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Патент USA US3038023

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3,033,13
Patented June 5, 1952
2
'
acting tertiarydodecyl mercaptan with sulfur in the pres
ence of a catalytic amount of phosphorus pentasul?de and
3,638,013
COLOR INIPROVENENT IN SYNSIS
0F POLYSULFIDES
a color inhibitor comprising water and a ?nely divided
Paul F. Warner, Phillips, Tex., assignor to Phillips Petro
leum Company, a corporation of Delaware
metal selected from the group consisting of iron, alumi
5 num and zinc. Also according to this invention, there is
provided tertiarydodecyl tri- and tetrasul?des having im
proved color characteristics, prepared ‘from the reaction
of tertiarydodecyl mercaptan in the presence of a catalylst,
This invention relates to the preparation of organic
using ?nely divided metal particles and water to inhibit
sul?des. In one aspect, it relates to the preparation of 10 color formation.
organic polysul?des by reacting mercaptans with sulfur
In the synthesis of ditertiarydodecyl tri- and tetrasul
in the presence of a catalyst and a color inhibitor. In
?des from alkyl-mercaptans and sulfur, hydrated lime has
another aspect, it relates to the preparation of dialkyl
been found to be a desirable catalyst. Among the advan
polysul?des by reacting alkyl mercaptans with sulfur in
tages of using lime as the catalyst are included (1) rapid
No Drawing. Filed Aug. 25, 1959, Ser. No. 835,832
11 Claims. (6i. 26tl-—608)
the presence of a catalyst and a ?nely divided metal. In 15 reaction rates at relatively low temperatures, for example
another aspect, it relates to the preparation of dialkyl poly
sul?des by reacting valkyl mercaptans with sulfur in the
between 200 and 250° F. and (2) relatively slow rates of
decomposition of the mercap-tan and the product at reac
presence of a catalytic amount of lime and a color in
tion temperatures. Equations illlustrating the manufac
hibitor comprising a ?nely divided metal. In another
ture of the tri- and tetrasul?des are as follows:
aspect, it relates to the preparation of dialkyl polysul 20
?des by reacting alkyl mercaptains with sulfur in the
presence of a catalytic amount of phosphorus pentasul?de
and a color inhibitor comprising a ?nely divided metal.‘
In runs made to produce ditertiarydodecyl tri- and tetra
Organic polysul?des, and particularly dialkyl polysul
sul?des by reacting mercaptans with sulfur in the presence.
?des, have been found useful for many purposes such as 25 of lime as the catalyst, each run producing approximately
additives for elastomers, anti-oxidants for lubricating oils,
50 to 100 gallons of product, for use in the pesticide
intermediates for the production of valuable organic
market, the products were so dark in color that they were
chemicals, insecticides, germicides, and additives to diesel
not suitable for their intended purpose. The color of
fuels to improve the number and the ignition qualities of
these tri- and tetrasul?des was in the vrange of 18+
these fuels. These compounds have also been found use 30 Gardner. .-The runs were made in a stainless steel reactor
ful in the compound of extreme pressure lubricants and
which was cleaned prior to use.
.
> .
in the acceleration of rubber treating processes.
I have ‘found that, in the preparation of organic poly
It has been previously disclosed that aliphatic polysul
sul?des from mercaptans and sulfur, the addition of a
?des in general may be synthesized by reacting sulfur with‘
small amount of metal dust, for example, iron, alumi
a mercaptan in the present of metal hydroxides. How 35 num, or zinc, and water to the reaction mixture very mark
ever, in the synthesesis of these materials in this manner
edly inhibits the color formation. Other metal dusts may
the products were so dark in color that they were not suit
also be used, a particular metal being chosen for its ef
able for use for some of their intended purposes.
For
fectiveness ‘in inhibiting the color formation when using
example, the products were too dark to ‘be desirable for
40
use as insecticides.
It is an object of this invention to provide an improved
Standard charges for laboratory runs illustrating this
invention, using lime as a catalyst, were as follows:
process for the preparation of organic polysul?des by
the reaction of organic mercaptans with sulfur.
speci?c mercaptans.
It is
Trisul?de if
another object of this invention to provide organic poly
sul?des having an improved, more desirable color. It is
another object of this invention to provide a color inhibitor
45
~
.
grams
‘mols
for use in synthesizing organic polysul?des.
Other aspects, objects, and the several advantages are
apparent from a study of this disclosure and the appended
Tetrasul?de
.
.
v
grams_
mols
200
48
1O
CA?
claims.
Thus, according to the present invention, there is pro
vided an improved process ‘for the preparation of organic
sul?des from the reaction of mercaptans with sulfur using
The reactions were carried out in a 600 ml. beaker
equipped with a motor driven ‘stirrer. The temperature
Was accurately controlled through the use of an ‘automatic
a basic catalyst and a color inhibitor. Also according
temperature controller. The following examples illustrate
to this invention, there is provided a process for the prepa 55 the invention.
ration of dialkyl polysul?des from alkyl mercaptans and
Example I
sulfur in the presence of a catalytic amount of lime, using
?nely divided metal particles as a color inhibitor. Also,
according to this invention, there is provided a process
TW0 hundred grams of tertiarydodecyl mercaptan, 32
grams of sulfur ‘and 10 grams of calcium hydroxide were
for the preparation of dialkyl polysul?des from alkyl 60 placed in a beaker and stirred continuously .while main
taining the temperature at 300° .F., thus forming 'diterti
mercaptans and sulfur in the presence of a catalytic
amount of phosphorus pentasul?de using ?nely divided
arydodecyl trisul?de. The Gardner color developed as
metal particles as a color inhibitor. Also according to
this invention, there is provided a process for the prepa
follows:
ration of \ditertiarydodecyl trisul?de ‘and dietertiarydo
decyl tetrasul?de by reacting tertiarydodecyl mercaptan'
Hours;
65
1.0
with sulfur in the present of a catalytic amount of lime
and a color inhibitor comprising water and a ?nely divided
metal selected from the group consisting of iron, alumi
num and zinc. Also according to the invention, there is,
provided a process for the preparation of ditertiary
dodecyl trisul?de and ditertiarydodecyl tetrasul?de by re
vGardner color
‘0.5
~
V
‘
5
2.0
4.0
70
'
Example II
_
7
____
ll
'
A reaction as described in ‘Example I was duplicated ex-V
cept that 1 gram of aluminum dust and 1 gram of water
3,038,013
,
p
_
_
4
3
were added "to the reaction mixture. The results of the 0
tertiarydodecyl trisul?de. ‘The results of the color tests
color tests follow:
Hours:
were:
0.5
_
1.0
‘
4.0
Gardner color
____
4
1.0
____
5
2.0 ____________________________________ __
15
___"... 6
3.0 ____________________________________ __
16
>_
__
2.0
Hours:
Gardner color
,
_
______ __
__
'
‘
The reaction described in Example VII was duplicated
'
except that 1.0 gram of iron dust was added to the mix
Example [11
ture. The results of the color tests were:
The reaction of Example I was duplicated except that
l gram of zinc dust and 1 gram of water were added to
the reaction mixture.
'
Hours:
"
0.5
‘
7 Hours:
,
Gardner color
1.0 ___
.15
'
'
3.0
4
4.0
_
8
___
'
___- 5
l0 '
14
1.0 ___; _______________________ __' _________ __ 4
2.0.
6
2.0 ___
Gardner color
4.0
18
Example VIII
Puri?ed Grade, a ?aky material similar to‘that'use’d 'in
i
13
___---
___ 8.
e The aluminum powder used in this example was Baker’s
aluminum paints.
___
Example IX
20
The following data, taken from a run to produce di
_____ __ 5
tertiarydodecyl tetrasul?de illustrate the effect "of the tem
perature on the reaction using lime as a catalyst and
The zinc dust used in this example was Mallinkrodt’s
Analytical Reagent Grade, assay 95+ percent zinc.
Example IV
Two hundred grams of tertiarydodecyl mercaptan, 48
methanol as a promoter for the reaction.
Pounds
Mols
grams of sulfur, and 10 grams of calcium hydroxide were
mixed in a beaker and stirred continuously whilemain- > » Charge:
>
Tertiarydodecyl mercaptan _________ __
taining _the temperature at .300“ F., thus forming di
tertiarydodecyl tetrasul?de.
follow:
The color tests were as 30
'
'
Hours:
'
Sulfur _______________________________ _-
7.14
1. 70
0. 0357
0. 0531
Calcium hydroxide __________________ __
0. 09
____________ __
Methanol _________________________ -‘___
0. 09
____________ __
'
Gardner color
0.5
8
1.0
9
2.0
10
3.0
11
4.0
—
CONDITIONS
Time,
The reaction described in Example IV was duplicated
7 except that 1 gram of iron dust was added to the reaction
mixture. The results of the color tests follows:
Gardner color
0.5
'
45
7
1 .0
2.0
3.0
4.0
° F.
0 _________ __
80
15 ________ _20 ________ __
'
150
170
180
250
1. 94
215 _______ .-
300
0. 98
Product Recovered
Properties of product:
'
‘
‘
Shut down.
___
7. 814 lbs.
'
25.5
Gardner ___________________________ _-
IBP
’
.
6
400
5
10
" 50
50
447
478
'
00 (decomposed at 310° F.) ____________ __
1 Ran on the liquid phase Only.
2‘Ban at 5 mm. Hg, corrected to 760 mm. Hg.
The reaction was progressing nicelyat 180° F. After
except that 1 gram of iron dust and 1 gram of water were
, added to the reaction'mixture. The results of the color
two hours, however, approximately half the mercaptan
remained unconverted. Thetemperature was raised to
300° F. andthe reaction was substantially complete in
tests follow:
an hour.
Gardner color
60
0.5 '
1.0
2.0
'
'
Using lime as a catalyst, the process operates successful
ly between about 100° and 350° F. Since the reaction
proceeds slowly at 150° F. with some decomposition of
‘ the polysul?de at or near 350° FL, the‘ preferred range
for the reaction is 200° to 300".- F.'
3.0
4.0
Most H18 liberated.
Speci?c gravity 20/4 _______________________ ___. 0.9680
‘
‘The reaction described in Example IV was duplicated
'
7. 0
D'stillation 2 ____________________________ __ F at 760
Example ‘VI
Hours; '
H38 Started Coming off.
Shut of!‘ Heat to control
reaction rate.
Total sulfur
was Baker’s Analyzed Low Nitrogen Grade.
'
15.0
____________ __
____________ __
125 _______ __
'
15
the ,following enamples
Remarks
155 _______ -_
Color,
this
Sulfur Wt.
Percent (l)
Refractive index 20/ D _____________________ __ 1.5243
.9
12
The iron dust used
'
'
Example V
Hours:
Temperature, Mercaptan
Min.
i
I
g
V
I
V
‘
For the reaction using phosphorus pentasul?de as the
catalyst, a temperature within the range of 200° ‘F. to
400° F. can be employed in most instances, but tempera
tures wit-hin‘the range of 250° F. to 350° F. are generally '
As noted, all of the above six examples are made using
a lime catalyst. ‘To illustrate the applicationfof, the‘inveu
tion to The reaction using phosphorus pentasul?de vas a
catalyst, the runs of Examples VII and VIII werenjiade. ,
70
' ‘ Two-hundred grams ofrtentiarydodecyl mercaptan, 32,
grams of sulfur, and 1.2" grams of phosphorus pentasul?de
were placed in a beaker and stirred continuously while
.
the temperature at 300° F., thus forming di
preferred.’
7'
g
The invention is applicable to the reaction of’ mer
ccaptans having lower and higher molecular weights than
the tertiarydodecyl mercaptan used in the speci?c ex
amples. It is noted that with the lower boiling materials
it is'ne'cessary to carry out the reaction in a pressure
75
vessel to prevent loss of mercaptan. ., At the present time,
3,038,013
5
6
it is preferred to use mercaptans having up to 16 carbon
3. A process for preparing a dialkyl polysul?de which
comprises reacting an alky mercaptan with sulfur in the
atoms in the molecule.
In the speci?cation, “metal dust” has been used to
refer to ?nely divided metals, the particles of which
presence of a catalytic amount of lime, having present
in the reaction one water and a ?nely divided metal
range in size from about —325 mesh (0.‘045-0060 mm.
diameter) to +100 and which are produced by ma
selected from the group consisting of iron, aluminum,
chining, milling, shotting, granulation, atomizing, con
densation, reduction, chemical precipitation, or electro
4. A process for preparing a ditertiary alkyl poly
sul?de which comprises reacting a tertiary alkyl mer
and zinc.
deposition, however, in general, a range of about 100
captan with sulfur in the presence of a catalytic amount
to about 200 mesh is preferred.
10 of lime, having present in the reaction zone water and ‘a
Although the invention has been described in connec
?nely divided metal selected from the group consisting
tion with a batch operation, it is obvious that the process
of iron, aluminum, and zinc.
can be carried out continuously if desired, for example,
5. A process for preparing ditertiarydodecyl polysul~
by ‘feeding the reactants and the catalyst and color in
?de which comprises reacting tertiary dodecyl mercap
hibitor continuously to a reaction zone and providing 15 tan with sulfur in the presence of a catalytic amount of
suitable separation facilities on the outlet from the re
lime, having present in the reaction zone water and a
?nely divided metal selected from the group consisting
The Gardner color referred to in the examples relates
of aluminum, iron, and zinc.
to the Gardner Scale which is designed speci?cally to
6. A process for preparing ditertiarydodecyl polysul
measure the yellow-amber colors of oils and varnishes 20 ?de which comprises reacting tertiary dodecyl mercaptan
with sulfur in the presence of a catalytic amount of phos
using eighteen standard concentrations of ferric chloride,
phorus pentasul?de, having present in the reaction zone
in hermetically sealed tubes. Each color is two-thirds
the intensity of the next higher color. The darkest color
water and a ?nely divided metal selected from the group
matches that of 3 grams of potassium dichromate in
consisting of aluminum, iron, and zinc.
7. A process according to claim 5 in which the re
100 ml. of sulfuric acid. The Gardner Scale is described 25
action is carried out at a temperature of about 200° F.
in Physical and Chemical Examination of Paints, Var
to 300° F.
nishes, Lacquers and Colors, Gardner, H. A. and Sward,
8. A process according to claim 6 in which the reac
G. 6., 10th Ed., Gardner Lab., Bethesda, Maryland,
1946.
tion is carried out at a temperature of about 250° F.
Reasonable variation and modi?cation are possible 30 to 350° F.
9. A process according to claim 3 in which said alkyl
within the scope of this disclosure and the appended
mercaptan contains ‘from 1 to 16 carbon atoms.
claims to the invention, the essence of which is a process
for the preparation of organic polysul?des from mer
10. A process according to claim ‘4 wherein said
tertiary alkyl mercaptan contains from 1 to 16 carbon
captans which comprises reacting a mercaptan with sul
action zone.
for in the presence of a catalyst and a color inhibitor com 35 atoms.
prising a metal dust.
I claim:
1. A process for preparing an organic polysul?de which
comprises reacting a mercaptan with sulfur in the pres
ence of a catalytic amount of lime, having present in the 40
reaction zone a ?nely divided metal selected from the
group consisting of iron, aluminum, and zinc.
2. A process for preparing an organic polysul?de
which comprises reacting a mercaptan with sulfur in the
presence of a catalytic amount of phosphorus penta 45
sul?de, having present in the reaction zone a ‘?nely
divided metal selected from the group consisting of iron,
aluminum, and zinc.
11. Dialkyl polysul?des having improved color char
acteristics prepared by the reaction of alkyl mercaptan
and sulfur in the presence of a catalyst and a color
inhibitor comprising a metal dust selected from the
group consisting of iron, aluminum, and zinc.
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,237,625
2,279,711
2,411,236
2,527,948
Olin _______________ .._
Luten et a1. __________ __
Thacker _____________ __
Lyon et a1. __________ __
Apr.
Apr.
Nov.
Oct.
8,
14,
19,
31,
1941
1942
1946
1950
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