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Патент USA US2404771

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Patented July 30, 1946
2,404,771
‘UNITED STATES “PATENT OFFICE
2,404,771
MONOTHIAZYL
METHOD FOR
DITHIOCARBONATES
PREPARING SAME
Edward S. Blake, Nitro, W. Va., assignor to Mon
santo Chemical Company, St. Louis, Mo., a cor
poration of Delaware
No Drawing. Original application February 26,
1941, Serial No. 380,677. Divided and thisap- ‘
plication June 23, 1943, Serial No. 491,921
18 Claims. (01. 260-306)
1
2
The present invention relates to new vulcaniza
tion accelerators, to a process of vulcanizing rub
small amount of aluminum chloride. The solu
tions were mixed cold as for example at 0° C.
and gradually allowed to come to room tempera-_
ture. After HCl had ceased to be evolved the
product was distilled from the solvent under a
ber and to the vulcanized rubber products‘ob
tained with the aid of said new accelerators.
The accelerators of this inVention are the
monothiazyl dithiocarbonates. This class of ma»
mild vacuum and puri?ed by distillation. Low'
boiling solvents have been used with equally good
results in which case the solvent is removed ?rst,
preferably by distillation, and the residue puri?ed‘
terials is represented by the structural formula
'as-c-s-ra
t v
where R2 may be one of a wide variety of suitable
substituting groups in which carbon is linked to
the sulfur as hereinafter disclosed and R1 is a
10 as described. The pure thio ethyl chlor carbon
ate boiled at 129-132“ C'. This product was re
acted with the sodium salt of mercaptobenzothh
azole in aqueous solution and also with the po
tassium salt of mercaptobenzothiaz‘ole in ethyl
thiazyl radical. Typical examples of the latter
comprise benzothiazyl, methyl thiazyl, methyl 15 alcohol.’ It will be appreciated that other sol
vents may be used in either step and other me
benzothiazyl, nitro benzothiazyl, chlor benze
thiazyl, amino benzothiazyl, 4 phenyl benzo
tallic salts or. even the free mercaptothiazoles
thiazyl,
may be used where desired.
naphthothiazyl,
dihydrothiazyl ‘ (thi
‘
Other mercaptans and thio ‘phenols which may
the aforementioned radicals are illustrative of 20 be used‘ for preparing the new accelerators in
azolyl) and 6 phenyl benzothiazyl radicals. While
clude methyl mercaptan, propyl mercaptan, bu
tyl mercaptan, amyl mercaptan, thio phenol,
some of the thiazyl radicals which may be em»
ployed, the invention is by no means limited
thereto.
,
benzyl mercaptan, lauryl mercaptan, nitrophenyl
‘
mercaptan, thio cresol, 'xylyl mercaptan, pinene
While the new compounds may be employed
alone as vulcanization accelerators they are used 25 mercaptan and cyclohexyl mercaptan. Thus, R2
in the above formula may be an alkyl, aralkyl,
with greater advantage in conjunction with basic
aryl or alicyclic radical including terpene radi
nitrogen containing accelerators as activators
cals.
'
thereof and are preferably so employed. As suit
As speci?c embodiments of the invention illus-,
able basic nitrogen containing accelerators there
trating the use of the new accelerators and the‘
may be mentioned diphenyl guanidine, 'di-o-tolyl
guanidine, thiocarbam'lide, hexamethylene tetra;
mine, para phenylene diamine, anhydro formal
desirable results attainable thereby, but without
limiting the invention, rubber stocks were com
pounded comprising
dehyde aniline, diphenyl guanidine phthalate, tri
phenyl guanidine and butylaldehyde aniline.
' Again the foregoing list is by no means complete 35
Stock
being illustrative of activators which may be used
with the new accelerators but it is in nowise limi
tative of the invention.
The new accelerators may be prepared by
methods well‘ known to chemists.
For example >
they may be manufactured by reacting a mer->
captothiazole, usually in the form of a metallic
salt such as a Zn, K or Na salt, and a thio ester
of chloro carbonic acid. ‘Somewhat better yields
Stearic acid __________ ____ .
Bcnzothiazyl, benzyl d1
thiocarb onate ______ _ __l .
Benzothiazyl,
propyl d1
are obtained by carrying out the reaction in an 45 thio carbonate______ _ ___ _
Benzothiazyl, ethyl d1~
organic solvent such as alcohol although aqueous
Benzothiazyl. butyl di
solution may be used where desired, in which
thiocarbonate ________ _ .
case a water soluble salt of the thiazole should
be used. A thio ester of chloro carbonic acid
thiocarbonata.
Thus, one
at the temperature of twenty pounds steam pres
half molecular proportion of ethyl mercaptan was
dissolved in dry decalin and this solution added
sure-per square inch. The modulus anditensile
properties of the cured rubber products are set
to a solution of one molecular proportion of
phosgeue dissolved in dry decalin containing a
__
The stocks so compounded were vulcanized in
a press by heating for different periods of time
may in turn be prepared by reacting phosgene
with a mercaptan or thio phenol.
_
55
forth below.
i
e
2,404,771
,
Stock
1 y m 1of
s.elastic‘;
m. a
Modulus
T ensi_1 e
tigllgin
elongations of— at break 9531112"
minutes 7
4
present invention is not limited to the specific
examples hereinbefore set forth wherein the pre
Table I
' ‘
lbs?liniz
500%
percent
700%
45
45
175
135
550
355
1, 930
1, 575
45
160
' 400
1,740
930
950
940
45
90
90
90
90
130
300
240
290
235
275
980
v 775
1, 030
665
1, 740
2, 290
2, 4,35,
2, 225
2, 450
l, 035
845
885
830
915
ferred accelerators are employed. Other ratios
of the compounding ingredients than those men
5 tioned in the examples as Well as other Well known
?llers, pigments and the like may be employed in '
the production of various types of rubber com
pounds and are apparent to those skilled in the
art to which this invention pertains. The inven
10 tion is limited solely by the claims attached here
to as part of the present speci?cation.
This application is a division of co-pending
application Serial No. 380,677, ?led February 26, V
1941, Patent 2,336,217,
As noted, the new accelerators are used with 15
nitrogen containing accelerators as- activators
thereof. As exemplary of such use but again
without limiting the invention, rubber stocks were
compounded comprising
G
H
carbonate nucleus and a radical selected from
20 the group consisting of alkyl, aralkyl, aryl, ali
cyclic and terpene radicals is directly' linked to
.7
Parts by Paris by Parts by Parts by Parts by
~
Pale crepe rubber
Zinc oxide
weight
100
5
weight
100
5
weight
100
5
weight
100
5
weight
100
5
3
3
3
3
5
Sulfur. _
Stearic ac ,
F
‘
the second sulfur atom of the same dithiocar‘L
bonate nucleus.
2. The chemical product comprising a com’
25 pound possessing the structure
Stock
E '
What is claimed is:
.1. The chemical product comprising a mono
thiazyl dithiocarbonate in which the said thiazyl
radical is linked to one sulfur atom of the dithio
particular advantage in conjunction with basic
, ,
Diphenyl guanidlne
.
_o. s
.
0. 15
10. 5
0.15
Benzothiazyl, ben'zyl di-
-
thiocarbonatmrr____ _»_
0. 6
0. 5
,0, 5
0,5
0. l5
0. 15
0.15
36» containing carbon and hydrogen only.
3. The chemical product ‘comprisinga com=
"
_-_..-_.;-_
Benzothiazyl, propyl di
....... .; ________ _.
, _
thiocarbon'ate ______ _-_ _______ __
Benzothiazyl, plienyl di-
R,-s-<li-s-R¢
where-R1 is a thiazyl radical and R2 is a radical
pound possessing the structure
.
0.6
_______ .
_~_ ____ __
'
»______ _.
‘
thiocarbonate _______________________ _.
0.6
Benzothiazyl, ethyl di-
______________ __
>
,thlocarbonate ________________ _
_; ____ _.
>._.-_____
0.6
where R1 is an aryl thiazyl radical and R2 is a
______ ,.
Benzothiazyl, butyl di-
‘
thiccarbonate; ___________ __-.-._ .-_-____________________ __
radical containing carbon and hydrogen only.
0.6
4. The chemical product comprising a com
pound possessing the structure
~ The stocks so compounded were Vulcanized in
the same manner as stocks A-D the vulcanizing
ares-gasses?
temperature being as before, the temperature of
twenty pounds of steam pressure per square inch.
The modulus and tensile propertiesof the cured
rubber products are set forth below‘:
where R1 is a benzothiazyl radical and R2 is a
radical containing carbon and hydrogen only.
415
‘ Table Ii
Mozduluslgf
lelaszticé
T ensn e
iyln
sin.
a
,
S-tbck
tgrerg ‘minutes
elo'ngations oi'— » at break
'
'
"
‘
500%
'
5. The chemical product comprising a com
pound possessing the structure
'
‘
lbsl‘lnm? ‘
(U) .
R1'—'S-—‘—G‘—'S'—_R2
‘_
61212;’
‘percent
700%
'50‘Where R1 is a benzothiazyl radical and R2 is an
aliphatic hydrocarbon radical containing less
than5_carbon atoms.-
45
450
1, 74b
3, 350
820
45
45
45
45
90
415
330
410
335
630
1, 700
l, 230
1, 860
l, 160
2, 450
3, 450
2, 870
3, 100
3, 275
3, 850
820
830
780
870
785
90
525
90
420
1, 670
3, 290
810
90
640
2, 650
2, 255
‘
3, 950
3, 550
V 750
90
410
1, 460
3, 435
840
,
'
‘
6. The chemical product corn-prising a com
pound possessing the structure
.
800
60 - '7. The chemical product comprising
"com
pound possessing the structure
The data set forth in Tables I and II show the
desirable physical properties of vulcanizates cured
in the presence of the new accelerators alone and
in conjunction with basic nitrogen containing ac
celerators as activators thereof. Moreover, al
though the mixture of accelerators is effective
and fast, it is not so fast in action as to produce
SJI‘he: chemical product comprising .3, 105m;
prevulcanization or scorching of the stock during
the milling, calendering or other handling opera
tions.
,
Again resort may be had to other methods of
preparing the new accelerators Where convenient
or desirable.
Pound possessing the structure’
70
.
N
/
'
'-
_
1
o
This invention is not concerned
' with the preparation of the compounds and is not
in any Way limited thereto. Furthermore, the
‘r 9. ‘The-method of making a monothiaz'yl-di
.
2,404,771
5
thiocarbonate which comprises reacting a mer
captothiazole with an ester of chlor mono thio
carbonic acid the ester forming group being
linked to the sulfur atom.
10. The method of making a monothiazyl di
thiocarbonate which comprises reacting a mer
captothiazole with a product of the structure
6
where R2 is an aliphatic hydrocarbon radical con—
taining less than 5 carbon atoms.
14. The method of making benzothiazyl ethyl
dithiocarbonate which comprises reacting mer
captobenzothiazole with ethyl mono thio chlor
carbonate the ethyl radical being linked to the
sulfur atom.
15. The method of making benzothiazy‘l benzyl
dithiocarbonate which comprises reacting mer
10 captobenzothiazole with benzyl mono thio chlor
where R2 is a hydrocarbon radical.
11'. The method of making a monothiazyl di
thiocarbonate which comprises reacting a mer
capto aryl thiazole with a product of the struc
ture
carbonate the benzyl radical being linked to the
sulfur atom.
16. The method of making benzothiazyl phenyl
dithiocarbonate which comprises reacting mer
captobenzothiazole with phenyl mono thio chlor
carbonate the phenyl radical being linked to the
sulfur atom.
where R2 is a hydrocarbon radical.
12. The method of making a monothiazyl di
thiocarbonate which comprises reacting mer
captobenzothiazole with a product of the struc
ture
gene with an aliphatic mercaptan under sub
stantially anhydrous conditions to remove one of
the chlorine atoms as HCl and condensing the
product with a. mercapto thiazole in the form of
its alkali metal salt.
25
where R2 is a hydrocarbon radical.
13. The method ‘of making a monothiazyl di
thiocarbonate which comprises reacting mer
captobenzothiazole wtih a product of the struc
ture
'
17. The method of making‘a monothiazyl di
thiocarbonate which comprises reacting phos
-
18. The method of making a monothiazyl di
thiocarbonate which comprises reacting phos
gene with a thio phenol under substantially an
hydrous conditions to remove one of the chlo
rine atoms as HCl and condensing the product
30 with a mercapto thiazole in the form. of its al
kali metal salt.
EDWARD S. BLAKE.
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