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Патент USA US2406722

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Patented Aug. 27, 1946
2,406,722
UNITED STATES PATENT OFFICE
2,406,722
" 'PRESERVING RUBBER
John R. Vincent, Wilmington, DeL, assignor to
E._ I. du Pont de Nemours & Company, Wil
mington, DeL, a corporation of Delaware
No Drawing. Application February 24, 1944,
Serial No. 523,746
15 Claims.
1
2
This invention relates to preserving rubber and
more particularly to increasing the effectiveness
of antioxidants in rubber.
(Cl. 260-800)
‘
It has long been proposed to preserve rubber,
that is, to inhibit the deterioration of rubber due
to the action of light, heat and oxygen, by in
corporating in the rubber Various organic com
pounds, commonly termed antioxidants. Since
the discovery of rubber antioxidants, their ei‘?
amine rubber antioxidant, the antioxidant effi
ciency of the antioxidant is very materially in
creased so that much greater protection of the
rubber is obtained with no increase in the amount
of antioxidant and smaller amounts of antioxi
dant may be employed to obtain a desired amount
of protection of the rubber. This was particu
larly surprising in view of the fact that the
phthalocyanine compounds employed are, in and
ciency, that is, the degree of protection aiiorded 10 of themselves, substantially ine?ective as anti
rubber by their use, has been gradually improved
oxidants.
by the discovery of new and better types of anti
The antioxidants, which may be employed in
oxidant compounds and by the use of mixtures
accordance with my invention, are those second
of antioxidants. At the present time, the best re
ary aromatic amines which are e?ective by them
sults are generally obtained by mixtures of two 15 selves to substantially inhibit the deterioration
or more compounds, each of which is effective
of rubber due to the action of light, heat and oxy
as an antioxidant when employed by itself. While
gen. It will be understood that by a secondary
this art is rather highly developed, those skilled
aromatic amine, I mean one in which both radi
in the art continue to search for improved anti
cals attached to the nitrogen atom are aromatic
oxidants and antioxidant compositions.
20 radicals. Particularly satisfactory antioxidants
It is an object of the present invention to pro
are—
vide an improved method of inhibiting the de
para,para'
-Dimethoxydiphenylamine
terioration of rubber. Another object is to pro
N ,N'-diphenyl-para-pheny1enediamine
vide a method for improving, or boosting, the ef
-phenyl-beta-naphthylamine
?ciency of secondary aromatic amine antioxi 25 N
Diphenylamine
dants in rubber. A further object is to employ,
The phthalocyanine compounds, which may be
with a rubber antioxidant, a compound which is
not an antioxidant for rubber but which in
creases the e?‘iciency of the rubber antioxidant.
A still further object is to provide new and im
employed in accordance with my invention, are
the metal-free phthalocyanines which consist of
carbon, hydrogen and nitrogen and the metal
proved rubber antioxidant compositions. Other
complexes thereof in which the metals are se
objects are to provide new compositions of mat
lected from copper, silver, tin, cobalt, nickel,
magnesium, zinc and aluminum. Certain other
ter and to advance the art. Still other objects
will appear hereinafter.
The above and other objects may be accom- @
phthalocyanines, such as the iron, lead and chro
mium phthalocyanines, do not have the property
of improving or boosting the e?iciencies of sec
ondary aromatic amine antioxidants and hence
plished in accordance with my invention which.
comprises incorporating in rubber a small pro
are excluded from my invention. The phthalo
portion of a secondary aromatic amine antioxi
cyanines, consisting of carbon, hydrogen and ni
dant and a small proportion of a phthalocyanine
consisting of carbon, hydrogen and nitrogen or 40 trogen, include phthalocyanine and the alkyl, aryl
of a metal complex of such a phthalocyanine
and aralkyl substituted derivatives of phthalo
cyanine, but exclude non-hydrocarbon substit
in which the metal is selected from copper, silver,
uents.
tin, cobalt, nickel, magnesium, zinc and alumi
num. The above and other objects may also be
The amount of phthalocyanine compound,
accomplished by mixing one of the aforesaid
which may be employed in accordance with my
phthalocyanines or meta1 complexes thereof with
invention, may be widely varied. Proportions of
a secondary aromatic amine rubber antioxidant
from about 0.00001% to about 1.0% of the
to provide a novel rubber antioxidant composition.
phthalocyanine compound, based on the rubber,
have been satisfactorily employed.
Larger
I have found that, by the. use of such phthalo
cyanine compounds with a secondary aromatic, 50 amounts may be employed if desired, but such
2,406,722
3
TABLE I
larger amounts will generally be wasteful as no
substantial improvement in results is obtained
with such larger amounts. Preferably, the
phthalocyanine compound is employed in the pro
portion of from about 0.00001% to about 0.1%
by weight, based on the rubber, as substantially
all of the boosting e?ect is obtained within such
range.
Unaged
Parts per
Compound 7
Co
In general, the antioxidantwill be em
Parts per E?iciency
oxi-
100 parts
dant
of rubber dant=l00)
None
________ __
er hthalocyanine 1.
P115019.
Anti-
100 parts
of rubber
0. 045
____
1.0
0.45
'
ployed in the proportion of about 0.25% to about
2.0% by Weight of the rubber. The e?ectiveness
(antioxi
150
l0
1.0
100
119
11
of the phthalocyanine compounds will vary some
137
142
what with their constitution and. also with the
antioxidant‘ employed. It will also generally be
desirable to Vary the amount of the phthalocya
110
100
113
110
4
100
nine compound with variations in the amount of
antioxidant employed. From about 0.0001 part ‘to
about 0.5 part of phthalocyanine compound may
be employed for each part of antioxidant. Usu
ally, it will be desirable to employ from about
0.0001 part to about 0.1 part of phthalocyanine 20
compound to each part of antioxidant. Prefer
ably, I employ from about 0.0001 part to about
0.01 part of phthalocyanine compound to each
part of antioxidant.
The phthalocyanine compound and the antioxi 25
12
1"Added directly‘ t'olthcirubber as a dispersion in rubber.
2 Dispersed in the antioxidant before addition to the rubber.
TABLE II
Flew-cracking resistance after being bomb aged
Partsper
Compound
dant may be added’ to the rubber together or
separately, it being immaterial which is addedv
?rst. However, I generally prefer to‘ mix the
phthalocyanine compound’ With- the antioxidant
Do‘ 1'__________ __
which is to be added to~the rubber.
,
Do 1;.
_of-rubber
dant
0. 045
._.
__._._._r___--._- ~
#1 _
1,0
150
(I45
#I
1.0
147
None
‘02075
#I'
______ __~__1
10
Tin chloride phthalocy-
'
,
‘
'
L-
.
127
. #11
120»
10
#1f ‘
100’
'#2
'
135v
#2‘ ‘
133'
None
nation D-430—35-T) of a rubber sample contain
ing a standard rubber‘ antioxidant tov that. of. a
similar rubber sample containing. the same ani
tioxidant plus aphthalocyanine of the described
class. The resistance. to ?ex-cracking was test.
ed before aging, after aging’ in the ‘70° C. oxygen.
bomb and in‘ the 70° C. air oven. All tests were
made in the following stock, which was cured
for 60 minutes at 25‘ pounds per square’ inch
steam pressure. The amounts are in parts by'
.
7'
#2
166
#2‘
150
#2- .
1'12
#2
132
#2- _
100
#3‘ '
_
134.
#3‘ '
137
#3
.
120'
#3 ~
100‘
#4‘
103
None
'
5
‘
#4'
133-’
None:
weight.
‘
6
#4
None
sheet. ____ __._____.__ _______ __.__,__.
(antioxi
of'rubber clant=l00)\
0145
The. efficiency of the antioxidant compositions
of my invention was determined by comparing
the resistance to ?ex-cracking on the: Du. Pont
Flexing Machine (see Method- C, ASTMZ, Desig
Smoked
Par-ts per E?iciency
ox-i- ' 'l00lparts‘
Copper phthalocyanine 1.
to-provide a new rubber antioxidant composition
Anti-
-100 parts
100
_> ________ __
10
100
Zinc oxide ___________________________ __
5
Channel black _______________________ _-
50
Stearic acid ______________ __. ____ __._____
3
Pine tar _____________________________ __
1.5
Sulfur
3“
______ __. _______ ________________ __
Accelerator1
________________ __.__- ____ __
1.25
Antioxidant
____ __- _______ __. __________ __
1.0
501
{Added directly to therubber as a dispersioninrubber. I
1 Dispersed in the antioxidant‘ b‘eforaadditi'on to the‘ rubber.
TABEEIII
Oven aged
55
Compound
7 'Parts per- ' Anti- .Barts per 'E?iciencvy
l00pa1‘ts" oxi; ‘100 parts ' (antioxiy
Booster _____________________ __-___ As‘ indicated
fotrubb'erti dant
ofru'bber. .dant=l00)
1A. mixture of the Zinc‘ salt of. mercaptobenzothiaizole,
9% inert hydrocarbon and 9%> diortho-tolylguanidine;
In the following tables are listed‘ the efficiencies
of phthalocyanine. and certain metal derivatives
_
of phthalocyanine. The e?iciency is expressed in
Copper phthalocyanine"
terms of‘ the standard’ antioxidant having an ef
Tin chloride phthalocy-
ficiency of 100, that is, the antioxidant plus boost
er is compared directly to' the antioxidant alone.
The antioxidants in the tables: are- designated: by
numbers wherein
#1=para,para' -dimethexydiphenylamine V
#2=para,para' - dimethoxydiphenylamine+
N,N' -diphenyl~para-phenylenediamine+~
N-phenyl-beta‘-naphthylamine
#3 =N—phenyl-beta-naphthylamihe
#4=Diphenylamine
'
#2- .
1Z0-
#2
1.0
None
#2‘
0:045
o_____.__.,_>_____v______'
05
7
0.45
.
anine.__ ________ ._
-
Do__._____._-..._
_-;
Cobalt phthalocyanine“
D0...v ________ __
_
,
~. ....... __
‘
1.0
#l' -
‘ None
V
1.0 >
__.1 _______ _.
.
107.
108
7
l7
100.
140"
,20
v
0075-
#1
'1
1‘46
0._25. jNone" ,
0.075‘ I
0:25
-
g
p #1
‘22*
127
None‘
18"
#1
188_E
1 None» _
20
V
#1 j
> None .
208;
29.
»
100
#1
' None
_
From‘. the; above tests: and‘ results,
_20'“
will heap-
parent that? the phthalocyanine compounds of;
2,406,722
5
my invention are substantially ineffective as anti
6
about 0.1% by weight, based on the rubber, of
oxidants by themselves, but that small amounts
phthalocyanine.
are extremely effective for increasing the anti
oxidant power of secondary aromatic amine anti
ll. The method of inhibiting the deterioration
of rubber which comprises incorporating in the
oxidants.
rubber a small proportion of a secondary aromatic
-
It will be understood that the above tests and
speci?c embodiments are given for illustrative
purposes solely and that many variations and
modi?cations can be made in the phthalocya
nines, antioxidants and other ingredients of the
rubber compositions employed without departing
from the spirit or scope of my invention.
For
example, other secondary aromatic amine rubber
antioxidants, such as N-phenyl-alpha-naphthyl
amine antioxidant and from about 0.00001% to
about 0.1% by weight, based on the rubber, of a
copper complex of a phthalocyanine consisting
of carbon, hydrogen and nitrogen.
5. The method of inhibiting the deterioration
of rubber which comprises incorporating in the
rubber a small proportion of a secondary aromatic
amine antioxidant and from about 0.00001% to
about 0.1% by weight, based on the rubber, of
amine, the alkoxydiphenylamines, the alkenoxy 15 copper phthalocyanine.
diphenylamines, the alkoxyphenyl-naphthyl
6. Rubber having incorporated therein a small
amines, the alkenoxyphenyl-naphthylamines,
proportion of a secondary aromatic amine anti
N ,N’-diphenyl-para-phenylenediamine and N,N'
oxidant and from about 0.00001% to about 0.1%
diphenyl-benzidine, may be employed in place of
by weight, based on the rubber, of a member of
the antioxidants used in the above tests. iAC
the group consisting of phthalocyanines which
cordingly, my invention is not to be limited to the
consist of carbon, hydrogen and nitrogen and
speci?c embodiments particularly disclosed, but
metal complexes of such phthalocyanines which
I intend to cover my invention broadly as in the
consist of carbon, hydrogen and nitrogen in which
appended claims.
the metals are selected from the class consisting
It will be apparent that, by my invention, I
have discovered a class of phthalocyanine com
pounds which, when incorporated in rubber with
a secondary aromatic amine rubber antioxidant,
Will very materially improve the ef?ciency of the
antioxidant. Mixtures of the phthalocyanine
compounds and the antioxidants constitute novel
rubber antioxidant compositions which are un
usually and unexpectedly effective for inhibiting
the deterioration of rubber. Therefore, by the
practice of my invention, it is possible to obtain
much greater protection of the rubber with any
particular amount of secondary aromatic amine
antioxidant. Also, by the use of my invention,
it is possible to obtain a desired amount of pro
tection of the rubber with materially smaller
amounts of antioxidant. These results are ob
tained by the use of phthalocyanines which have
of copper, silver, tin, cobalt, nickel, magnesium,
zinc and aluminum.
7. Rubber having incorporated therein a small
proportion of a secondary aromatic amine anti
oxidant and from about 0.0000l% to about 0.1%
by weight, based on the rubber, of a phthalocya
nine consisting of carbon, hydrogen and nitrogen.
8. Rubber having incorporated therein a small
proportion of a secondary aromatic amine anti
oxidant and from about 0.00001% to about 0.1%
by weight, based on the rubber, of phthalocya
nine.
.
9. Rubber having incorporated therein a small
proportion of a secondary aromatic amine anti
oxidant and from about 0.00001% to about 0.1%
by weight, based on the rubber, of a copper com
plex of a phthalocyanine consisting of carbon,
hydrogen and nitrogen.
substantially no antioxidant effect when employed
10. Rubber having incorporated therein a small
by themselves, that is, in the absence of an anti
proportion of a secondary aromatic amine anti
oxidant. My invention is of particular value in 45 oxidant and from about 0.00001% to about 0.1%
colored rubber stocks as the phthalocyanine com
by weight, based on the rubber, of copper phthalo
pounds employed are colored and tend to color
cyanine.
white or light colored rubber stocks. However,
11. A rubber antioxidant composition compris
where the coloring effect of the phthalocyanine
ing a mixture of 1 part of a secondary aromatic
compound is unobjectionable, it may be satisfac 50 amine antioxidant and from about 0.0001 to about
torily employed in white and light colored rubber
0.5 part of a member of the group consisting of
stocks.
phthalocyanines which consist of carbon, hydro
I claim:
gen and nitrogen and metal complexes of such
1. The method of inhibiting the deterioration
phthalocyanines in which the metals are selected
of rubber which comprises incorporating in the 55 from the class consisting of copper, silver, tin,
rubber a small proportion of a secondary aromatic
cobalt, nickel, magnesium, zinc and aluminum.
amine antioxidant and from about 0.00001% to
12. A rubber antioxidant composition compris
about 0.1% by weight, based on the rubber. of a
ing a mixture of 1 part of a secondary aromatic
member of the group consisting of phthalocya
amine antioxidant and from about 0.0001 to about
nines which consist of carbon, hydrogen and 60 0.5 part of a phthalocyanine consisting of carbon,
nitrogen and metal complexes of such phthalo
hydrogen and nitrogen.
cyanines in which the metals are selected from
13. A rubber antioxidant composition compris
the class consisting of copper, silver, tin, cobalt,
ing a mixture of 1 part of a secondary aromatic
nickel. magnesium, zinc and aluminum.
amine antioxidant and from about 0.0001 to about
2. The method of inhibiting the deterioration 65 0.5 part of phthalocyanine.
of rubber which comprises incorporating in the
14. A rubber antioxidant composition compris
rubber a small proportion of a secondary aro
ing a mixture of 1 part of a secondary aromatic
matic amine antioxidant and from about
amine antioxidant and from about 0.0001 to about
0.00001% to about 0.1% by weight, based on the
0.5 part of a copper complex of a phthalocyanine
rubber, of a phthalocyanine consisting of carbon, 70 consisting of carbon, hydrogen and nitrogen.
hydrogen and nitrogen.
15. A rubber antioxidant composition compris
3. The method of inhibiting the deterioration
ing a mixture of 1 part of a secondary aromatic
of rubber which comprises incorporating in the
amine antioxidant and from about 0.0001 to about
rubber a small proportion of a secondary aromatic
0.5 part of copper phthalocyanine.
amine antioxidant and from about 0.00001% to 75
JOHN R. VINCENT.
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