DAVID L-LADD
v
Commissioner of Patents
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