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Патент USA US3043834

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United States Patent C?
3,M3,824
n
Patented July 10, 1962
1
‘
3,043,824
HYDR?PERigélhlzgogll‘igssl-lLF?mE
Alexis A. Oswald
where the- R groups are ‘as herein de?ned. The ?rst re
action product reoresents an organic hydroperoxide, while
Charles B. Rupar and Sydney H. J.
5
Greenwood, Sarnia, Ontario, Canada, assignors to Esso
*
.
a
.
p
.
_
Research and Engineering Company, a corporation of
:26
Second prfzidléict is an grimecanhylgéoigjgleigxldgt‘
wjiktlh
' ough co'oxl a on, mac 1°
0
Delaware
three components, 11.6. mercaptans, ole?ns, and oxygen
No Drawing. Filed Sept. 28, 1959, Ser.No. 842,582
11 Claims. (Cl. 260-935)
alone, it is generally preferable to use a solvent. If
10 isolation of the ?nal product is desirable, it is, of course,
advisable to choose a solvent in which the starting com
The present invention relates to a new and useful class
of organic compounds from the cmoxidation of mama?
Pounds are m°re§°1ub1e than the Teactlon Products
The molar ratlos of the reactants mercaptan, ole?ns,
tans withole?ns or diola?ns_
oxygen, that can, be used may vary considerably.
The
More particularly, the invention teaches the formation 15 merFaptan‘ole?n ‘ratio “between ‘(1001's ' For the prep‘
of organic hydroperoxides and hydroxysulfoxides; the
‘aratio‘n of hydroperoxides and hydroxysulfoxides as
pmpara?on of new and useful compound therefrom’ in_
chem1cal products ratiosclose to equlrnolar are preferred.
cluding surface-active agents; their use in stabilizing pe-
Such a ‘preferre?i r3510 15 bfat‘weel} 05*2; dThe 3mm‘ of
troleum fractions, and as polymerization catalysts; and
9Xygen_preSe’nt m e reach?“ mlxture as epen cut on
other uses as herein described.
20 Its Pamal pliessure and Solublhty‘
The mercaptans which may be used in this invention
The Teactlon System may vary from an oxygen pressure
include aromatic mercaptans and aliphatic mercaptans
and their derivatives. Examples of these compounds are
zmaphthalene ‘thiol, 4_ch1 omthiophenol, and mdodecYl
of 0'05 am‘ ‘It? 50 _atm" ‘preferably betwee,“ 0'2 am" and
5 atm‘ Esp?cl.any “.11 the case of ‘less reactlve merfiaptans
and ole?ns, 1t1s necessary to use super atmospheric pres
mercapta-n. The ole?ns which may be co-oxidized with 25
110x55“! ngaayt It’; mimdlucid to a. oltosed sylstetfz
these compounds include aliphatic ole?ns such as n-octa- through v .vils’ tll . te
esid way?ls 0. SEEP‘ y I1‘
decene-l, and cyclic ole?ns such ‘as cyclohexene and in-
‘
dene. 'Ilhe diole?ns which may he co-oxidized with the
ftbove mei-oaptans Include both ahpliatlc and cyrchc c-on
211: Case of the ge?n'néercgptaslz) cigoildgtlog’ 121mm:
temperature ranges the hydroperoxide reaction products
pen‘tadlene
‘and ‘ahghaml
double ‘bonds’ sue ‘35 ’
pose at various temperatures depending upon their indi
.
‘
.
.
_
oug
an m us or m o ‘ e lqm
esmayrange
omaou-
mac. on. m ‘e’
°
.0
.
n
suc
Jugated dienes, such as ibutadiene, piperylene and cyclo- 30 can be isolated
cygihc dlzriles
1mm tszliated
FYC'OPen a F116‘
The hydroperoxides produced by this invention decom
‘ exa 'ene’
The Mil/g6?1 necessary "E0 the“: cif'oxldatlon Teactlons
vidual structures. By selecting suitable mercaptan and
may be?upplled ‘35 a PHIe gas or 1l¢l{11d§ molecular Oxygen 35 ole?n reactants, it is possible to prepare hydroperoxides
in mixture ‘With other ‘gases, e-g- all‘, may 3150 be usedwhich are stable at relatively high temperatures. A few
In the goo-oxidation of the mercaptans with ole?ns, the
representative reactions of this co-oxidation process are
following reaction mechanism is suggested.
showninTable I.
TABLE I
Ole?nic compound
Starting materials
Mercaptan
‘i311.
Ores + its-Q
1
CH3
~
Oxygen
Hydroperoxide
(‘3H3
+ 0* - @‘HIHQ
02H
.
‘CH3
<:>~(]>=crn + BIS-Q01 + 02 -—> C>—(lJ~—CHr-—S~‘C>Cl
02H
52H
H
+ Hs-<:>
+ 01 -
S_
0211
(‘3H3
C>_<:=orr2 + HS—
(EH3
+
02 _’
C~CHz-—S
02H
"
3,043,824
Table I-Continued
Starting materials
Mercaptan
Ole?nic' compound
:Hydroperonde
Oxygen
LB
“e6.
+
ns-ounn '
merization. of the diole?n excess. The ratio of oxygen
'Ilhe co-oxidation of mercaptans with diole?ns to pro
duce liydroperoxide compounds is a further advantage
is again dependent on the partial pressure of oxygen,
in this invention becauseof the great ease and rapidity 25 which varies between 0.01-50 atrn., preferentially be
at which the reaction proceeds. The suggested reaction
tween 0.1 and 3 atrns. In the case of the very reactive
mechanism for the co-oxidation of mercaptans with con
conjugated diole?ns the use of a pressure greater than 1
jugated diole?ns is as follows:
.
atm. is never necessary. The simplest way to supply
lo,
The formation takes place so readily and simply from
oxygen is by bubbling it through an inductor into the
petrochemical raw materials as to offer an important ad
vantage over common organic peroxides which are pre
liquid reaction mixture.
pared only with great di?iculty. It is usually preferable
hydroperoxides produced according to this embodiment
'
I
The ease of formation of free radicals makes the
tokeep the reaction mixture IbeloW room temperature to 45 of the invention uniquely suitable“ as catalysts for a low
'avoid decomposition of the hydroperoxide reaction prod-.
temperature polymerization. Also, they can be used as
uots.
' ‘The molar ratios of the reactants, diole?ns, mercaptans
and oxygen can be varied considerably. The mercaptan
curing agents, reactants for the removal of pyrrole-type
compounds from petroleum, monomers for manufactur
ing plastics, and as a starting material for a variety of
diole?n ratio is 0.000l—l0 preferably 0.001—2. vA small 50 chemical syntheses.
mercaptan-diole?n ratio can be especially useful, when
Representative reactions are as follows:
TABLE II
Starting materials
Diole?nic compound
Mercaptan
U
Oxygen
@411 + 0, @ii- _ 02H
Cl
srr + 0, (HQ
v
the hydroperoxide formed is used for the in situ poly
Reaction product
7
HO
I
—
CH2
‘
In a further embodiment of the invention, it has been
3,043,824
..
5
‘radical containing from C2 to C32 carbon atoms, prefer
ably from C2 to C18. These hydrocarbons include
found that the co-oxidation of mercaptans with ole?nsor "
diole?ns can be catalyzed by agents abstracting hydrogen
aromatic and aliphatic groups which may be de?ned as‘
from mercaptans. This abstraction results in the forma
follows.
tion of mercapto radicals which start the co-oxidation
The term “aromatic mercaptan” shall be interpreted to
chain. The use of such chain initiators, e.g. ultraviolet 5
include ‘both a non-substituted aromatic mercaptan and a
light, peroxide compounds, is especially important when
halogen-substituted aromatic mercaptan where one or
aliphatic mercaptans or n-ole?ns are co-oxidized. In the v
more halogen atoms are substituted for hydrogen atoms
absence of such catalysts, some co-oxidation reactions
connected to a carbon atom of the aromatic ring. In the
have extremely long induction periods and are not prac'-'
10
case of aliphatic mercaptans R is an open chain radical.
tical to carry out because of sluggishness of the reaction.
The ole?ns may be represented by the general formula
In the presence of ultraviolet irradiation or a peroxide
CRR’=CR”R"' where R, R’, R" and R'” are, hydrogen,
catalyst, suitable initiation can be effected within a few
cyclic or aliphatic hydrocarbon radicals.
hours, and the reaction can be completed in a few days
“Cyclic” include radicals wherein a ring structure is
at room temperature.
15
present. The aliphatic radical includes saturated open
As suitable catalyst a 250 v., 100 w., 60 cycle ultra
chain hydrocarbon radicals, such as n-hexadecyl.
violet lamp can be used. For instance, this lamp- may be
The diole?ns may be represented by the general formula
placed about 1 inch from a 500 ml. quartz reaction bottle.
CRR1—CR2—X—CR3=CR4R5 where R, R1, R2,‘ R3, R4
Gamma irradiation can also catalyze such co-oxidation.
It is usually enough to use irradiation only during the 20 and R5 is hydrogen, cyclic or aliphatic hydrocarbon radi
cals; X is non-existent or a two valent, cyclic or aliphatic
?rst half hour of the reaction. Among the peroxide
hydrocarbon radical. R, R1, R2, R3, R4 and R5 can be
initiators of the reaction, hydroperoxides, such as t-butyl
satis?ed, e.g. by cyclohexyl and methyl groups. X can
hydroperoxide, cumene hydroperoxide, and (Z-hydro
peroxy-2-phenyl-) ethyl phenyl sul?de, are especially suit
be methylene, tetramethylene, cyclohexylene, and their
able to use. Such hydroperoxide catalysts'may be pre
substituted derivatives.
pared from reactive hydrocanbons (and mercaptans) in
To more fully illustrate the invention, the following
examples are given:
situ. If they are added to the reaction mixture, their
amount varies from 0.5 to 0.0001 mole preferably from
0.1 to 0.001 mole per mole of mercaptan or ole?n.
'
EXAMPLE 1
30
The general procedure in this series of experiments was
The mercaptans of this reaction may be represented by
the general formula RSH wherein R is a hydrocarbon
to mix on ole?n and a mercaptan in a diluent.
Air was
TABLE III
Reaction product precipitated 5
Reactants
Diluent .
Reaction
time,
Mercaptan
'
Name
hrs.
Yield,
Peroxide
content,
Percent '1 Percent G
Styrene ___________ __
Mole
-Thiol
Mole
Name
Ml.
300
2-(l-hydroperoxy-)indany1 2-naphtyl
0. 1
2-naphthalene___
0. 1
n-Heptane- _
Benzene. _ __
125
0. 05
Benzene_________
0.05
n-Heptane. _
150
0. 05
_ _ . __do _________ _ _
0.05
_ __ _ -do _____ _ .
150
n-Heptane. _
300
6. 5
(2 - hydroperoxy - 2 — phenyl -)propyl
Benzene"...
Petroleum
dist.3
0. 05 _____do.3____-
50
300
20
2 - naphthyl sul?de.
(2 - hydroperoxy - 2 - phenyl -) propyl
300
20
(2 - hydroperoxy - 2 - phenyl -) propyl
0. l
2-naphthalene___
0. 05
4-chlorobenzene.
0. 05
Benzene _______ __
0. 2
'
1 98
sul?de
Z 12
2 10
(2 - hydroperoxy - 2 - phenyl -) ethyl
phenyl sul?de.
0.05
1 81,2 2
67
2 30
42. 6
2 18
4-ch10rophenyl sul?de.4
1 Iodine method.
2 Ferrous sulfate titanous chloride method.
3 Boiling range 300° to 600° F.
4 Upon standing at room temp. converted to a White cryst. solid-(2-hydroxy-2-phenyl-) propyl 4-chlorophenyl sulfoxide.
.
i'
5 All reaction products were colorless, viscous, oil products at room temperature except 2-(1-hydroperoxy)-lndanyl Z-naphthyl sul?de, which was'a
white crystalline solid melting with decomp. at 70° O.
6 Percent of the calculated value for the hydroperoxide co-oxidation product.
1 Precipitated by cooling the solution to —5° 0.
then introduced into the mixture through a sintered glass
’ EXAMPLE 2
inductor while the solution was cooled in ice to 0°. C.
The ‘following table illustrates the reaction of diole?ns
Where the reaction temperature was other than 0" C.,
and mercaptans in accordance with the invention. Unj
the table below so indicates. By the end of the oxida
less otherwise indicated, the reaction was carried out at
tion period, the reaction product separated on the bottom 70 0° C_ In an Cases, air was usedv as the oxidizing agent
of the reaction ?ask. The reaction product was analyzed
and was introduced through a sintered glass inductor.
for hydroperoxide content after isolation. The results are
The products of conjugated diole?n mercaptan co-oxida
shown in Table III.
tion separated as almost colorless viscous oils and were
This table shows the reaction of ole?ns with mercap
analyzed for peroxide content by the iodine method. The
tans typical of this invention.
75 results are shown in Table IV.
3,043,824
TABLE IV
Reactants
\
Run No.
Diene
.
n-Heptane
Reaction
Ppt.
diluent
ml.)
time
(Hrs)
temp.
(° 0-)
Mercaptan
Name
Mole
l?-hutadiene
do- -
0.2
Excess
-Thiol
Mole
0. 1
0. 1
60
100
4
5
0.2
0, 2
0. 1
0. 1
200
300
16
16
0
0
5 ....... -_ ,Dicyclopentadieue __________________ __
0. 1
0. 1
300
6
0
6‘ '
74
a
0. 1
O. 05
0, 1
0.1
0. 1
0. 1
800
300
300
16
16
16
20
20
0
Piperylene
Cyclopontarliprm
Benzene ____________________________ -.
Yield
Run
No.
Reaction product
~
1- _ __
2-
Peroxide
Isomer
content,
percent
.P.
(° 0.)
Percent Grams
1-hydroperoxy-4phenyl mercapto-Z-butene ________ _ _
do- _
40
Carbon
Celcd.
8
41
Hydrogen
Sulfur
Found Calcd. Found Oalcd. Found
61. 54
6. 23
16. 3
8. 2
3_--_ 1-hydroperox'y-4, 2’uaphthyl-rnereapto-2-peutene..__
77
2 20
L--- 2-ltiydroperoxy-4-2’naphthyl
mercapto-Zcyclopcn-
73
2 19
5--.- 4,7 - methylene - 5,2’ - naphthyl - mercapto - 6 -hy-
48
0
0
16. 3
° 65. 68
6v 20
6. 21
67. 40
6. 46
62. 37
5. 55
14. 8
14. 9
12. 31
° 11. 1
5. 91
12. 41
11. 4
5. 58
10. 39
10. 25
one.
I
14. 7
a 12
droperoxy-tt,5,6,7,8;9-hexahydroindene.
6--.. ...._d0__
3210-2
62. 20
"@232
’
33
10.2
12
8210-2
61. 85
5. 63
ll203-6
10. 25
'
185-7
7---- -_-__d0.
10. 2
12
8---- -.-.-d0--
Z). 8
12
3210-2
u203~5
185-7
3210-2
60.82
5. 63
10. 46
“203-5
185-7
IDeeomposed.
1 Air and butadiene introduced at about equimolar rates into thiophenol-heptane solution.
3 After washing with n-heptane.
\
‘ Decreased 5.5% after 2-mo. standing at room temp.
‘ Reaction at room temperature.
_
| Water cooled during ?rst two hours to maintain room temperature.
- ' The lower than theoretical carbon and sulfur values suggest some peroxidetion of diole?n alone.
It will be noted from run 7 on the above table that
H, 10.75; S, 8.9. The calculated values for CZOHHSOQ
an attempt to co-oxidize one mole of dicyclopentadiene
are the following: C, 70.95; H, 10.12; S, 9.47.
>
The mother liquor ‘from the second ?ltration was cooled
in a solid carbon dioxide-methanol bath and ?ltered
again. About 2.5 grams, i.e., a yield of 10.4% white
with two moles of 4~chlorothiophenol failed. This shows 45
that the second double bond of the diole?n is less re
active. 3.6 grams of the 4-chl0r0thiophenol were un
changed on the basis of a mercaptan number determina
crystalline product remained on the ?lter. After recrystal
lization from benzene-n-heptane, the puri?ed product was
tion; The ,co-oxidation product precipitate contained
only one mole of mercaptan per mole of dichloropenta 50 found to melt at 66—'69° C. An elemental analysis rc~
vealed the ‘following: C, 70.37; H, 10.31; S, 9.1. The
diene: a product identical with that obtained in run 6.
The following examples indicate the e?icacy of ultra
violet light as a catalyst in the co-oxidation reaction.
EXAMPLE 3
co-oxidation reaction described in the example proceeds
- through an unstable peroxide intermediate and gives a
55
20.2 grams (0.1 mol) of n-dodecyl mercaptan and 10.4
grams (0.1 mol) of styrene were dissolved in 150 ml.’
n-heptane in a 500 ml. Vycor (quartz) bottle. The solu
tion was placed about 1 inch away from an ultraviolet
lamp (250 v., 100 w., 60 cycle; G.E.-9T64Y20) and air 60
' was introduced through a ?ne sintered glass gas induc
mixture of crystalline isomeric Z-phenyl-Z-hydroxy-ethyl
n-dodecyl sulfoxides in 79.1% overall yield. In a con
trol solution unexposed to ultraviolet light, no hydroxy
sulfoxide precipitate was formed during the same period -
of air introduction.
EXAMPLE 4
11.6 grams (0.1 m.) indene and 20.2 grams (0.1 m.)
n-dodecyl mercaptan were dissolved in 300 ml. n-heptane.
of air, the precipitate formed in the solution was ?ltered
Air was introduced into the solution which was placed
off. 4.5 grams, i.e. ‘18.7% crystalline substance was ob
Vycor (quartz) round bottom ?ask and
65 into a 500
tained. This substance contains 12% peroxide (calcu
irradiated with an ultraviolet lamp (250 v., 100 w., 60
lated for 2-phenyl-2-hydroperoxy-ethyl n-dodecyl sul?de).
cyc1e—-G.E.—9T64Y20) at a half inch distance. After.
The introduction of air into the ?ltrate was continued
one day, an orange reaction mixture resulted which on
for another 6 hours. This resulted in the formation of
one more day‘ air introduction without ultraviolet light
more crystalline precipitate. By repeated ?ltration an
deposits 14.7 g., i.e. 42% product. This product had
other 12pgrams, i.e. a yield of 50% product was obtained.
3% peroxide content of the 2-(l-hydroperoxy)—indany1
This was recrystallized from benzene/n-heptane mixture
dodecyl sul?de. On recrystallization of the product the
and gave 9 grams of puri?ed 2-phenyl-2-hydroxy-ethyl
peroxide content disappeared and the isomeric 2-(1-hy
n-dodecyl sulfoxide, ~M.P. 107-109° C. The following’
droxy)-inda'nyl dodecyl sulfoxides shown at No. 16 in
values were found after elemental analyses: C, 70.50‘; 75 Table V.
tor during irradiation. A half hour after the introduction
3,043,824
TABLE V——Continued
Carbon
No.
Structural Formula
'
Oalc’d.
16“.--
Hydrogen
Sulphur
Melting
point, ° C.
107 -109
67
71.95
- 68.5
Found
Gale’d.
Found
69.85
9.77
9.59
71.73
?-CuHa
O
9.53
Oalc’d.
Foimn
9.15
....... ..
9.6
9.3
./
OH
I Decomposed.
EXAMPLE 5
After 24 hours’ air introduction, the mixture contained
only 0.004 mol mercaptan, i.e. 4% of the original but
0.02 mol hydroperoxide. After removal of the naheptane
solvent, 31.3 lgrams of a colorless liquid remained, which
25.2 grams (0.1 m.) l-n-octadecene and 11.0 grams
(0.1 m.) thiophenol were co-oxidized by air in heptane
solution in a manner described in the previous example.
After four. hours’ irradiation and a total of twenty hours 20 had the following composition: C, 68.69; H, 11.29; S,
10.0 The calculated composition of (2-hydroperoxy-2
of
introduction, half of the original amount of mer
phenyl)-propyl dodecyl sul?de is: C, 71.52; H, 10.30; S,
captan had been converted according to mercaptan num~
9.1. The peroxidic product yielded (2-hydroxy-2
ber determination. Eight grams, i.e. a yield of 20.3% of
phenyl)-propyl dodecyl sulfoxide shown at No. 11 in
a product containing 3% peroxide, was removed by ?l
Table V on low temperature crystallization.
tration. On recrystallization the peroxidic product was
25
As it was mentioned, the primary products of such
converted to isomeric 2-hydroxy-octadecyl phenyl sul
reactions are new hydroperoxides. It is well known that
foxides with properties shown at No. 2 in Table V.
hydroperoxides generally can be used as polymerization
Further introduction of air into the once ?ltered mixture
‘ catalysts. In this respect, these new hydroperoxides can
resulted in the precipitation of more co-oxidation product.
No solid co-oxidation product was formed in a parallel 30 have new applications for vulcanization of rubber or
similar products because of their sulfur and ole?n content.
co-oxidation experiment carried out without ultraviolet
initiation.
The hydroxysulfoxide secondary products of dicyclo
pentadiene mercaptan co-oxidations are potential petro
leum additives, antistatic agents and pesticides depending
‘
EXAMPLE 6
13.2 grams (0.1 mol) dicyclopentadiene and 20.2
grams (0.1 mol) of n-dodecyl mercaptan' were co-oxidized
in n-heptane solution with air in the usual manner for 1
day. After this period, a mercaptan number determina
on
the the
reaction.
type of mercaptan and dicyclopentadiene used
The following two examples show the use of the hydro
‘ peroxide products in accordance with the invention in
- tion showed only 5% mercaptan conversion. When an
radical polymerization.
other mixture of the same composition was irradiated
EXAMPLE 9
with an ultraviolet lamp (250 v., 100 w., ‘60 cycle-GE. 40
9T64Y20) at V2 inch distance while air was introduced
0.3 grams (0.001 mol) of 2-(1-hydroperoxy)-indanyl
into it, 85% mercaptan conversion was achieved after the
Z-naphthyl sul?de prepared 'by the method given in run
same reaction time. A liquid co-oxidation product with
No. 1 of Example 1 was added to 34.6 grams (0.3 mol)
a light yellow color remained after the solvent was re- of styrene as a polymerization catalyst. The mixture
moved by distillation.
was then placed into a cold box at +5“ C. for 3 months.
The following two examples are illustrative of the
At the end of this period, the mixture was a very viscous
ef?cacy of added hydroperoxide catalysts in the co-oxid'a
liquid with a refractive index, nD2° 1.5584. On distilla
tion reaction.
'
tion at 20 mm. from a steam bath, only 75% of the
'
EXAMPLE 7
material could be removed. The remaining 25% .isa
10.4 grams (0.1 mol) styrene and 20.2 grams (0.1 50 solid, rubbery substance, polystyrene. Styrene without
added hydroperoxide in a control experiment had up”
mol) n-dodecyl mercaptan were dissolved in 300 ml. n
1.5468 and could 1be distilled under the same circumstances
heptane. The solution was placed into a 500 ml. measur
ing cylinder and air was introduced into it for 12 days. l
- Immediately after the start of the air introduction, 0.18
in 99%.
7
gram (0.002 mol) t-butyl hydroperoxide was added to 55
the reaction mixture as a catalyst.
From time to time,
on a ?ltrate sample showed only 0.002 mol'unconverted
so
By ?ltration of the heterogeneous
mixture, 23.9 grams (70.7%) white, solid peroxidic prod-‘
tillated at 10
pressure from a water bath.
gram of residue on distillation.
65
5.8
'
'
'
It can be seen from these two “examples that these new
sulfur containing hydroperoxide catalysts are particu
larly advantageous for inducing low temperature poly
merization between —60 and +70° C. The quantity
the ?ltrate to -—15° C. and subsequent ?ltration, 3.3 g.
(8.9%) more solid, peroxidic product was obtained. On
recrystallization, the product yielded the peroxide free
isomeric (2-hydroxy-2-phenyl)-ethyl dodecyl ,sulfoxides
EXAMPLE 8
room temperature. The resulting viscous liquid was dis
‘A control experiment with styrene alone gave only 0.05
14% of the peroxide content calculated for the (2
shown at No. 8 in Table V. H
0.5 gram of the product of 1,3-but-adiene co-oxidation
grams of white, solid polymer remained. This means
that 5.3 grams, i.e. 17.6% of the styrene was polymerized.
uct was obtained. According to a hydroperoxide deter
mination by the sodium iodide method, this product was 7,
hydroperoxy-2-phenyl) -ethyl dodecyl sul?de. By cooling
‘
shown in run No. 1 of Example 2 was dissolved in 30
grams of styrene. ,The solution was stored in an air
, tight bottle of about 35 ml. volume for two weeks at
the n-heptane evaporated was replaced. At the end of
the 12-day reaction period, a mercaptan determination
mercaptan sulfur.
I,
EXAMPLE 1o
of these catalysts may vary from 0.0001 mol to 0.1 mol
_ 70
per moleyof ole?nic compound to be polymerized. It
~ ~ was already mentioned in Examples 3, 4, and 5 that the
hydroperoxides of the co-oxidation reaction gave hydroxy~
sulfoxides on recrystallization. The use of hydroperox
11.8 grams (0.1 mol) a-methyl styrene and- 20.2 grams
nddodecyl mercaptan were dissolved in 300 ml. n-heptane.
ides as a. chemical intermediate for the preparation of
The solution was aerated as in the previous example. 75 hydroxysulfoxides is shown in the following examples.
35,042,824"
13
14
EXAMPLE 11
derivative can be added to the liquid reaction mixture
.
.
u
3.18 grams (0.01 mol) of 2-‘(l-hydroperoxy)-indanyl
of ole?n, mercaptan and possibly solvent before the
2-naphthyl sul?de were dissolved in 50 mls. of benzene.
The hydroperoxide was prepared in accordance with run
No. 1 of Example 1. The solution was kept 16 hours
addition of oxygen or simultaneously with oxygen. The
simultaneous introduction of sulfur dioxide gas and air
is preferred. Another preferable arrangement is the in
at 43° C. and then allowed to cool to room temperature.
troduction of air into an emulsion consisting of the
The precipitate formed was vacuum ?ltered and recrystal
hydrocarbon solution of the mercaptan and ole?n and
lized from benzene.
water solution of sodium bisul?te. In the latter manner,
the sulfuric acid half ester sodium salt is obtained in a
About 1.5 grams or a yield of
47.1% of 2-(1-hydroxy)-indanyl Z-naphthyl sulfoxide as
a white crystalline substance was obtained.
A melting 10 one-step operation according to the following summarize
point of 138-l41° C. with decomposition was observed.
By the concentration of the benzene ?ltrate other crystal
line 2-(1-hydroxy)-indanyl Z-naphthyl sulfoxide isomers
can be obtained. Analytical data for these different
equation:
-
R—S-—I-I+CH2=CR2’+O2+NaHSO3-—>
'
15 Generally speaking, the presence of an alkyl radical
isomers are shown at No. 15 in Table V.
having from 6-30 ‘carbon atoms is necessary in the sur
Some physical and analytical data of other new hy
droxyethyl-sulfoxides prepared by heating the corre
face active molecules.
sponding hydroperoxides in benzene solution on a steam
bath are shown in Table V.
can be used as detergents, emulgents, impregnates, dis
Such surface-active compounds
persants, solubilizers, wetting agents and foam producers.
The removal of dienes from steam cracked naphtha 20
by co-oxidation is also contemplated by this invention.
The following example illustrates this.
The following examples show the preparation of sur
face-active compounds.
EXAMPLE 13
EXAMPLE 12
10.4 grams (0.1 m.) styrene and 20.2 grams (0.1 m.)
16 grams (0.1 mol) Z-naphthalene thiol were dissolved 25 n-dodecyl mercaptan were dissolved in 300 ml. n-heptane.
in 100 mls. (82 grams) steam cracked naphtha of diene
The solution was placed into a 500 ml. measuring cylinder
number 34. Air was introduced into the solution at
room temperature for three hours. After three hours,
the solution was cooled down to 0° C. and the air in
troduction was continued for another 3 hours. At the
end of this period, the clear, orange colored reaction
mixture was placed into a cool box at —15° C.
and oxygen and sulphur dioxide were introduced into it
at the same time for three hours while cooling it with
ice water. After three hours 7.5 g. (18.6%) yellow oily
30 product separated on the bottom of the reaction mixture.
The supernatant hexane solution deposited 5 g. (12.4%)
At
more oil on cooling to —15° C.
this temperature an almost colorless solid precipitated.
The united oily fractions were Washed by n-heptane,
It was ?ltered off by suction and washed by cold n
freed from volatile components in a vacuum desiccator
heptane. In this manner, 0.4 gram of substance resulted, 35 and analyzed. The following composition was revealed:
which had a high peroxide content (peroxide equivalent
C, 56.36; H, 8.09; S, 12.93. The calculated values for
‘242). The ?ltrate (653 grams) has been diluted with
(2-phenyl-l-dodecylmercapto)-ethyl alcohol sulphuric
an equal volume of n-heptane, when 24 grams of orange
colored co-oxidized product separated as a bottom phase
at room temperature.
The latter product had a peroxide 40
equivalent to 393. The diene number of the steam
cracked naphtha decreased to one-third of the original
as a result of the treatment.
In another experiment, a steam cracked naphtha of
14 diene number was treated in the presence of 2
naphthalene thiol in the presence of oxygen in a similar
manner. After the treatment, a product of 1.6 diene
number was obtained after distillation.
‘It is noted that with the clay treatment, which is
usually used for the removal of dienes from steam
cracked naphthas, only about.50% reduction in diene
number was obtained.
_
acid half ester are: C, 59.66; H, 8.51; S, 15.93.
_
Co-oxidation reactions for the removal of reactive
EXAMPLE 14
10.4 grams (0.1 m.) styrene and 20.2 grams n~dodecyl
mercaptan were dissolved in 300 ml. n-heptane. The solu
tion was placed into a 1 liter measuring cylinder and solu
tion of 9.1 grams (0.05 m.) Na2S2O7 in 200 ml. water was
added to it. Air was introduced into the two—phase sys
item at room temperature.
Within a few minutes after
the start of air introduction, an emulsion with a tendency
to foam was formed. After three days’ air introduction, a
.mercaptan number determination showed a 50% conver
50 sion and a stable emulsion was obtained.
The emulsion was broken by the addition of 50 ml. a1
cohol and the reaction mixture was separated in two
phases. The water phase was concentrated in vacuum by
heating with a steam bath and left 20.2 g. of the solid
ole?ns and/or mercaptans can be carried out in other
petroleum fractions in similar manner. Depending on
emulgent containing (Z-phenyl-l-dodecyl-mercapto)-ethyl
the composition of the particular fraction diole?n or 55 alcohol sulfuric acid half ester sodium salt.
mercaptan can be added to achieve about an equimolar
The hydroxy group of the hydroxysulfoxides can be
concentration of the reaction components.
also 'esteri?ed with sulfuric acid (S03) and the half ester
Hydroperoxides with suitable alkyl substituents can be
can be converted to a salt to give a detergent. An illus
converted to surface active agents by the following se~
60 trative example of such a reaction is described in Ex
quence of reactions:
ample 15.
EXAMPLE 15
Me+z metal cation as Na+, K+, Lit, Ca++, Ba++, Pb“, etc. in
6.76 grams (0.02 mol) of 2-phenyl-2-hydroxy-ethyl
n-dodecyl sulfoxide (alternative name (2-dodecylsul?nyl
65 2-phenyl)-ethanol), 5 grams (0.224 mol) of sodium pyro
sulfate and 1.77 grams (0.0224 mol) pyridine Were mixed
in a round bottom ?ask. Then the contents were heated
on a water bath and stirred effectively until a product
soluble in warm water resulted. Consequently, 70 mls.
Hydroperoxides containing sulfur in a divalent vform
are generally not stable enough for isolation. Another 70 of water and 18 grams of sodium chloride were added to
the reaction mixture. The stirring was continued for an
feature of the present invention overcomes that difficulty.
the form of a metal oxide or hydroxide or a base, e.g. an
amine as triethanolamine and the like.
other l1/2 hours. Then the precipitated white, pasty prod
Sulfuric acid half esters can be prepared by adding sul
fur dioxide or a suitably acidic sulfur dioxide salt (e.g.
uct was ?ltered off and dried to give an almost white
sodium hydrogen sul?te, formaldehyde sodium sulfoxilate)
product with detergent properties. The product amounts
to the co-oxidation mixture.
The sulfur dioxide or its 75 to 8.6 grams, i.e. 96% yield calculated for C18H33O5S2Na
3,043,824
is
15 ~
(2-dodecylsul?nyl-l-phenyl)-ethyl alcohol sulfuric .acid
at a temperature in the range of from about —10 to '
100° C. during a period of from about 5 minutes to 3
monoester sodium salt.
days, wherein R is selected from the group consisting of
The formation of a sulfuric acid half ester and its
sodium salt ‘from the hydroperoxide obtained by co
oxidation in coker gas oil isillustrated in the following
aryl, alkyl, cycloalkyl, alkaryl, and aralkyl; and R" is
selected from the group consisting of an aromatic and ali
phatic hydrocarbon radical, and R’ is a C2 to C10 saturated
two examples.
hydrocarbon radical.
EXAMPLE 16
3. A method of removing a diene from a liquid hydro
p 4 1. fresh untreated coker gas oil having 31.68 mer
carbon fraction containing a diene which comprises the
captan number was placed into a 5 litre'separating funnel.
Air and sulfur dioxide were introduced into the solution 10 introduction of from 0.01 to 1 mol of a mercaptan per
diole?n into said hydrocarbon fraction, co-oxidizing said
at room temperature for 1% hours. After 15 minutes of
diene and mercaptan with molecular oxygen and separat
reaction time, a black oil began to separate from the oil.
ing out the reaction products from said oxidation.
At the end of the reaction time, 8.7 g. sludge was sepa
4. A hydroperoxide having the general formula:
rated. The analysis of this sludge revealed the follow
ing: C, 62.96; H, 7.86; S, 6.43; N, 3.05. (The oil had
15
a mercaptan number of 10.56 after this procedure.) The
high nitrogen content of the sludge shows that the acidic
wherein R and R’ together contain a total of 2 to 18
carbon atoms, R being selected from the group consisting
sulfuric acid half ester precipitated some nitrogen com
ponents of the oil. Therefore, the reaction is alsouseful
for the removal of nitrogen from petroleum fractions.
20
EXAMPLE 17
of hydrogen, alkyl, alkenyl, cycloalkyl and cycloalkenyl
radicals and R’ being a C2 to C10 saturated hydrocarbon
radical, and R” is selected from the group consisting of
naphthyl and halogen-substituted aryl radicals, the hydro
3 litre coker gas oil (the same as in the previous ex
periment) and the solution of 34.6 grams Na2S2Oq in
peroxy group and sulfur atom of said hydroperoxide be
600 ml. water were placed into a 6 litre measuring cylin 25 ing bonded to different carbon atoms of R’.
' '
der. Air was introduced into the solution for 24 hours,
5. A process forproducing a sulfur-containing hydro
while it was stirred by a magnet. At the end of the reac~
peroxide which comprises passing a gas containing mo
tion period, the water phase was separated and the solvent
lecular oxygen into a liquid reaction mixture containing a
evaporated. The remaining solid consists of a mixture
C2 to C18 hydrocarbon selected from the group consist
of unchanged sodium bisul?te and the half ester salt. 30 ing of aliphatic monoole?ns, cycloaliphatic monoole?ns,
An analysis of that solid revealed 5.91% carbon content,
aliphatic diole?ns, cycloaliphatic diole?ns and indene and
which shows some reaction with the oil, although to a
a C6 to C18 mercaptan selected from the group consisting
limited extent.
What is claimed is:
of naphthyl and halogen-substituted aryl mercaptans while
1. A polymerization process ‘which comprises polymer
izing an ole?n monomer polymerizable by free radicals
in the presence of a hydroperoxide of general formula:
maintaining said reaction mixture at a temperature be
35 tween —50° and 0° C.
6. A process in accordance with claim 5 wherein said
gas is ‘air.
'
7. A process in accordance with claim 5 wherein said
liquid mixture is irradiated with ultraviolet light while
40 said gas is passed thereinto.
8. A process in accordance with claim 5 wherein said
liquid mixture contains a catalytic amount of an organic
wherein Rand R’ together contain a total of 2 to 18
carbon atoms, R being selected from the group consisting .
of hydrogen, alkyl, alkenyl, cycloalkyl and cycloalkenyl
radicals and R’ being a C2 to C10 saturated hydrocarbon
radical, ‘and R" is selected from the group consisting of
peroxide.
'
.
9. A hydroperoxide of the general formula:
45
wherein HO2—X- is a 2-(1-'hydroperoxy)indanyl radi
cal, the sulfur atom being bonded to the 2-position of
peroxy group and sulfur atom of said hydroperoxide be
said radical. and R’” is a C2 to C13 alkyl radical.
ing bonded to different carbon atoms of R’.
'
10. A hydroperoxide of the general formula:
50
2. A method of preparing an organic sulfoxide having
S
I!!!
naphthyl and halogemsubstituted aryl radicals, the hydro
the formula
R-R'——S—R"
0211
wherein H02——X-- is a 2-(l-hydroperoxy)indanyl radi
cal, the sulfur atom being bonded to the 2-position of
55 said radical, and R"" is a C6 to C18 aryl radical.
11. 2-( l-hydroperoxy)indany1 phenyl sul?de.
‘which comprises passing a gas comprising molecular oxy
References Cited in the ?le of this patent
UNITED STATES ‘PATENTS
gen through a solution of a sulfur containing organic
hydroperoxide having the formula
60
2,386,774
2,398,479
Badertscher _....'_ ______ __ Oct. 16, 1945
Vaughan et a1 _________ .._ Apr. 16, 1946
2,515,120
2,531,602
Harman _____________ ..._ July 11, 1950
Bell ________________ _._ Nov. 28, 1950
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