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Patented Dec. 24, 1946
_ s'r'r
Ernst Zerner, New York, and William Kaplan,
Brooklyn, N. Y., assignors, by mesne assign
ments, to Sun Chemical Corporation, New York,
N. Y., a corporation of Delaware
'No Drawing. Application June 22, 1944,
Serial No. 541,664
1 Claim. (Cl. 260-505)
This invention relates to improvements in
methods of producing alkyl-aromatic sulfonates
useful as surface active agents and for detergent,
it is unnecessary to separate the unsaturated part
out of a cracked mineral oil before condensation
even when only 10-35 per cent unsaturated hy
wetting and similar purposes. It relates more
drocarbons are present. The condensation of the
particularly to improvements in methods of pro
unsaturated material with an aromatic hydro
ducing higher alkyl-aromatio sulfonates from
carbon as benzene, toluene, xylene still takes
non-aromatic hydrocarbon mixtures by conden
place with a reasonable yield. After condensa
sation with aromatic compounds with the aid of
tion, ?rst the excess of the aromatic hydrocarbon
aluminium chloride as a condensation catalyst,
and then the higher boiling saturated hydrocar
followed by sulfonation of the condensation 10 bon is distilled off; the latter being deodorized
and water-clear and thus presenting a product
It is a well known fact that nuclearly sulfon
of increased value.
ated alkyl-aromatic compounds are valuable de
Another object of this invention is to increase
tergents, either as such or'in the form of their
the yield of the process. This can be performed
alkali salts. Due to their excellent qualities and 15 according to this invention by using gaseous hy
their comparatively low cost, they are dominating
drogen chloride as an additional catalytic agent.
the market.
It is probable that some part of the hydrogen
One known method of preparing said sulfon
chloride adds to the double bond and is split off
ated alkyl-ar0matic compounds consists in chlo
again in condensation so that a new addition to
rinating re?ned Pennsylvanian kerosene, con 20 another part of so far una?ected unsaturated
densing the chlorinated product with benzene,
hydrocarbon may take place. Without using hy
toluene, or xylene in the presence of aluminium
drogen chloride, a substantial part of the un
chloride and sulfonating the reaction product
saturated hydrocarbon does not condense, it
thereafter. Although the chemical character of
rather undergoes some other reaction leading to
the ?nal product is known in general, it repre 25 formation of tar.
sents a mixture of numerous compounds differing
Another advantage of promoting the condens
according to the raw material used and the work
ing effect of aluminium chloride as described, is
ing and re?ning methods applied.
the fact that fewer undesirable by-products are
The chlorination needs a very expensive equip
formed. While ‘the yield of the condensation
ment. Furthermore, mono, di, and poly-chlori 30 product without the addition of hydrogen chlo
nated compounds are simultaneously formed and
ride amounts to about 30 per cent of the theo
have to be separated at some stage of manufac
retical value (based on content of unsaturated
turing by certain purifying methods.
hydrocarbon), it is raised to about 45 per cent
when hydrogen chloride is bubbled through the
reaction mixture, in the ?rst ?ve minutes.
We have found that bromine and hydrogen
bromide are still more effective, apparently be
It is one object of this invention to eliminate
the step of chlorination. This is performed ac
cording to this invention by working with unsat- '
urated instead of saturated hydrocarbons as a
raw material for the Friedel—Crafts condensa
tion. This enables us to use a raw material which
cause the addition of these materials to the dou
ble bond proceeds much faster than the addi
is otherwise of very little value.
40 tion of hydrogen chloride. This method of oper
The condensation of unsaturated aliphatic hy
ation raises the yield to about 60 per cent of the
theoretical value.
drocarbons with aromatic hydrocarbons like ben
The main object of this invention is to use
zene, toluene, xylene, by a Friedel-Crafts reac
cracked mineral oil containing only 35 per cent or
tion is well known. The use of this reaction for
manufacturing detergents by sulfonating the 45 less unsaturated hydrocarbon as a raw material
alkyl-aromatic condensation products is equally
for a Friedel-Crafts reaction with benzene, tolu
known and disclosed in several patents. Accord
ene or xylene and to sulfonate the so-obtained
condensation product after removing the excess
of aromatic and the unattacked saturated hy
ization of gaseous ole?ns as formed in cracking 50 drocarbon by distillation.
of mineral oils for the condensation. According
Other objects of the invention will be obvious
ing to one of the known processes, e. g. ole?ns are
used as starting material, obtained by polymer
to another process the unsaturated part of a
, and will appear hereinafter.
cracked kerosene is extracted e. g. with liquid
The cracked mineral oils which we employ
sulfur dioxide and is used as a starting material.
must not be too low in boiling point and/molecu
Now, we have found the surprising fact that 55 lar weight. It is common knowledge that any
surface active product has to contain a hydro
After standing for twelve hours, the sulfonation
mixture separates into three layers: A lower layer
philic and a hydrophobic part and there. has to
of' spent acid, a middle layer oi’ 40 parts of alkyi
be a certain balance between these constituents.
Therefore, only such sulfonated alkyl aromatic
benzene sulfonate, and an upper layer of hydro
compounds are appreciable detergents in which
carbon. The alkyl-benzene sulionate has an acid
the side chain which represents particularly the
number of about 400 indicating that about 20 per
hydrophobic part has a certain minimum length.
cent of free sulfuric acid is present. The alkyl
On the other hand, this side chain can not be
benzene sulfonate is treated with a small quan
too long because the hydrophobic properties oi’
tity of water and enough sodium bicarbonate
the sulfonated products would be too high and, 10 togive a paste which, when dried, contains about
therefore, their calcium and magnesium salts
40 per cent of active‘ material. The paste is
then dried and ground. A powder possessing ex
would not be soluble enough. In other words. if
cellent detergent properties is obtained.
the side chain is too lens, the detergent would
not be fast enough to hard water. It has been
our experience that the boiling range of our un
saturated hydrocarbon serving as a raw material
Similar results are obtained by working with
toluene or xylene instead of benzene.
should be about 150 to 300° C. under atmospheric
pressure. Expressed in length of the molecule,
they should contain between’ 8 and 16 carbon
The same vprocedure as described in Example
Most of the sulfonated alkyl aromatic deter
gents on the market are manufactured by using
Pennsylvanian petroleum as a starting material,
Example I]
I is performed again, except that dry hydrogen
chloride is bubbled through the condensation
mixture for the ?rst ?ve minutes. The con
densation is then continued for only two hours
and the reaction mixture is worked up as de
scribed before.v A yield of 60 parts of alkyl-ben
or other petroleum which, by re?ning, has been
made similar to Pennsylvanian petroleum. With 25 zene sulfonate is obtained.
out insisting on some exact chemical constitution
Example III
of our compounds, we would like to emphasize
that we are not forced to work with just Pennsyl
vanian mineral oil which primarily contains open
The same procedure as described in Example
I is performed again, except that 2 parts of dry
chain hydrocarbons. As shown in the examples 30 bromine are added to the kerosene and the re
action is stopped after two hours. A yield of
given below, for our purposes mineral oil frac
80 parts of alkyl-benzene sulfonate is obtained.
tions from Texas containing a considerable part
of naphthenic hydrocarbons are suitable without
Example IV
any previous re?ning.
as described in Example
The invention will be illustrated by the fol 35
lowing speci?c examples. It will be realized by r II is performed again except that hydrogen bro;
mide is substituted for hydrogen chloride. A
those skilled in the art that the invention is
yield of 75 parts or alkyl-benzene sulfonate is
not limited thereto except as indicated in the
appended patent claim. The parts are by weight,
We claim:
the temperatures are in degrees centigrade.
In the process of manufacturing sulfonated a1
Example I
kylated monocyclic aromatic hydrocarbons by
condensation of unsaturated aliphatic hydrocar
400 parts of a kerosene fraction, containing ap
bons with benzene and its homologues under the
proximately 25 per cent of unsaturated hydrocar
in?uence of aluminum chloride by means of a
bon, boiling from 160 to 240°, obtained by the
cracking of a Texas oil, is added with agitation ' Friedel-Crafts synthesis and by sulfonating the
condensation product, the step which comprises
to 400 parts of benzene and 20 parts aluminium
condensing cracked mineral oil fractions boiling
chloride over a period of 20 minutes. The mix
under normal pressure between 150-300” C., and
ture is vigorously stirred at 55° for three hours.
After 12 hours, the clear upper layer is decanted 50 containing not more than 10-35 per cent. of un
saturated hydrocarbons with monocyclic hydro
from the tarry residue and stirred for 10 minutes
carbons of the class consisting of benzene, tolu
with one part water and four parts Filtrol. After
ene, and xylene, in the presence of aluminum
?ltration, the liquid is distilled until a boiling
point of 240° is reached. The residue is sulfonat
ed with an equal volume of 100 per cent sulfuric
acid for one hour at 55°. The sulfonation mixture
is stirred for a few minutes with 5 parts of water.
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