Note: Descriptions are shown in the official language in which they were submitted.
3 j ,i
WO 93/03128 PCT/EP9Z/01704
Free- ~lowing water-con~aining ~lkyl ~ul f ate pa~te~
This invention relates to free-flowing, pumpable
water-containing alkyl sulfate pastes, to a process for
the production of alkyl sulfate pastes having improved
flow properties by addition of alkenyl sulfates and to
the use of such pastes for the production o~ detergents
and cleaning preparations.
Anionic surfactants of the alkyl sul~ate type, more
especially those containing C~61~ alkyl radicals, show
excellent detergent properties and ar~ used both in li-
0 quid and in powder-form detergents and cleaning prepar~
ations.
The detergents in question are c~enerally produced
from water-containing alkyl sulfate pastes. To avoid
unnecessary mass transport, it is an advan~age if water-
containing surfactant pastes have a high solids content.However, alkyl sulfate pastes can only be concentrated to
a certain solids content. In addition, pastes such as
these show non-newtonian flow behavior. Above a limit o~
around 55~ by weigh~ solids, the viscosity generally
reaches such high values that the pumpability of the
surfactant solutions is no longer guaranteed, even at
elevated temperatures. Thus, water-containing fatty
alcohol sulfate pastes with solids contents of 30 to 70%
by weight have such high viscosities and yield points,
even at ambient temperature, that they often cannot be
transferred from one vessel to another or pump-circu-
lated.
According to EP 024 711, polyalkyl ether glycol
sulfates are added to high~viscosity surfactant concen-
trates to reduce their viscosity Whereas compounds suchas these are eminently suitable for reducing the vis-
cosity of alkyl ether sulfate, alkylaryl ether sulfate,
, ,i, .1. ~1 ~ c) ,,i ''
Wo 93/03128 2 PCT/EP92/0170~
alkyl benzenesulPonate and alkylaryl ~ulfosuccinate
solutions, their performance in the presence vf alkyl
sulfates, particularly linear primary alkyl sulfates, is
often unsatisfactory.
DE-OS 34 47 ~59 describes the use of alkanesul-
fonates as viscosi~y regulators for high-viscosity
anionic surfactant concentra~es, more especially salts of
~-sulfofatty acid esters~
DE-O~ 37 18 8g6 describes the use of alkoxylated
alcohols as viscosity regulators for high-viscosity alkyl
benzenesulfonate concentrates.
It has now surprising1y been found that water-
containing mixtures of unsaturated and saturated alkyl
sulfates have a low viscosity and a low yield point so
that the unfavorable flow behavior typical of alkyl
sulfates based solely on saturated alcohols is o~ercome.
It is thus possible to produce high-solids alkyl sulfate
pastes which are flowable and pumpable, even at low
temperatures ~nd low shear rates.
Accordingly, the present invention relates to a
water-containing, free-flowing and pum~able alkyl sulfate
paste having a viscosity, as measured at a shear rate of
10 s~1, of 5 Pa.s to 100 Pa.s and preferably 5 Pa.s to S0
Pa.s at temperatures of~50 to 90C which contain from 15%
by weight to 65~ by weight and more particularly from 25%
by weight to 50~ by wei~ht of an alkyl sulfate corre-
sponding to formula I:~
.
~ Rl-O-SO3M~
..
in which Rl is a linear or branched Cl222 alkyl radical and
Ml is an alkali~ metal,~ ammonium, alkyl ammonium or
hydroxyalkyl ammonium ion,~ ~
f~om 5% by weight to 65% by wei~ht and more particularly
from 15%~by weight to 65% by weight of an alkenyl sulfate
:~:
5~
Wo 93/03128 3 PCT/EP92/0170
corresponding to formula II:
R2-0-S03M2 (II)
in which ~2 is an alkenyl rad.ical containing 16 to 22
carbon atoms and 1, 2 or 3 double bonds and M2 is an
alkali metal, ammonium, alkyl ammoni.um or hydroxyalkyl
ammonium ion, ~`
and from 20% by weight to S0% by weight o~ water.
The present invention also relates to a process ~or
the production o~ a free-flowing, pumpable water-contain-
ing alkyl ~ulfate paste having a solidis content of 50~ by
weight to 80% by weight and, m~re particularly, 60% by
weight to 75~ by weight, characterized in that an aqueous
paste containing 50% ~y weight to 80~ by weight of an
alkyl sulfate corresponding to fo~mula I:
R1-0-SO3~1 (I)
, .,
in which Rl is a linear or branched C1~22 alkyl radical and
M1 is an alkali metal, ammonium, alkyl ammonium or
hydroxyalkyl ammonium ion,
is mixed with an alkenyl sulfate corresponding to formula
II:
R2-0-SO3M~ (II)
:,
in which R2 is an alkenyl radical containing 16 to 22
carbon atoms and 1, 2 or 3 double bonds and M2 is an
alkali metaI, ammonium, alkyl ammonium or hydroxyalkyl
. , I j , ,
ammonium lon,
in a ratio by weight of alkyl sulfate (I) to alkenyl
sulfate (II) Oc lO:1 to 1:3.
The alkyl sulfate corresponding to formula I and the
alkenyl sulfate oorresponding to formula II are prefer-
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WO 93/03128 4 PCT/EP92/01704
ably mixed with one another in a ratio by weight of alkyl
sulfate to alkenyl sulfate of 7:1 to 1:2.
In one preferred embodiment of the process according
to the invention, a water-containing paste containing an
alkenyl sulfate corresponding to formula II is mixed with
such a quantity of a water-containing paste containing an
alkyl sulPate corresponding to ~ormula I that the sum
total of alkyl sulfate and alkenyl sulfakQ in the result-
ing water-containiny paste is 45% by weight to 80~ by
weight and more particularly 50% by weight to 75% by
weight and the resulting paste contains 20% by weight to
55% by weight and more particularly 25% by weight to 50
by weight of water.
The alkyl sul,fates corresponding to formula I are
known anîonic surfactants which are generally obtained by
reaction of aliphatic primary alcohols with a sulfating
agent, for example sulfur trioxide or chlorosulfonic
acid. Alkyl sulfates to which the process according to
the invention extends are preferably derived from C1222
fatty alcohols. Typical examples of such alcohols are
lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl
alcohol or behenyl alcohol. A particularly drastic
reduction in the viscosity o~ the paste is obser~ed in
the case of alkyl sulfates derived from alcohols contain-
ing 12 to 18 carbon atoms and more particularly 16 to 18
carbon atoms.
The alkyl sulfates may also be derived from techni-
cal alcohol mixtures such as~are ~ormed, for example, in
the hydrogenation of technical fatty acid ester mixtures
30, of natural origin or in the h~drogenation of aldehydes
from Roelen's oxo synthesis. Alkyl sulfates based on
- technical coconut oil or hydrogenated palm oil alcohol
; ; cuts are pre~erred. Alcohols~such as these are under-
stood to be primary fatty alcohoIs which have on average
the following C chain distribution:
,
,., l 1 ~1 .~ i '~
Wo 93/03128 5 PCT/EP92/01704
Coconut oil alcohol Hydrogenated palm oil
alcohol
__ _
C10:0 - 3% by weight
C1248 - 58% by weight
C1419 - 24% by weight 0 - 3~ by weight
C16:9 ~ 12% by weight45 ~ 55% by weight
C18:11 ~ 14~ by weight45 ~ 55% by weight
C2~ 0 - 3% by weight
The sulfation products of unsaturated alcohols to b~
added to the alkyl sulfate pastes in accordance with the
invention are compounds which are obtained by reaction of
mono-, di- or tri-unsaturated alcohols with sulfating
agents, more particularly gaseous sulfur trioxide, and
subsequent neutralization and hydrolysis of the reaction
products formed. One process for the production of such
compounds is described, for example, by M. Morak and R.
Audiova in Tenside Detergénts 15 ~1978), 299. ..
Since, where unsaturated alcohols are used, the
sulfation reactior can also be accompanied by addition of
the sulfur trioxide onto the double bond, the alkenyl
sulfate paste may also contain substances which contain
an internal sulfonate group or a sulfonate group and a :.
sulfate group. The percentage content of these internal
sulfonation products is normally from 3 to 20% by weight,
based on the quantity of alkenyl sulfate corresponding to
formula II. If desired, this quantity may be reduced to
zero by corresponding~purifying operations.
Typical examples of` unsaturated alcohols of which
the sulfates corresponding to formula II may be used as
the viscosity-reducing component according to the inven-
tion are, in particular, p~lmitoleyl alcohol, oleyl
alcohol, elaidyl alcohol,;petroselinyl alcohol, linoleyl
alcohol, linolenyl alcohol, gadoleyl alcohol or erucyl
alcohol. Oleyl alcohol is preferably used. Sulfation
~ '
, '
,~ ) 5 ';',
Wo 93/03128 6 PcT/EPs~/01704
products of technical mixtures of the unsaturated alco
hols mentioned with one another or with certain quanti-
ties of saturated alcohols of corresponding chain length
may also be used in the process according to khe inven-
tion. Pastes such as these preferably contain no morethan 70% by weight and, more preferably, from 2~ by
weight to 60~ by weight of saturated alkyl sulfate~
The two starting pastes and also the alkyl sulfate
paste according to the invention may contain as ~urther
constituents small quantities o~ generally not more than
10% by weight and more particularly from ~ to 5% by
weight, based on the particular paste, of inorganic
salts, particularly sulfates, resulting from the reaction
,. ~
of any excess sulfating agent with the neutralization
base in the production process.
The highly concentrated alkyl sulfate pastes accord-
ing to the invention have excellent detergent properties
and high solubility in cold water. Accordingly, they are
preferably used for the production of powder-f~rm or
liquid laundry detergents, dishwashing detergents and
cleaning products and also cosmetic products, more
particularly hair-care and body-care products.
The products in question may readily be prepared by
diluting the pastès produced by the process according to
the invention with water to the desired active substance
concentration~ Other constituents typical of such
products may also be added, including in particular
builders, such as zeolites and layer silicates, corrosion
inhibitors, bleaching agents, bleach activators, optical
30j brighteners, enzymes, redeposition inhibitors~ antlmicro
bial agents, water-miscible solvents, abrasives, foam
stabilizers, preservatives, pH regulators, dyes and
frayrances and additional~surfactants.
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wo 93/03128 - 7 pcT/Eps2~ol7o4
Examples
Example 1
2~0 g (1 molP) of a technical oleyl/cetyl alcohol
(HD-Ocenol~ 50-55, a product of Henkel KGaA) with the
followiny composition: .:
Myristyl alcohol : 5% by weighk
Cetyl alcohol : 30% by weight
10 Oleyl alcohol : 65% by weighk
Io~ine value : 53
Hydroxyl value : 215
were introduced into a 1 liter sulfonation reactor
equipped with a jacket cooling system and gas inlet pipe
and reacted at 45C with 84 g (1.05 mole~ of sulfur
trioxide. The sulfur trio~ide was driven out by heating
from a corresponding quantity of 65~ by weight oleum,
diluted with nitrogen to a concentration of 5~ by volume
and introduced into the starting product over a period of
30 minutes. The crude sul~onation product was neutral- :
ized and, at the same time, hydrolyzed at 80C with 2~4 -;
g of a 20% by weight a~ueous sodium hydroxide solution.
The reaction product was then adjusted with sodium
hydroxide to a pH value of 10. A paste-form product
having the following characteristic data was obtained:
Anionic surfactant content : 59.7% by weight
30, - Alkenyl sulfate component : 27.5% by weight
- Alkyl sulfate component : 20.7% by weight
- Sulfonate component : 11.5% by weight
Unsulfonated components : 2.0% by weight
50dium sulfate ~ : 2.8% by weight
35 Water : : 35.5% by weight
:
v 1 . `.1 c) ,~
WO 93/03128 8 PCT/EP92~~01704
The an.ionic surfactant content and the unsulfonated
components were determined in accordance with D~F-E~n-
heitsmetho~en, Btuttgaxt~ 1950-19~4t ~-III-10 and G~
6b. The sulfate conten~ was calculated as sodium sul-
fate, khe water content being determined by the Fischer
method.
Example 2
Pastes P1 to P3 according to the invention charac-
terized in the followiny Table were prepared ~y addingthe product according to Example 1 to a 55~ by weight
water-containing paste of a saturated C16/18 alkyl sulfate
(Sulfopon~ T 55, a product of Henkel KGaA) in the quanti-
ties shown in the following Table and mixing. The yield
points and viscosities (at a shear rate D of 10 ,5-1~ of
the pastes thus prepared were measured at 60C using a
shear-stress-controlled rotational rheometer (Carri-Med~ .
CS 100) with a plate/plate measuring system. The simil-
arly determined values of a solution (C1) free from
alkenyl sulfate are shown ~or comparison.
Table : Alkenyl and alkyl sul~ate conten~s I % by wei~ht
active substance~ and flow data of the pastes
__ _
P1 P2 P3 ~1
_ _ _ _
Alkenyl sulfatea) 6.88 13.75 20.62 _
_
Alkyl sulfateb) ~ 46.43 37.85 29.28 55
.~ I Yield point CPa~ 105 60 25 138
Viscosity CPa.s] 19 12 7.5 32
a) From corresponding quantities of th~ product of
Example 1
b) Sum of Na C16/18 alkyl :sulfate (Sulfopon~ T 55, a
product of Henkel KGa~) and alkyl sulfate from the
: product of~Example l
,:
