close

Вход

Забыли?

вход по аккаунту

?

Патент USA US2134139

код для вставки
Patented Oct. 25, 1938
2,134,139‘
UNITED STATES;
PATENT OFFICE
2,134,139
PRESERVATION OF RUBBER
George D. Martin, Nitro, W. Va., assignor, by
mesne assignments, to Monsanto Chemical
Company, Wilmington, Del., a corporation of
Delaware
No Drawing. Application June 15, 1935,
Serial No. 26,870
18 Claims.
A
The present invention relates to the art of
rubber manufacture, and particularly relates to
the preparation of rubber compositions which
resist deterioration
to the atmosphere.
such deterioration
treating the rubber
(CI. 18—50) '
phenylene diamine, formaldehyde and glycerine;
reaction product of diphenyl-p-phenylene di
amine, formaldehyde and methyl alcohol; re
due to aging or to exposure ‘ action product of diphenyl-p-phenylene diamine,
It has long been known that formaldehyde and amyl alcohol; reaction prod
can be greatly retarded by uct of diphenyl-p-phenylene diamine, formalde
either before or after vulcan
hyde and cyclohexanol; reaction. product of di
ization with certain substances known as age
resistors or antioxidants. One object of this in
10. vention is to provide a new and superior class of
phenyl-p-phenylene diamine, formaldehyde and
lauryl alcohol; reaction product of diphenyl-p
phenylene diamine,vv formaldehyde and benzyl 10
antioxidants for rubber. A further object of this
alcohol; reaction product of diphenyl-meta
invention is to provide a new and superior class
of materials which when incorporated into rub
phenylene diamine, formaldehyde‘and butyl alco
ber, preferably before the vulcanization thereof,
imparts thereto properties markedly resistant to
tear and cracking when portions thereof have been
repeatedly and alternately stretched and the ten
sion removed. Such a process is analogous to the
?exing of an automobile tire in actual road service.
The age resisting characteristics of a vulcan
ized rubber product can be readily ascertained by
subjecting samples of the vulcanized product in
a bomb to the action of oxygen under elevated
pressure and at an elevated temperature. The
aged rubber samples are then examined and
hol; reaction product of diphenyl-o-phenylene
diamine, formaldehyde and lauryl alcohol; re
action product of dibeta naphthyl-p-phenylene
diamine, formaldehyde and butyl alcohol; re
15
action product of di ortho tolyl-p-phenylene
diamine, formaldehyde and butyl alcohol; re
action product of diphenyl-p-phenylene diamine,
butyl aldehyde and butyl alcohol.
.
20
In place of the alcohols hereinbefore set forth
I may employ heptyl alcohol, octyl alcohol, cetyl
alcohol and analogous alcohols. In place of the
amines hereinbefore set forth I may use di alpha
tested and the test data compared with the re
naphthyl-p-phenylene diamine, di biphenyl-p 25
phenylene diamine and analogues and chemical
sults obtained on testing the unaged rubber sam
ples. The deterioration in properties effected as
a result of the oxidation treatment is indicative
hydes as for example acetaldehyde, propionalde
hyde and the like maybeemployed in the prepa
30 of the result that would normally be expected
of that particular stock during actual service.
Such a test is .known as the Bierer-Davis aging
test and produces an effect on a vulcanized rub
ber stock comparable with that resulting from"
(20 UL several years of natural ageing of the rubber de
pending upon the condition of the test. In all the
oxygen bomb tests hereinafter set forth, the aging
Was carried out at temperatures of 70° C. and an
oxygen pressure of 300 pounds per square inch.
The ?ex cracking resistance of the vulcanized
~10
rubber products was determined on a flexing ma
chine as set forth by L. V. Cooper, Analytical
Edition of Industrial 8; Engineering Chemistry,
vol. 2, No. ll, 1930, pages 391-394.
'
According to the present invention, a new class ’
of anti-oxidants or age-resisters has been found
which, upon incorporating into a rubber stock,
equivalents thereof.
Again the use of other alde
ration of the new and preferred class of com
pounds.
.
I
The compounds falling within the scope of the
present invention‘may be prepared by reacting
equi-molecular proportions of amine,vformalde—
hyde and alcohol or by reacting one molecular 35
proportion of amine with substantially two mo
lecular proportions each of formaldehyde and
alcohol. Any one or a mixture of the above
enumerated substances or of these substances
with other anti-‘oxidants may be incorporated
into rubber ‘with good effect on its properties.
The compounds of the present invention are be
40
lieved'to possess the following structural formula:
R
.
lay-HI
45
imparts exceptional age resisting and ?ex crack
ing resistance to the vulcanized rubber product.
The compounds herein disclosed as imparting
such desirable properties to vulcanized rubber
comprise the products obtainable by reacting a
diaryl phenylene diamine with an aldehyde and
an alcohol.
For example, the following are typical members
of the new and preferred class of materials which
has beennprepared and tested in the manner
hereinbefore set forth: Reaction product of di
phenyl-p-phenylene diamine, formaldehyde and
butyl alcohol; reaction product of diphenyl-p
50
wherein R is an aromatic radical, R’ is alkyl,
aralkyl or aryl, Y is a methylene or alkylidene
radical, and X isrhydrogen or a Y O R’ group, 55
although the invention is not limited as to any
possible structure of the new compounds.v
The following are to be understood as illustra
tive only and not in any sense vlimitative of the
scope of the present invention.
60
2
2,134,139
Example I
260 parts by weight of diphenyl-p-phenylene
diamine (substantially one molecular proportion) ,
200 parts by weight of 40% formaldehyde solu
tion (substantially a 33% excess over two molec#
ular proportions) and 200 parts by weight of
n-butyl alcohol (substantially a 33% excess over
two molecular proportions) were reacted in the
presence of a suitable solvent, as for example
benzene, and a suitable condensing agent, as for .
example sodium carbonate, by re?uxing said
reactants. After re?uxing for substantially 2 to
4 hours, the oily top layer was separated off,
washed with water, and the benzene distilled
15 therefrom, whereupon a high yield of a brown
viscous oil was obtained. It is thought the fol
lowing reaction takes place as‘ indicated by
McLeod and Robinson, Journal of the Chemical
Society, vol. 119 (1921) page 1471;
20
25
7
shown that‘the new and preferred class of ma
terials possess exceptionally strong antioxidant
action when employed in a typical rubber tread
stock. An important improvement of the new
class. of antioxidants, for example the reaction
product of diphenyl-p-phenylene diamine, formal
dehyde and n-butyl alcohol described above over a
diaryl-phenylene diamine, for example diphenyl
p-phenylerle diamine, is that of decreased bloom
10
ing to the surface of the vulcanized rubber prod
uct. This fact is of great value to the rubber
trade. Another important advantage in the use
of the preferred class of materials, for example
the reaction product of ,diphenyl-p-phenylene di 15
amine, formaldehyde and butyl alcohol over the
use of a diaryl-phenylene diamine, for example
diphenyl-p—phenylene diamine, in particular
when employed in a so-called gum stock, lies in
the fact that the initial cures are retarded, 20
whereas at the optimum cures activation is
effected. Furthermore, from a “scorch” stand
point the new and preferred class of materials
show a greater ease of handling and greater re
sistance vto “scorch” than do stocks employing 25
a diaryl phenylene diamine, for example diphenyl
p-phenylene diamine. Furthermore, on ?exing
the cured rubber product in the manner above de
scribed, it was found to be markedly superior in
0
NH
'
From the data set forth in Table I it is readily
?ex cracking resistance to a similar stock con
taining no antioxidant.
30
»
A stock was compounded comprising: '
Parts
The product prepared as'described was incor
35 porated in a typical rubber tread stock compris
ing:
Smoked sheet rubber___ ______ _-__' _______ __ 100
Carbon
45
“P33? carbon black ____________________ __
40
Zinc oxide ____________________________ __
5
black _________________________ __
50
oxide _____________________ _'_ _____ __
5
Sulfur __________ _; ________________ __‘____
3
Stearic acid ___________ _; _______________ __
3
Pine
2
tar ______________________ __, ______ __
Sulfur; _______________________________ __
0.8
Benzothiazyl ester of thiobenzoic acid..-"
2.0
Diphenyl guanidine phthalate __________ __
0.8
Stearic acid ____________________________ __
1.0
alcohol described above ______________ __
0.8
The stock so compounded was vulcanized and
0.2
portions of the cured rubber product were elon
gated 50% and heated at 121° C. under an air
molecular
proportion
of diphenyl-p- '
pressure of 100 pounds per square inch.
phenylene diamine and substantially‘ two
molecular proportions each of, formalde
hyde and n-butyl alcohol___V_'___-_ ____ __
1.0
'
96 hours at a temperature of ‘70° C. and an
oxygen pressure of 300 pounds of oxygen per
square inch. A comparison between the aged and
unaged rubber product is given in Table I.
60
Table .I
ins.
Lbs.
Hrs
steam
pressure
'
aged
ticity in lbs/in.2 at
elongotions ol—
M
labs
ins.
seam
Hrs
17
‘
500
7
700
Ult.
break in
elong.,
lbs/in.2
percent
a
50
V0
1120
2750
3150
730
6
50
8
1160
_______ __
2480
675
Modulus of elas
9
50
0
1170
2905
3485
770
ticity in lbs/in.2 at
9
50
8
1060
_______ __
2150
665
760
(7
300
0
7
500
_
0
Tensile at
Ult.
12
50
0
1105
2830
v 3415
break in
elong.,
12
50
8
095
2250
2250
700
lbs/1n.z
percent
15
50
0
1085
2830
3240
735
15
50
8
095
_______ __
1920
065
0
75
30
0
2055
3980
4145
75
30
06
2165
_______ __
2830
90
90
a0
30
' o
96
2130
2180
4150
_______ _-
4150
2610
'
'
0
I
Tensile at
aged
elongations of-.—
M
Cure
pressure
65
535
'
~
that rubber stocks containing small proportions
500
365
of the new and preferred class of antioxidants
resist to a marked degree the extremely ex
105
30
0
2210
4060
4060
500
30
96
2520
_______ __
2540
345
00
65
It is seen from the above results of the test
410
105
50
Table II
Modulus of elas
vulcanized product were then arti?cially aged
by heating in the Bierer-Davis oxygen bomb for
Oure
A com
parison between the unaged and aged vulcanized
rubber products follows in Table II.
The rubber stock so compounded was vulcanized
in the well known manner and portions of the
75
1.5
Benzothiazyl ester of thiobenzoic acid____
guanidine ___________________ __
40
The reaction product of diphenyl-p-phenyl
ene diamine, formaldehyde and butyl
Diphenyl
The reaction product of substantially one
70
35
‘
Parts
_ Zinc
Smoked sheet rubber __________________ __ 100
aggerated aging conditions of the air bomb tests
described above. An identical stock with that de
described above with the exception that it con 75
2,134,139
tains no antioxidant will disintegrate when sub
jected to the conditions of the test set forth above.
Table IV
ticity in s 7319.3
in!
MOdlllllS]%f
Example ‘II
Cure
at elongetions
As another example of the use of the preferred
class of antioxidants, a reaction product was
of-
10
analogous to that described above in Example I.
A wax-like product so obtained, distilling at
Ult.
at break el0ng.,
in lbs/in.2 percent
prepared by reacting substantially equi-molecu
lar proportions of diphenyl-p-phenylene diamine, '
formaldehyde and methyl alcohol in a manner
.
Tensile
Mins.
Lbs.
steam
Hrs
a ed‘
200%
‘pressure g_
400%
00
30
0
1310
3160
4070 ~
530
60
30
96
1418
2970
2865
415
235°-238° C. at 3 m. In. pressure, was incorporated
in a rubber stock comprising:
15
'
/
Parts
Smoked sheet rubber ___________________ __ 100
Carbon black ___________________________ __
50
Zinc oxide ____________________________ _5
Sulfur ________________________________ __
3
.Pine tar ______________________________ __
Stearic acid __________________________ __
2
3
75
30
0
1320
75
30
96
1485
90
30
0
1415
90
30
96
1585
3110
_______ __
3435
_______ ..
3890
500
2630
355
3975
480
2490
330
Flexing tests on the unaged stocks and on the’
stocks after aging for 3 days in the Geer oven
at 70° C. showed the stocks to ?ex exceptionally 20
well.
Example IV
Benzothiazyl ester of thiobenzoic acid_____
0.8
Diphenyl guanidinein ______ -I __________ __
0.2
The antioxidant described above ________ __
1.0
Substantially one molecular proportion of di
phenyl-p-phenylene diamine was reacted ‘with
The rubber stock was vulcanized and portions of
the cured rubber product aged in the Bierer
substantially two molecular proportions of 40%
formaldehyde solution and substantially two
Davis oxygen bomb in the manner described
above. A comparison between the aged and un
aged rubber product is given‘in Table III.
molecular proportions of cyclohexanol in a man
ner analogous to that employed for Example I
described above. The viscous reaction product
so obtained was milled into a typical tread stock
comprising:
Table III
Parts
Smoked sheet rubber __________________ __' 100
Modulus of elas
Cure
ticity in lbs/in.2 at
elongations of—
Carbon black __________ _: ______________ __
_
Tensile
at break elong..
in lbs/in.2 percent
Lbs
Mins.
steam
pressure
Ult.
552%
300%
500%
40
70
30
0
2205
4000
70
30
96
2320
90
30
0
2130
90
30
06
2300
105
30
0
' 2310
105
30
96
2410
50
Zinc oxide ____________________________ __
5
Sulfur_____ ____________________________ __
Pine tar ______________________________ __
3
2
Stearic
3
acid __________________________ __
Benzothiazyl ester of thiobenzoic acid_____
0.8
Diphenyl guanidine _____________________ _ _
0.2
1.0
4180
520
_______ -_
3000
410
The antioxidant described above ________ __
4060
4085
505
The compounded rubber stock was vulcanized
and the cured rubber product aged in the Biere
Davis oxygen bomb. A ccmparison was made
between the modulus and tensile properties of
the unaged and aged cured rubber product with
the results given in Table V.
_______ _ _
2760
360
4200
4200
500
_______ __
2690
330
Fl'exing tests on the above unaged stocks and
also on the above stocks aged for 3 days in the
Table V
Geer oven at 70° C. showed them to possess ex
cellent ?exing properties.
Example III
lgioztluluslzéf
elas
ici yin s/in.2
Cure
Substantially one molecular proportion of di
phenyl-p—phenylene diamine was reacted with
substantially two molecular proportions each or"
amyl alcohol and 40% formaldehyde solution in
at elongaticns
0f‘
Mins.
Lbs‘
steam
pressure
Hrs
awed‘
200%
_
60
60
Parts
75
30
0
1350
75
30
96
1488
90
30
0
1440
90
30
96
1468
Zinc oxide ____________________________ __
5
Sulfur___'_ _____________________________ .. ‘
3
Pine tar ______________________________ __
2
Stearic acid __________________________ __
3
Benzothiazyl ester of thiobenzoic acid_____
0.8
Diphenyl guanidine ____________________ __
0.2
The antioxidant described above ________ __
1.0
The rubber stock so compounded was vulcanized
and aged in the Bierer-Davis oxygen bomb. A
comparison between the aged and unaged rubber
_.product is given in Table IV.
Ult.
along,
30
30
400%
B
a manner analogous to that set forth above for
Example I. The dark brittle resin so obtained
60 was incorporated in a tread stock comprising:
Smoked sheet rubber __________________ __ 100
Carbon black __________________________ __ 50
Tensile
at break
in lbs/in? percent
0
96
1275
1340
3170
2770
3165
_______ ._
3300
_______ __
4020
2820
525
405
3830
495
2580
365
3730
460
2205
320
The above stocks also showed good ?exing prop
erties, both when unaged and after aging for 3
days in the Geer oven at 70° C.
Example V
As another example of the preferred new anti
oxidants substantially equi-molecular propor
tions of diphenyl-p-phenylene diamine, 40%
formaldehyde and lauric alcohol were reacted in a
manner analogous to that described above for
4
2, 134,139 .
Example I. The oily reaction product was in
above on the unaged cured rubber product and on
stock comprising:
the same cured rubber product after aging in the
Geer oven for 3 days at 70° C. showed the re
Parts
Smoked sheet rubber __________________ __ 100
10
Flexing tests carried out in the manner described
corporated in the well known manner in a tread
Carbon black __________________________ __
Zinc oxide ____________________________ __
50
5
Sulfur ________________________ ___ _______ ..
3
action product employed in Example VI to have
excellent ?exing properties.
Example VII
Pine tar ______________________________ __
2
Substantially one molecular proportion of di
Stearic acid __________________________ __
3
' phenyl-p-phenylene diamine was reacted with 10
Benzothiazyl ester of thiobenzoic‘ acid"---
0.8
Diphenyl guanidine ____________________ __
The antioxidant described above ________ __
0.2
1.0
After vulcanizing the rubber stock was aged in
the Bierer-Davis oxygen bomb with the folloW-_
ing results:
substantially two molecular proportions each of
butyl aldehyde and butyl alcohol in a manner
analogous to that employed in Example I, with
the exception that calcium chloride was employed
as the‘catalyst.
The product so obtained was in
Parts
Table VI
Smoked sheet rubber __________________ __ 100
Carbon black ___________________________ __ 50
Moduluslrgf
ticity in s lelas
in.2
at elongations
Cure
°f—
Zinc
Tensile
at break
Ult.
elong.,
inlbs/in.2 percent
_
Lbs.
Mins.
steam
pressure
rs
a ed
g
60
60
30
30
75
30
0
1215
75
30
96
1260
90
30
0
1345
30
96
90
V
0
90
200%
400%
1208
1228
2990
2405
4025
2590
530
420
3095
3820
500
_______ A
3275
1323 '
15
corporated in a tread stock comprising:
_______ __
2450
380
3885
475
2205
345
oxide _____________________________ __
5
Sulfur _________________________________ __
3
Pine tar ________________________________ __
Stearic acid ____________________________ _._
Mercapto-benzo-thiazole ________________ __
2
3
1
The antioxidant described above _________ __
1
20
25
After vulcanizing the cured rubber stock was aged
in the Bierer-Davis oxygen bomb and the results
obtained as given in Table VIII.
30
Table VIII
Flexing tests carried out in the manner described
above on the unaged cured rubber stock and on
the same stock after aging 3 days in the Geer
oven at 70° C. showed the product set. forth in
Example V to have particularly good ?exing prop
Moduluslgf
elas
ticity in sin."
at elongations
Cure
°f—
Tensile
at break
on.
elong.
35
inlbs/in.2 percent
Mins.
Lbs.
Hrs
steam
pressure
3 ed
g
200%
400%
erties.
Example VI
Substantially equi~molecular proportions of di
phenyl-p-phenylene diamine, formaldehyde and
benzyl alcohol were reacted in a manner'ana
logous to that employed in Example I. The res
inous product so obtained was incorporated in
the usual manner in a tread stock comprising:
Parts
Smoked sheet rubber ______ __' __________ __ 100
Carbon
Zinc
black _________________________ __
50
oxide ____________________________ __
5
Sulfur ________________________________ __
3
Pine
2
tar____
_
__
Stearic acid ___________________________ __
3
Benzothiazyl ester of thiobenzoic acid____
0.8
Diphenyl guanidine ____________________ __
The antioxidant described above ________ __
0.2
1.0
After vulcanizing the rubber stock was aged in
the Bierer-Davis oxygen bomb and the results
obtained as given in Table VII.
Table VII
0f‘-
Tensile
at break
65
Mins.
60
60
75
Ult.
along,
in lbs/in.2 percent
Lbs.
steam
pressure
30
30
Hrs
a ed
g
200%
30
60
30 ,
75
30
75
30
r
0
1500
96
1-100
3660
_______ ._
4005
430
1955
280
0
1550
3720
4100
450
96
1358
_______ _.
1765
270
40
Among other examples prepared and on testing 45
found to possess the desirable antioxidant and
?exing properties'typical of the class is the re
action product of diphenyl-p-phenylene diamine,
formaldehyde and glycerine.
From the data hereinbefore set forth it is read
ily shown that the preferred class of compounds
comprises an important class of rubber antioxi
dants which markedly resist the deterioration
in?uences due to heat, oxidation and ?exing.
In the preparation of the new and preferred
class of chemical products, other methods may
be employed which are clearly apparent to those
skilled in the art to which the invention pertains
inview of the present disclosure. Thus, other
condensing and/or dehydrating agents, as for 60
example anhydrous calcium chloride have been
so employed.
ticity in s elas
in.2
Modulusloof
at elongations
Cure
60
Obviously, practice of the present invention is
not limited to the speci?c compositions given
above, such compositions being merely illustrative 65
of the manner of employing the antioxidants or
age-resistors of this invention. The antioxi
400%
dants or age-resistors may be employed in con
0
90
1230
1385
75
30
0
1255
75
30
96
1418
90
30
0
1360
90
30
96
1438
3085
2760
3140
_______ __
3310
_________.
4055
2780
530
405
3865
505
2040
380
3900
475
2350
335
junction with other vulcanizing agents than
those speci?cally disclosed, for this invention is 70
applicable generally to pure rubber or rubber
compositions of the most varied nature. Fur
thermore, the preferred class of materials may
be employed in rubber stocks in conjunction with
other accelerators than the one speci?cally shown
2,134,139
with varying differences in tensile and modulus
properties but still exhibiting the desirable qual
ities of the class. Thus, for example the anti-~
oxidants of the present invention have been em
ployed in-a stock in which mercaptobenzothiazole
was used as the accelerator, and the vulcanized
rubber product found to possess the desirable
aging, ?exing and like properties typical of the
new class of compounds.
10
,
It is to be understood that the term “treating”
as employed in the appended claims is used in a
5
tainable by reacting substantially one molecular
proportion of N, N’ diphenyl-p-phenylene di
amine with substantially two molecular propor
tions each of formaldehyde and .n-butyl alco
hol in the presence of a condensing agent;
a 8. The method of preserving rubber which
comprises treating rubber with a reaction product
obtainable by reacting substantially one molecu
lar proportion of N, N’ diphenyl-p-phenylene
diamine with substantially two molecular ‘pro 10"
portions each of formaldehyde and amyl alcohol
generic sense to include either the incorporating
of the preferred class of materials into the rub—
ber by milling or similar process, or their addi
15 tion to the rubber latex before its coagulation,
or to the application thereof to the surface of a
mass of crude or vulcanized rubber. The term
“rubber” is likewise employed in the claims in a
generic sense to include caoutchouc, whether nat
in the presence of a condensing agent.
20 ural or synthetic, reclaimed rubber, balata, gutta
10. The vulcanized rubber product produced 20
by heating rubber and sulfur in the presence of
a product obtainable by reacting substantially one
molecular proportion of a N, N’ diaryl phenylene
diamine with not more than substantially two
molecular proportions each of an aliphatic alde 25
percha, rubber isomers and like products whether
or not admixed with ?llers, pigments or accelerat
ing agents.
'
This application is a continuation in part of
25 my prior application Serial No. 728,753, ?led June
2, 1934.
The present invention is limited solely by the
claims attached hereto as part of the present
speci?cation.
.
9. The method of preserving rubber which
comprises treating rubber with a reaction prod
uct obtainable by reacting substantially one mo 15
lecular proportion of N, N’ dipheyl-p-phenylene
diamine with substantially one molecular propor
tion each of formaldehyde and lauryl alcohol in
the presence of a condensing agent.
hyde and an alcohol in the presence of a con
densing agent.
11. The vulcanized rubber product produced
by heating rubber and sulfur in the presence of
What is claimed is:
_1. The method of preserving rubber which
comprises treating rubber with a product ob
tainable by reacting substantially one molecular
proportion of a N, N’ diaryl phenylene diamine
35 with not more than substantially two molecular
proportions each of an aliphatic aldehyde and
stantially one molecular proportion of a N, N’
diaryl phenylene diamine with not more than
substantially two molecular proportions each
of formaldehyde and an alcohol in the presence
of a condensing agent.
an alcohol in the presence of a condensing agent.
2. The method of preserving rubber which com
heating rubber and sulfur in the presence of a
?prises treating rubber with a reaction product
40 obtainable by reacting substantially one molecu
lar proportion of a N, N’ diaryl phenylene dia
a reaction product obtainable by reacting sub
12. The vulcanized rubber product produced by
reaction product obtainable by reacting substan
tially one molecular proportion of N, N’ diphenyl
p-phenylene diamine with not more than sub
40
stantially two molecular proportions each of
mine with not more than substantially two mo
formaldehyde and an alcohol in the presence of
lecular proportions each of formaldehyde and
a condensing agent.
13. The vulcanized rubber product produced
an alcohol in the presence of a condensing agent.
3. The method of preserving rubber which com
45
prises treating rubber with a reaction product
30
by heating rubber and sulfur in the presence of a 45
reaction product obtainable by reacting substan
obtainable by reacting substantially one molecu
tially one molecular proportion of a N, N’ diaryl
lar proportion of N, N’ diphenyl-p-phenylene phenylene diamine with substantially two molec
diamine with not more than substantially'two' ular proportions each of formaldehyde and an
molecular proportions each of formaldehyde and ' alcohol in the presence of a condensing agent.
an alcohol in the presence of a condensing agent.
14. The vulcanized rubber product produced
4. The method of preserving rubber which com
by heating rubber and sulfur in the presence of a
prises treating rubber with a reaction product reaction product obtainable by reacting substan
obtainable by reacting substantially one molecu
tially one molecular proportion of a N, N’ di
lar proportion of a N, N’ diaryl phenylene dia
phenyl phenylene diamine with substantially two 55.
mine with substantially two molecular propor
molecular proportions each of formaldehyde and
tions each of formaldehyde and an alcohol in the
presence of a condensing agent.
5. The method of preserving rubber which com
60 prises treating rubber with a reaction product
obtainable by reacting substantially one molecu
lar proportion of a N, N’ diphenyl phenylene di
amine with substantially two molecular propor
tions each of formaldehyde and an aliphatic al
65 cohol in the presence of a condensing agent.
6. The method of preserving rubber which'com
prises treating rubber with a reaction product
obtainable by reacting substantially one molecu
lar proportion of N, N’ diphenyl-p-phenylene di
amine with not more than substantially two mo
an aliphatic alcohol in the presence of a con
densing agent.
15. The vulcanized rubber product produced
by heating rubber and sulfur in the presence of a 60
reaction product obtainable by reacting substan
tially one molecular proportion of N, N’ diphenyl
p-phenylene diamine with not more than sub
stantially two molecular proportions each, of
formaldehyde and butyl alcohol in the presence 65
of a condensing agent.
16. The vulcanized rubber product produced by
heating rubber and sulfur in the presence of a
reaction product obtainable by reacting substan
butyl alcohol in the presence of a condensing
tially one molecular proportion of N, N’ diphenyl 70
p-phenylene diamine with substantially two mo
lecular proportions each of formaldehyde and
agent.
n-butyl alcohol in the presence of a condensing
lecular proportions each, of formaldehyde and
7. The method of preserving rubber which com
75 prises treating rubber with a reaction product ob
agent.
17. The vulcanized rubber product produced 75
'6
2,134,139
by heating rubber and sulfur in the presence of
a reaction product obtainable by reacting sub
_ ,stantially one molecular proportion of N, N’ di
by heating rubber and sulfur in the presence of
a reaction product obtainable by reacting sub
. stantially one molecularrproportion of N, N’ di
phenyl-p-phenylene diamine with substantially
two molecular proportions each of Vformaldehyde one molecular proportion each of formaldehyde
and amyl ~alcohol in the presence of a condensing and lauryl alcohol inrthe presence of a condensing
phenyl-p-phenylene diamine with substantially
agent.
18. The vulcanized rubber product produced
‘agent,
‘
_
GEORGE D. MARTIN.
Документ
Категория
Без категории
Просмотров
0
Размер файла
779 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа