Patented Mar.

14, 1933
1901,507
UNITED STATES PATENT OFFICE
FRITZ GUENTHER, OF LUDwIGsHAFEN-ON-THE-RHINE, GERMANY, AssIGNOR. To I. G.
FARBENINDUSTRIE
AN AKTIENGESELLSCHAFT, OF FRANKFORT-ON-THE-MAIN, GER
MIXTURES OF SULPHONATED ALKYLATED NONIDYEING AROMATIC CARBOCYCLIC
COMPOUNDS AND BER SALS
No Drawing. Application filed August 4, 1931, Serial No. 555,070, and in Germany July 11, 1924.
The present invention relates to the pro fatty oils, mineral oils, waxes, hydrocarbons,
duction of soap-like substances. dyestuffs and like water-insoluble materials
It has already been proposed, inter alia. is similarly increased. Moreover, the level
by the present inventor, to produce wetting, ling action of the products obtainable under
cleansing and dispersing agents by introduc
ing aiki groups into naphthalene or other the er by
specified condition is considerably great 55
comparison with those already known,
aromatic hydrocarbons, and sulphonating this being particularly manifest in dyeing
the hydrocarbons before or after alkylation, wool in an acid bath with dyestuffs which do
the quantity of alkyl groups and especially not readily distribute uniformly.
O of butyl groups being always below 2.2 Substances particularly adapted for the 60
molecular proportions for each molecular production of the said sulphonic
proportion
duct.
of hydrocarbon in the final pro E. the polynuclear aromatic acids com
hydrocar
ons, such as naphthalene, diphenyl, phen
I have now found that particularly valua anthrene or tetrahydronaphthalene or com
5 ble products are obtained by condensing aro mercial mixtures containing the said hydro
matic non-dyeing compounds, such as hydro carbons though mono-nuclear hydrocarbons, 5
carbons or their derivatives, as for example such as benzene or toluene, and the afore
halogenated hydrocarbons, phenols, naph said derivatives of the said hydrocarbons
thols, anilines or naphthylamines, or the sul may be also employed. As has been point
20 phonic acids of these compounds with a butyl ed out above the different primary, second
alcohol, the proportions being such that, for ary, or tertiary butyl alcohols with straight 70
each molecule of the hydrocarbon, more than or branched chain, such as n-butyl alcohol,
2.2 molecules, but not substantially more methylethylcarbinol
than 4 molecules of the aforesaid alcohol are brought to actionor ontrimethyl the
carbinol,
initial mate
25 come into operation, the resulting products rials, and they may be employed as such or
being sulphonated if they do not already in the form of their esters such as sulphuric 75
contain any sulphonic groups. Non-dyeing or
aromatic compounds must be chosen, since thephosphoric esters, dialkyl sulphates and
otherwise products might be obtained which employed singly oralcohols
like. These
as
or esters may be
mixtures. In order to
30 are inoperative for the desired purposes.
facilitate the reaction it is advantageous
The properties of the new sulphonic acid operate in the presence of inert solvents or to 80
substances obtained, i. e. of the free sul diluents, such as carbon tetrachloride, tri
phonic acids and their water-soluble chemi chlorethylene,
cal combinations or salts with alkalies, such The process ethyl may
ether and the like.
be carried out in various
35 as alkali metals, ammonia, aliphatic or aro ways, for example by first
matic amines or hydroxy-alkyl amines, ex aromatic hydrocarbons andsulphonating then
the 85
introduc
hibit, as compared with the properties of ing the alkyl radicles, or the hydrocarbons
those already known, a substantially in may first be alkylated and the sulphonation
creased efficiency, and indeed to a degree effected afterwards, or the alkylation and
40 that could not have been anticipated. Thus, sulphonation
for example, the wetting properties of the taneously. Themay usual
be performed simul 90
sulphonating agents,
products obtained even with 2.7 to 3 molec such as sulphuric acid, fuming
ular proportions of iso-butyl-, normal- or chlorsulphonic acid, sulphuric sulphuricanhydride
acid,
and
secondary butyl alcohols and 1 molecule of
45 naphthalene, in conjunction with the em the like, are suitable for the sulphonation
ployment of sulphuric acid, are approxi add treatment. In some cases it is preferable to 95
acid chlorides, such as phosphorus tri
mately twice as great as those obtained with chloride,
the corresponding dibutyl naphthalene sul sulphonic phosphorus
acid, acetyl
pentachloride, chloro
chloride with or with
phonic acids or their salts. The dispersive
50 capacity in respect of the dispersion of out phosphorus pentoxide, as catalysts if
desired in conjunction with the aforesaid 00
 2 1901,507
and similar liquors with sulphonic acids or
solvents or diluents. The duration of the their
reaction, concentration of the acid, tempera salts or aqueous solutions thereof, or
the use of the said substances for washing
ture, and so forth, depend on the substances and
employed, and may be varied accordingly. ing cleansing
wool or
purposes, for liquors for mill
for baths for dyeing in the O
The optimum amount of the alcohol or ester, lather.
within the prescribed limits, can be easily Faample 2
ascertained, by a preliminary experiment,
and will depend on the properties of the de 700 parts of n-butanol and 440 parts of
sired substance in respect of wetting, dis naphthalene are treated at a temperature 75
O persive and levelling properties, aid the of from 20° to 25°C. with 2700 parts of sul
like. In most cases, the best products will phuric acid, containing about 16 per cent of
be obtained with a quantity of alcohol rang sulphur trioxide, and are stirred at a tem
ing between 2.5 and 3.6 molecular propor perature of 45° to 55° C. until a sample shows
tions, referred to the amount of the aromatic that the product has become completely sol
5 hydrocarbon employed. Larger quantities uble in water. After standing a short time,
80
. . than about 4 molecules of alcohol or ester
are generally not used according to the pres; two layersmulti-butylated
taining are obtained thenaphthalene
upper one con
sul
ent invention, since they effect only a
further improvement in the wetting prop
slight phonic acid, which is then separated from the
spent sulphuric acid in the usual manner9 85
20 erties, so that their employment is uneco and may, if desired, be converted into the
nomical. alkali salt. By comparison with the sodium
The following examples will further illus salt of dibutylnaphthalene sulphonic acid,
trate how the said invention may be carried this product displays substantially higher
out in practice but the invention is not re
stricted to these examples. The parts are by
Yeting, levelling and emulsifying capaci. 90
leS.
weight. Eacample 3
Eavample 1 200 parts of chlorsulphonic acid, followed
128 parts of naphthalene are converted by 600 parts of concentrated sulphuric acid, 95
30 into beta-naphthalene sulphonic acid by heat are stirred into 200 parts of n-butanol at
ing with 128 parts of sulphuric acid of 67 about from 20 to 25 C., cooling measures
B6. to about 150° C. for 5 hours. The mass being applied for maintaining the said tem
is cooled to 120° C., mixed with 100 parts of perature. 87 parts of naphthalene are then
sulphuric acid of 67 Bé. and further cooled added and the mixture is stirred, at from 45°
35 to from 80 to 85°C. While maintaining the to 55 C. until a sample is found to be com 100
mixture of the sulphonic acid and sulphuric pletely soluble in water. Stirring is then
acid at this temperature, a mixture of 200 stopped, and after standing for a short time,
parts of ordinary commercial concentrated the reaction product separates into two layers.
The upper layer, containing the highly bu
sulphuric acid of 66° Bé, and 222 parts of iso 105
O butyl alcohol is allowed to run into the sul tylated naphthalene sulphonic acid, is sep
phonic acid mixture in the course of 2 hours arated from the spent sulphuric acid beneath,
while vigorously stirring. When all of this and, if desired, is converted into the corre.
mixture has run in, the temperature of the sponding alkali salts by neutralization with
mixture is raised to about 100° C. at which alkalies. The preparations constitute very O
45 temperature the reaction is completed in the high-grade wetting, emulsifying and disper.
course of a few additional hours. There sion agents,
upon the mass is poured into water and sep Eaample 4
arated from any oil, neutralized with lime,
filtrated and decomposed with sodium car.
bonate in the usual manner. By evaporating, 750 parts of sulphuric acid containing 16 5
the poly-butylated naphthalene sulphonic per cent of sulphur trioxide are introduced,
acid sodium salt is obtained in the form of a at about 40°C. into a mixture of 128 parts of
slightly yellowish powder. When normal naphthalene, 112 parts of n-butanol and 200
butyl alcohol is used the mass directly forms parts of an aliphatic alcohol, with a chain
two layers, the upper layer of which repre length of about 15 carbon atoms, and pre 20
sents chiefly the free butylated naphthalene pared from soya bean oil by catalytic hydro
sulphonic acid. genation. The mixture is stirred until com
The said sulphonic acids which may also pletely soluble in water and after the stirring
be employed in the form of their salts are of has been stopped, two layers will form which 25
60 special value as they are not decomposed by are separated in the usual manner. The up
acids or calcareous water in which cases soap per layer contains the multi-substituted
cannot be used. As examples of suitable naphthalene sulphonic acid, which may be
application I quote the preparation of so employed directly, or in the form of its alkali
lutions or emulsions of fats and oils, hydro salt, and represents an excellent washing and
carbons or derivatives thereof, chloroform emulsifying agent.
 2,901,507 3
Eacample 5 to the alkali metal salts of a phenanthrene
433 parts of naphthalene and 750 parts of sulphonic
only. acid containing -2 butyl radicles
pure isobutyl alcohol are treated at about
5 from 25 to 30° C. with 2800 parts by weight
of sulphuric acid, containing 16 per cent of
Evample 9 70
sulphur trioxide, and the mixture is stirred 270 parts of chlorsulphonic acid are stirred,
for a period of from 10 to 15 hours at 30° while cooling, into 200 parts of n-butanol and
C. After prolonged standing, the mixture then 600 parts of concentrated sulphuric acid
10 separates into two layers from the upper of and finally 163 parts of 3-chlornaphthalene
which multi-isobutylated naphthalene sul are introduced while stirring and cooling. 75
phonic acid is isolated. The mixture is then warmed to from 45° to
Eacample 6 50 C. and stirred at this temperature until
it is rendered soluble in water and 2 layers
s Naphthalene di-sulphonic acid is prepared are formed. The reaction product is worked
from 128 parts of naphthalene and 600 parts up as described in the foregoing examples. 80
of concentrated sulphuric acid by prolonged Eacample 10
stirring at 150° to 160° C., and after adding
300 parts of concentrated sulphuric acid, 150 parts of concentrated sulphuric acid
20 the melt is stirred at from 90° to 95° C. with and 220 parts of n-butanol are introduced at
a mixture of 200 parts of n-butanol and 300 25 C. into a mixture of 140 parts of purified. 85
parts of concentrated sulphuric acid, until tetrahydro-naphthalene and 150 parts of
the mixture has become completely soluble concentrated sulphuric acid and then 500
in water. In this case there is no separation parts of funing sulphuric acid containing
25 into layers. The corresponding alkali salts 25 per cent of sulphur trioxide are added and
can be recovered by neutralization with al the whole is stirred at from 35° to 40° C. for
kalies, and, if desired, may be purified from Several hours until it is rendered soluble in
sulphates by treatment with lime and Subse water. The sodium salt of the butylated
quent filtration. Since these products are also tetrahydro-naphthalene sulphonic acid is re
very soluble in concentrated acid and saline covered by means of lime and conversion of
solutions they are particularly suitable as the calcium salt with sodium carbonate. The 95
wetting agents for precipitation baths in the product obtained possesses a substantially
artificial silk industry. higher wetting, emulsifying and levelling
Eacample 7 power than a di-butyl tetrahydronaphtha
lene sulphonic acid.
35
260 parts of diphenyl (melting point about This application is a continuation in part (5.
70° C.) are stirred with 375 parts of n-bu of my ?opending application Ser. No 49,447
tanol and 1400 parts of fuming sulphuric filed August 10, 1925.
acid containing 8 per cent of sulphur trioxide What I claim is:-
4. at from 40° to 45° C. until 2 layers are 1. Sulphonic acid compositions selected 0.
formed in the reaction mass. After stand from the group consisting of mixtures of
ing for some time, the lower yer consisting Sulphonic acids of a mixture of non-dyeing
of sulphuric acid is drawn off. The butyl aromatic carbocyclic compounds, containing
ated diphenyl sulphonic acid can be converted from 2.8 to about 4 butyl radicles per each
45 into the desired alkalimetal salt and possesses molecular proportion of said carbocyclic
a considerably higher wetting power than compound, and salts of said sulphonic acid 10
a product prepared in the same manner from mixtures.
2 molecular proportions of butanol per molec 2. Sulphonic acid compositions selected
ular proportion of diphenyl. from the group consisting of mixtures of sul
50
Eacample 8 phonic acids of a mixture of non-dyeing aro
natic carbocyclic compounds, containing 5
375 parts of n-butanol are mixed, while from 2.5 to 3.6 butyl radicles per each molecu
carefully cooling, with 1400 parts of fuming lar proportion of said carbocyclic compound,
sulphuric acid containing 8 per cent of sul and salts of said sulphonic acid mixtures.
phur trioxide and then 300 parts of phenan 8. Sulphoic acid compositions, compris 120
threne are introduced and the mixture is ing a combination of an alkali with a sul
stirred at 40° C. until the tri-butyl phenan phonic acid mixture of a mixture of non
threne sulphonic acid separated from the dyeing aromatic carbocyclic compounds con
60
layer of concentrated sulphuric acid; the lat taining from 2.3 to about 4 butyl radicles.
ter is removed and the sulphonic acid is neu per each molecular proportion of said carbo 25
tralized and dried, the neutralization being cyclic compound. -
carried out either with lime or with an alkali 4. Sulphonic acid compositions, compris
metal compound. The alkali metal salts are ing alkali metal salts of a sulphonic acid of
65 valuable wetting, levelling and emulsifying a mixture of non-dyeing aromatic carbocyc
agents and are superior in their efficiency lic compounds containing from 2.5 to 3.6 30
 4 ..... .. :.... ... - .... 1,901,507 . .............................

;::
l, butyl radicles per each molecular proportion .
II of said carbocyclic compounds...}}
. . , . , ; . ; ;. . .
; ;;;;; ;;; ; ;;;
... .
5. Sulphonic acid compositions selected
from the group consisting of mixtures of
is sulphonic
not dyeingacids of a mixture
aromatic of polynuclear
carbocyclic compounds
containing from 2.3 to about 4 butyl radicles
per each molecular proportion of said carbo
yclic compound, and salts of said iii.
10 eid mixtires.
sulphonic iii.
i.e. Sulphonic acid compositions selected it is
from E. consisting of mixtures of sul
I phonic acids of a mixture of polynuclear aro ;::
:;;;;;;; imatic hydrocarbons containing fron 2.5 to
1536, butyl radicles per each, molecular pro: ;;;;;;;;;;
sportion of said Yictory and salts of :
:s said sulphonic acid mixtures: , , ,
iii. Suiphoniel acid compositions selected
from the group consisting of mixtures of sul
phonic acids of a mixtire of naphthalene
homologues containing from 2.3 to about 4
I
of aphthalene, and salts of said sulphonic
acid mixtures. . . . . . . . . . . . . .
l
8. A sulphonic acid composition consisting is ;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;;
of a sulphonic acid mixture of a mixture of ..................... . ...
naphthalene homologies containing from
25 to 3.6 n-butyl radicles per each molecular
proportion of naphthalene. . . . . .
809. A sulphonic acid: composition consist:
sing of a water-soluble salt of a sulphonic acid
mixture of a mixture of naphthalene homo: ;::
:;;; : ilogues containing from 2.5 to 3.6 in-buty ; : ;;; ;;; ; ; ; ; ; ; ; ; ;;
35
radicles per each molecular proportion of
naphthalene. ; : ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; : : : ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ;

i0. A sulphonic acid composition consist

ing, of an alkali metal salt of a sulphonic
acid mixture of a mixture of naphthalene
homologues containing from 2.5 to 3.6. n
40 butyl radicles per each molecular proportion
of naphthalene.
In testimony whereof I have hereunto set
my shand. FRITZ, GUENTHER.
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