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Патент USA US2412984

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Patented Dec. 24, 1946
2,412,984
UNITED STATES ‘PATENT OFFICE
2,412,984
VULCANIZATION 0F RUBBER
William H. Hill, Mount Lebanon, Pa.', assignor,
by mesne assignments, to Koppel-s Company,
Inc., a corporation of. Delaware
.
..
No Drawing. Application May 24, 1944,
‘
’
Serial No. 537,178
21 Claims.
1
The present invention relates to vulcanization
of rubber and to rubber compositions or such
compositions vulcanized in the presence of ac
celerators, and of accelerators and activators
herein described.
.
In connection with the present invention it
has been found that aldehyde condensation
products of amidine thiocyanates are highly de
sirable agents in vulcanization accelerators and
particularly as activators for accelerators such
as thiazole accelerators including mercapto-aryl
(Cl. 260-797)
2
in an open vessel. This is particularly desirable
if a hard, pulverizable resin product is to be
obtained for easier incorporation in ‘a rubber
5 mix.
. Other aldehydic substances‘ that are employed
besides those mentioned above in the preparation
of the condensation products, are acrolein, ben
zaldehyde, furfuraldehyde, and polymeric alde
10 hydes.
'
To illustrate the present invention, the follow
thiazoles, benzo-thiazyl thiobenzoate, dibenzo
thiazyl disul?de and others. The above-men
tioned condensation products have in themselves
accelerating properties, and in addition it is noted
.
after re?uxing, heat is applied to the material
ing compositions were prepared:
that they are particularly valuable for com 15
mercial purposes as activators for accelerators in
Composition,
parts by
weight
various rubber stocks.
Examples of the condensation products em
ployed in the rubber vulcanization to be described,
A
include diphenyl guanidine thiocyanate formal 20 Rubber ____________ ._
dehyde condensation product, diphenyl guanidine
Zinc oxide.___ _
thiocyanate acetaldehyde condensation product,
diphenyl guanidine thiocyanate crotonaldehyde
condensation product, diphenyl guanidine thio 25 Activator
B
100
Carbon black ______ __
_ _____ ._
_
cyanate butyraldehyde condensation product,
such alkaryl guanidine thiocyanate aldehyde
condensation‘products as diorthotolyl guanidine
“Ureka C” represents an example of a thiazole,
thiocyanate formaldehyde condensation product
and dixylylguanidine thiocyanate formaldehyde 30 namely, benzothiazolethiol benzoate.
Any of the amidine thiocyanate aldehyde con-r
condensation product, and also dinaphthylguan
idine thiocyanate formaldehyde condensation
product, orthotolylbiguanide thiocyanate formal
dehyde condensation product, guanyl urea thio
cyanate formaldehyde condensation product, and
thelike.
~
densation products herein mentioned, or the like,
is ‘employed as an, "activator” in the above com
positions.’ The activator is incorporated in rub
ber mixes, preferably in solid form, the particle
, size being reduced, and preferably such as will
passnthrough a 200 mesh sieve. .Substantial
Aldehyde condensation products of the amidine
traces of the above condensation products are
thiocyanates are prepared by gently re?uxing
under atmospheric pressure, or by heating in an
e?ective. Additions of between‘ substantially
enclosed vessel under pressure in case of low 40 0.1% ‘and 1% of ‘the vrubber in a mix are gener
boiling aldehydes, such as acetaldehyde, the thio
> ally satisfactory, a preferred proportion being
cyanates with equal or double molar proportions ‘ about 0.4% in the presence of thiazoles.
of the respective aldehydes. The ratio of re
~ The mixes A and B were vulcanized in'a heated
actants is not critical. Any, excess aldehyde is
mold' for varying times at temperatures indicated
readily removed'from a given reaction mixture 45 in the tables below. Cured rubber products,‘ were
by water washing, distillation or otherwise. To '" obtained in each case having the properties
continue the condensation and polymerization
tabulated.
-*
2,412,984
/_'_ i " "
Table I
Normal stress
Time
Activator (with mix A)
in
lbs/in.’ at elonga-
(1323111135)
nous of_
at 274 0 F
300% 500% ‘ 700%
180
d
D'o
l l
n'dine
thioc y anate crotonaldeh y do condensation pro uct ...... _.
‘r thotOygua
l
Diorthotolylguanidine thiocyanatc formaldehyde condensation product _______ __
620
Tensile
Elongation
at break,
at break,
lbs/in.a
per cent
'
2, 300
2, 730
730
a
a
290
320
,
3,090
3a
3,
3,420
7115
280
210
260
710
490
640
2, 800
1, 890
2, 570
2, 810
2, 980
3, 590
693
776
766
320
310
290
780
850
780
2,
3, 960
180
3, 000
3,610
3, 690
3, 260
736
720
713
a
Table II
Time
Normalstress
in lbs/in.2 at
elongations
Tensile
Elongation
(minutes)
oi—
at break,
at break,
'
Activator (with mix B)
of cure
.
at 274° F_
lbs/in.2
percent
300% 500%
2,420
.Diortllotolylgllanidine thiocyanate erotonaldehyde condensation, product............. ..
'
.
Diorthotoiylguanidine thiocyanateformaldehyde condensation product ............... _. 4
'
'
565
2, 890
560
g,, (6688
530
5 5
2,750
436
2,350
550
2, 910
550
g, ‘(7)33
50:3
2,930
445
,
50
The following table indicates results obtained
It is understood that the invention herein de
with an activator of the type herein used but
scribed is not limited solely to the speci?c em
ad'ded to rubber mixes at different stages of con- 33 bodiments set forth, and that it is obvious to
densation of the thiocyanate and the employed
those skilled in the art that many modi?cations
aldehyde, the condensed ‘products designated as
such as the application of equivalents and vary
solids being more extensively condensed than
ing proportions are within the spirit and scope of
those designated as viscous:
the invention de?ned in the appended claims.
Table III
_
Time of
Activator
curs at
274 F.
Moduh at_
_
Tens-1e
Elongation
Strength
at break,
per cent
300%‘ 500%‘ 100%
4,155
_
.
_
_
.
3,930
Diphenylguanidine thiocyanatc formaldehyde resin (solid) in mix A _____ _'_.__._
,
-
_
'
.
‘
7
.
.
.
.
.
.
.
.
Diphenylguanidinc thiocyanate formaldehyde resin (solid) in mm B .......... -.
.
.
.
‘
.
.
.
.
.
Diphcnylguamdine thiocyanntc formaldehyde resin (viscous) 1n mix B ________ _.
7
Other
amidine
Products
scope_ of
740
770
3,860
750
3,785
3,975
750
795
4,175
Diphenylgunnidine thiocyanate formaldehyde resin (viscous) in mix A ________ __
790
4, 220
4| 245
770
745
4,225‘
760
4, 000
760
2, 650
01s
3, 635
645
4, 015v
630
4,215 >
4,360 ‘
615
565
2, 620'
655
3,500-
675
3, 930
635
4,025
600
4,100-
550
accelerator compositions containing
What is claimedis: "
thiocyanate" aldehyde condensation
1. The improvement in vulcanization of rubber
may‘ be employed that are within the
containing accelerators, which, comprises incor
we Classes-119119111 de?ned and may be 65 poration in a rubber mix of a small amount of
Substltuted for the speFl?c compoundsexempl?‘
condensation product of the thiocyanate. salt of
?ed.
a'g-uanidme withvaldehyda
These condensation products are used in
I
the vulcamza‘tmp of any of the rubbery mammals,
a 2. Theimprovement in‘vulcanization of rubber
that are, vulcamzabler including natural rubbers
containing accelerators which comprises mum
233111121306iiléigiligughgakf'liia’tggdBigtgaofe
70 poration in» a rubber mix of a small amount of
types; or natural or arti?cially prepared latex
condensation- product of the thiocyanate salt of
These are all to be included-herein under- the
an aryl gu_amdme Wlth aldehyde
term “rubbery ,
v
‘
3; The improvement in vulcanization of rubber
The thiocyanates referred to herein arethio- 7 containing accelerators, which comprises, incor
cyanate salts.
porationv in a rubber mix of a small amount of
2,412,984
5
condensation product of the thiocyanate salt of
diphenyl guanidine with aldehyde.
6
condensation product of the thiocyanate salt of
an aryl guanidine with aldehyde.
The improvement in vulcanization of rubber
12. A composition comprising rubber, a vul
canizing agent and an accelerator containing
poration in a rubber mix of a small amount of
condensation product of the thiocyanate salt of
condensation product of the thiocyanate salt of
a diphenyl guanidine with aldehyde.
diorthotolylguanidine with aldehyde.
13. A composition comprising rubber, a vul
5. The improvement in vulcanization of rubber
canizing agent and an accelerator containing
containing accelerators, which comprises incor
condensation product of the thiocyanate salt of
poration in a rubber mix of a small amount of 10 a diorthotolylguanidine with aldehyde.
condensation product of the thiocyanate salt of
14. A composition comprising rubber, a vul
orthotolylbiguanide with aldehyde.
canizing agent and an accelerator containing
6. A process of preparing a vulcanized rubber
condensation product of the thiocyanate salt of
product, which comprises mixing a vulcanizable
an orthotolylbiguanid with aldehyde.
rubber composition with an accelerator contain
15. A rubber product comprising rubber vul
ing condensation product of the thiocyanate salt
canized in the presence of condensation product
of a guanidine with aldehyde, and vulcanizing
of the thiocyanate salt of a guanidine with alde
the rubber.
hyde.
7. A process of preparing a vulcanized rubber
16. A rubber product comprising rubber vul
product, which comprises mixing a vulcanizable
canized in the presence of a thiazole and con
rubber composition with an accelerator contain
densation product of the thiocyanate salt of a
ing condensation product of the thiocyanate salt
guanidine with aldehyde.
of a diphenylguanidine with aldehyde, and vul
17. A method comprising vulcanizing a rubber
canizing the rubber.
in the presence of condensation product of the
8. A process of preparing a vulcanized rubber
thiocyanate salt of a guanidine with aldehyde.
product, which comprises mixing a vulcanizable
18. A method comprising vulcanizing a rubber
rubber composition with an accelerator contain
in the presence of condensation product of the
ing condensation product of the thiocyanate salt
thiocyanate salt of an aryl substituted guanidine
of a diorthotolylguanidine with aldehyde, and
with aldehyde.
vulcanizing the rubber.
19. A method comprising vulcanizing a rubber
containing accelerators, which comprises incor—
9. A process of preparing a vulcanized rubber
product, which comprises mixing a vulcanizable
in the presence of condensation product of the
thiocyanate salt of a diphenylguanidine with
rubber composition with an accelerator contain
aldehyde.
ing condensation product of the thiocyanate salt
20. A method comprising vulcanizing a rub_
her in the presence of condensation product of
the thiocyanate salt of a diorthotolylguanidine
of an orthotolylbiguanid with aldehyde, and vul
canizing the rubber.
10. A composition comprising rubber, a vul
canizing agent and an accelerator containing
condensation product of the thiocyanate salt of
a guanidine With aldehyde.
11. A composition comprising rubber, a vul
canizing agent and an accelerator containing
with aldehyde.
21. A method comprising vulcanizing a rubber
in the presence of condensation product of the
thiocyanate salt of an orthotolylbiguanide with
aldehyde.
‘
WILLIAM H. HILL.
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