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Патент USA US2116978

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2,116,978
Patented May 10, 1938
UNlTED STATES PATENT OFFICE
2,116,978
VULGANIZATION 0F RUBBER
Ludwig Meuser, Naugatuck, C‘onn., assignor, by
mesne assignments, to United States Rubber
Company, New York, N. Y., a corporation of
New Jersey
No Drawing. Application July 14, 1934,
Serial No. 735,199
6 Claims. (Cl. 18-53)
This invention relates to the treatment of
rubber, and similar vulcanizable materials and
more particularly to the employment in a vul
5
canization process of the product of reaction of
arylene thiazyl sulphides, such as mercapto
arylene thiazoles or their alkaline salts, with a
furoyl halide.
The reaction products constitute new types of
so-called delayed action accelerators. These
slightly with further puri?cation. The product
has a sulphur content of about 25.2% and a total
nitrogen content of about 5.5%
By the above reaction a furoyl group replaces
the sodium of the sodium salt of mercaptoben- 5
zothiazole and the product may be called the
furoyl ester of mercaptobenzothiazole, or furoyl
benzothiazyl sulphide. It is believed it has the
probable formula
‘
10
new accelerators may be used alone as a vul
canization accelerator, or in conjunction with an
amine type of activator which term broadly in
cludes amides and imides and organic acid salts
of the amines. Examples of such activators are
15 given by U. S. P. 1,732,486, U. S. P. 1,893,846, U.
S. P. 1,950,067, U. S. P. 1,904,573. Activators
such as the substituted ammonias containing
acyl groups, and the salts of diphenylguanidine
(D. P. G.) and an organic carboxylic acid, have
acyl components exercising desirable vulcaniza
2 0 tion retarding in?uences at lower temperatures
at the same time that they have the desirable
characteristics of the amine component in pro
moting quicker acceleration or optimum cures in
a shorter time athigher vulcanizing tempera
tures, when used in conjunction with the new
delayed action accelerators. It has also been
found thatthe amount of the new accelerators
can be markedly reduced when used in conjunc
30
tion with amine activators without sacri?cing
desirable physical and commercial character
CH————CH
Instead of the chloride, the bromide or iodide 15
may be used, although the former is preferred.
A rubber stock was prepared in the usual man
her-‘comprising by weight
Smoked sheet rubber ________________ __ 100
Carbon black _______________________ __ 42
Zinc
oxide __________ ___ ______________ __
4.15
.85
Zinc soap of cocoanut oil acids _______ __
2.40
Sulphur ____________________________ __
3.25
Furoyl benzothiazylsulphide __________ __
TABLE I
Scorch test
Cure
970
Unaged tensiles
thereof, potassium hydroxide may be used, in
which case potassium mercaptobenzothiazole
125 grams or approximately 95.6% based on the
mercaptobenzothiazole used.
Melting‘ point of
the product is about 134-136" C. and would vary
_
No cure
N0 cure
stead of sodium hydroxide, to dissolve the mer
captobenzothiazole and form an alkaline salt
of sodium chloride and dried. The yield is about
at break
No cure
caustic soda solution by gentle heat thereby
forming sodium mercaptobenzothiazole. In
an hour. . The reaction product is washed free
elogation
lbs/sq. in.
No cure
35
Percent
Tensile at
break in
azole are dissolved in 190 grams of about a 10.5%
would be formed. The solution is ?ltered and
66.5 grams of furoyl chloride is added thereto
with gentle warming. The cream colored pre
cipitate or reaction product formed is ?ltered
off after allowing the reaction mix to stand about
.875
and tensiled at various intervals indicated in
minutes cure, at 5 pounds per sq. in. steam pres
sure for evaluation of scorching properties, and 30
also at 30 pounds per sq. in. steam pressure.
Results are given in Table I.
mixtures of the new accelerator and an amine
from the following description and examples.
sample 1.—‘84 grams of mercaptobenzothi
10
Pine tar ____________________________ __
Palm oil ___________________________ __
istics of the ?nal rubber products. Accordingly
type of activator form valuable accelerator com
binations.
The invention will be more fully understood
Parts
Cure
45
Tensile at
break in
lbs/sq. in.
1730
2010
2810
3330
3380
3640
3640
Percent
elogation
at break
620 50.
610
650
676
656
650
633
55
21 ‘
2,116,978
Corresponding tests were made on a "shoe
TABLE III
upper” stock comprising by weight:
Unaged tensiles
Parts
Smoked sheet rubber _________________ __ 100
Whiting _____________________________ __
O
D
E
4'7
Zinc oxide ——————————————————————————— ~—
6
sulphur ------ "T ““““““““ “i ----------- "
2
giieléa (]l1_i1__1 .35 Furoyl-gier-
Furoyl benzo thiazyl sulphlde _________ __
0.35
-p t __
a -.30
ate ______
Cum
Furoygl-gier
cap 0 enzo .35
thlazole-__
cap c 01170 .35
thiazole____
DPG-iuorate .33
10
and using therewith in one case A, as activator,
e. g. diphenylguanidine-phthalate 0.85 part, and
m another case B’ e‘ g‘ dlpheFylguimdnle'a-w'
tate 0.74: part.
Results are given in Table II.
15
T
E
7'.@40#:r ' 2380 ' ,
T
E
.
T
10
E
720
440
305
2370
22I@40#
2930"
703
1380
810
2820
770
720
30' @ 40#
2950
700
1540
823
2000
703
TABLE II
Scorch test
Scorch test
g
.
Cure
Stock
15
T811311?“
break in
lbSJSq- m
i
go cure.
A
No we
A
No cure
Percellt
elongation
at break
No cure 922
30' @ 5#. 1307
45, @ 5#
00' @ 5#
75'@5#
820
23352580
2902
0 cure
760
725
747
11:1Io cure
No cure 930
0 euro
No cure
101
203
003
.
s30 20
1250
972
922
850
2137
2530
2715
712
747
730
,
Unaged tensiles (cont d)
25
‘
A
A
F
G
t
B
572
830
B
B
B
B
B
2353
2880
2015
3107
3243
816
786
752
747
756
35
3 .
Stock
40
T
22 @
@ 40;?
30'
‘I‘ensiles at
Percent
break in
elongation
lbs/sq. in.
at break
i
258
3460
3460
3100
‘
T
e
30
E
2400'
2820
2840
00
700
73
720
Scorch test (cont’d)
-
-
.
No cure
No cure
3135i
5 .23
28?
60’ @ 5#
75'@5#
767 1647
752 2272
45"@ 5# 2025
746
770
720
benzo thiazo1c___. .35
DPG-acid tartrateh .985
E
292
3000
10’ @ 5#_
A
A
A
Furcyl-mercapto
benzo thiazole____ .35
DPG-tartrate _____ __ .78
@ ti
Unaged tensz- es
Cure
Furoyl-mercaptoCure
_
2862
3010
775
NO
312
40
750
757
737
B
3540
730
- B
4030
720
g
g
gggg
353
any with stock 0 and that stock G is markedly
' B
3240
713
superior in freedom from scorch with practically
It W111 be observed that stock E compares favor
45
no retardation in the rate of cure.
50
Diphenylguanidine-formate ' in place of di
phenylguanidine-ac'etate also gave'good results,
with no curing noted until' the 40 minute period
in scorch test.
55
In another example a white proo?ng compound
containing by weight
chanicals, and the like.
7
Instead of employing the furoyl derivative of
mercaptoarylthiazoles, the substituted‘iuroyl de
Parts
‘Pale crepe_;:'__'; ________________________ __ 100
su1phur-_.._'___' __________________________ __._.
60
Other advantages of the furoyl derivative of
mercaptobenzothiazole are that it is substantially 50
non-'discoloring and can bev used in mold and air
cured goods including footwear, proo?ng, me
3
Zinc oxide ______________________________ __
6
Whiting ________________________________ __
47
Titanium oxide _________________________ __
20
55
rivative of mercaptoarylthiazoles may be used
wherein the furoyl group contains one or more
alkyl or substituted alkyl constituents, e. g.
methyl, ethyl, etc. Instead of mercaptobenzo
thiazoles other mercaptoarylthiazoles may be
used wherein the aryl radical is substituted by
one or more ethyl, methyl or other alkyl radicals.
65
was used as the‘ba'sic stock. Tensile and scorch
data onthis stock‘ after admixture with ‘various
accelerator'combinations are indicated in Table
IIIbelow.
The various stocks are indicated as C, D, E,
F and G along with the parts by weight, based on
100 parts by weight 'of rubber, of the accelerator,
or accelerator and activator, used. Ureka C (be
'75
lieved to be benzoyl benzo thiaz‘yl sulphide) is a
representative commercial delayed action accel
orator.
The examples given‘are to be understood as
illustrative only and ‘not limitative of the inven
tion and it is to be understood that various modi 65
?cations will suggest themselves,—for instance
the use of other proportions and the use of
various compounding ingredients including anti
a'gers, softeners, etc. in conjunction with the
accelerator products-all without departing from
the spirit of the invention.
'
The term “rubber” is'to be considered broadly
as including caoutchouc and‘similar vulcanizable
materials such as guttapercha and balata etc.
3
2,116,978
Having thus described my invention, what I
claim and desire to protect by Letters Patent is:
1. A process which comprises adding to rubber,
a vulcanizing agent and a furoyl derivative of a
5
mercapto-aryl-thiazole having the thiol sulphur
atom directly linked to a furoyl group, and vul
canizing the rubber.
2. A process of producing a vulcanized rubber
product which comprises adding to rubber prior
10 to actual vulcanization a furoyl arylene thiazyl
sulphide corresponding to the formula
3. A product suitable for accelerating the vul
canization of rubber, comprising a furoyl deriva
tive of a mercaptoarylene-thiazole having the
thiol sulphur atom directly linked to a furoyl
group.
4. As a new product, suitable for accelerating
the vulcanization of rubber, a furoyl derivative of
mercapto-benzo-thiazole having the thiol sulphur
atom directly linked to a furoyl group, and hav
ing a melting point of about 134L136° C.
‘
5. A process of treating rubber which com
10
prises subjecting it to vulcanization in the pres
ence of furoyl benzothiazyl sulphide.
-
6. A rubber product which has been vulcanized
16
in the presence of furoyl benzothiazyl sulphide.
15
where AR represents an arylene group, and F
represents a furoyl group.
LUDWIG MEUSER.
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