[0001] The invention relates to a concentrated, liquid, pourable composition comprising
an alkali or earth alkali metal or ammonium salt or a salt of an organic base of an
internal olefin sulphonic acid, having 8 to 26 carbon atoms.
[0002] In the European patent application No. 89203337 has been described a detergent composition
comprising an alkali or earth alkali metal or ammonium salt or a salt of an organic
base of an internal olefin sulphonic acid, having from 8 to 26 carbon atoms, and containing
at least 25% by weight of beta-hydroxysulphonate, calculated on the total amount of
sulphonate. Especially compositions with 50 to 90% by weight of beta-hydroxysulphonate
are used.
[0003] There is further described that the compositions may contain other surfactants of
anionic, nonionic, amphoteric or cationic type and depending upon the formulations
to be used the compositions may contain builders, sequestring agents, bleaching agents,
bleach activators, greyness-preventing agents, soil release polymers, foam control
agents, fluorescent whiteners, enzymes and perfumes. The compositions are thus suitable
for a number of applications such as solid and liquid laundry detergents, dishwash
detergents, cleaning agents, liquid soaps, shampoos and liquid scouring agents.
[0004] There have now been found concentrated, liquid and pourable compositions which have
advantages over the compositions, disclosed in European patent application No. 89203337.
[0005] The invention relates to a concentrated liquid, pourable composition comprising:
a) from 50 to 95% by weight of an alkali or earth alkali metal or ammonium salt or
a salt of an organic base of an internal olefin sulphonic acid, having from 8 to 26
carbon atoms, these internal olefin sulphonates having at least 25% by weight of beta-hydroxy
sulphonates;
b) from 4 to 49% by weight of water; and
c) from 1 to 46% by weight of a lower alcohol, a nonionic surfactant, a polyethylene
glycol, a polypropylene glycol, a salt-tolerant anionic surfactant, or a mixture thereof.
[0006] The inventive compositions are easily storageable, handlable and transportable. Furthermore,
they may be easily spray-dried or converted into less concentrated compositions.
[0007] Component a), the internal olefin sulphonate, contains at least 25% by weight of
beta-hydroxy sulphonate, preferably at least 50%, more preferably more than 70% by
weight of beta-hydroxy sulphonate. Preferred internal olefin sulphonic acids contain
from 13 to 24 carbon atoms. The sulphonic acids may be present in the form of their
salts with sodium, potassium, ammonium or an organic base.
[0008] The internal olefin sulphonates, containing beta-hydroxy sulphonates, are generally
prepared by reacting in a film reactor an internal olefin having from 8 to 26 carbon
atoms with a sulphonating agent, in a mol ratio of sulphonating agent to internal
olefin of 1.3 to 0.9, preferably 1.15 to 0.95, while cooling the reactor with a cooling
means having a temperature not exceeding 35 °C and allowing the reaction product of
the sulphonating step to neutralize and hydrolyze.
[0009] The internal olefins used as starting material are those having 8 to 26 carbon atoms,
preferably 13 to 24 carbon atoms. Examples of the internal olefins are those having
the general formula:

wherein each of R₁, R₂, R₃ and R₄ independently are linear or branched alkyl groups
or hydrogen and the total carbon number of R₁, R₂, R₃ and R₄ is from 6 to 24, and
wherein at least one of R₁ and R₂ and one of R₃ and R₄ is an alkyl group.
[0010] In the process for preparing internal olefin sulphonates the neutralization/hydrolysis
step is carried out directly after the sulphonating step. An ageing step is consequently
avoided or minimized.
[0011] The sulphonation may be carried out batchwise, semi-continuously or continuously,
preferably continuously.
[0012] The neutralization/hydrolysis is preferably carried out continuously and at a temperature
of 20 to 50 °C, preferably 30 to 45 °C. Hydrolysis is preferably carried out continuously
and at temperatures of 140-190 °C.
[0013] For the neutralization/hydrolysis an aqueous base is generally used. To prepare concentrated
products, the amount of water is regulated accordingly.
[0014] Component c) may be included in the composition at the same time when water is added.
This third component is a lower alcohol, a nonionic surfactant, a polyethylene glycol,
a polypropylene glycol, a salt-tolerant anionic surfactant or a mixture thereof.
[0015] Examples of lower alcohols are methanol, ethanol, propanol, iso-propanol, butanol,
iso-butanol, tert.butanol, a pentanol or a hexanol, ethylene glycol, propylene glycol,
a linear or branched C₁ to C₆ mono-alkylether of mono- or di-ethylene glycol, a linear
or branched C₁ to C₆ mono-alkylether of mono- or di-propylene glycol, or a mixture
thereof.
[0016] Examples of nonionic surfactants are C₇ to C₁₈-alcohols that are alkoxylated with
ethylene oxide and/or propylene oxide with a minimum degree of alkoxylation of 2.
[0017] Further examples of nonionic surfactants are C₆ to C₁₂-alkylphenols, alkoxylated
with ethylene oxide and/or propylene oxide with a minimum degree of alkoxylation of
2.
[0018] Other examples of nonionic surfactants are hydrophilic C₈ to C₁₈-alkyl polyglycosides
with 1 to 4 carbohydrate units.
[0019] Polyethylene glycols may have a molecular weight from 300 to 5000, preferably from
800 to 4000.
[0020] Polypropylene glycols may have a molecular weight from 250 to 4000, preferably from
400 to 2500.
[0021] Examples of salt-tolerant anionic surfactants are a C₈ to C₁₈-alcoholalkoxy carboxylate
salt with a degree of alkoxylation of 1 to 10, or C₆ to C₁₀ aliphatic or aromatic
sulphonates.
[0022] A preferred composition according to the invention comprises from 60 to 90% by weight
of component a), from 8 to 38% by weight of water and from 2 to 32% by weight of component
c).
[0023] The composition according to the invention may comprise some impurities, such as
unreacted olefin and inorganic salt. The amounts of them generally do not exceed about
5% by weight each, calculated on the internal olefin sulphonate.
Examples 1-7
[0024] In a falling film reactor of stainless steel, having a length of 6 m and a diameter
of 2,54 cm, were introduced internal olefins of different compositions:
A. a mixture of internal olefins in the range of from C₁₄ to C₂₀, average molecular
weight 230 and a purity of 97%;
B. a mixture of C₁₄ internal olefins and C₁₆ internal olefins, in a weight ratio of
1:2, average molecular weight 214 and a purity of more than 99%; and
C. a mixture of C₁₄-, C₁₆- and C₁₈ internal olefins, in a weight ratio of 1:1:1, average
molecular weight 222 and a purity of more than 99%.
[0025] The sulphur trioxide was prepared by burning sulphur in dry air followed by conversion
of the sulphur dioxide to sulphur trioxide over a vanadium pentoxide catalyst at about
450 °C.
[0026] The reactor was cooled by flowing water of a temperature of 8 to 11 °C along the
outside of the stainless steel reactor tube. The internal olefin mixture (either A,
or B or C) flowed along the inner part of the reactor wall as a flowing film in downward
direction and was allowed to react cocurrently with the sulphur trioxide, which was
introduced at the same time in the top of the reactor, diluted with air. The reaction
proceeded continuously.
[0027] The reaction mixture coming out of the falling film sulphonation reactor was conducted
into a continuous neutralization loop, provided with a combined pump/high sheer mixer
and two heat exchangers, and having a volume of about 26 litres; in that continuous
neutralization loop the reaction mixture coming from the sulphonation reactor was
subjected to neutralization/hydrolysis at 30-45 °C by, at the same time, continuously
introducing into the loop streams of i) a concentrated (50% by weight) aqueous sodium
hydroxide solution, ii) water, and iii) water plus nonionic surfactant and intimately
mixing these streams by means of the combined pump/high sheer mixer and recycling
in the neutralization loop. The recycle rate in the loop was about 20 times greater
than the intake rate of the reaction mixture coming from the film reactor. The average
residence time of the neutralization/hydrolysis mixture in the continuous neutralization
loop was dependent on the precise composition of a particular product and of the initial
olefin feed rate, and amounted to 40-55 min. The intake rate of the concentrated aqueous
sodium hydroxide stream was adjusted on the basis of alkalinity measurements in the
end-product (i.e. after the continuous hydrolysis step), which was aimed to be slightly
basic. The amounts of water (total) and nonionic surfactant were calculated on the
basis of the desired composition. The anionic active matter concentration was actually
measured in the end-product (i.e. after the continuous hydrolysis step) during the
production.
[0028] From the continuous neutralization loop the product mixture exited continuously into
a continuous laminar tubular hydrolysis reactor that was heated externally with oil
having a temperature of 170-190 °C, the reactor being provided with a preheater section
heated with steam at 6 bar, a cooler, and a constant pressure valve; the volume of
the hydrolysis reactor was about 40 litres from which the average residence time for
each specific product could be estimated. The product flowing out of the constant
pressure valve was analysed and, if necessary, adjustments were made in, for instance,
the SO₃/olefin ratio, the feed rate of concentrated sodium hydroxide solution, water,
etc. on the basis of these analyses. After these adjustments sufficient time was allowed
to obtain representative samples which were then collected and analyzed. The specific
reaction conditions and analytical data of the products are given in the Table.

[0029] It is further observed that the compositions given in the Table are all liquid and
pourable at 20 °C and can be pumped at that temperature, whilst this holds also for
the materials during production in the continuous neutralization loop and the continuous
hydrolysis reactor. Reducing during production the amount of nonionic surfactant in
Examples 1 and 7 to zero leads to products that can not be pumped through the neutralization/hydrolysis
reactor even in spite of the higher temperature in the neutralization loop.
1. A concentrated, liquid, pourable composition comprising:
a) from 50 to 95% by weight of an alkali or earth alkali metal or ammonium salt or
a salt of an organic base of an internal olefin sulphonic acid, having from 8 to 26
carbon atoms, these internal olefin sulphonates having at least 25% by weight of beta-hydroxy
sulphonates;
b) from 4 to 49% by weight of water; and
c) from 1 to 46% by weight of a lower alcohol, a nonionic surfactant, a polyethylene
glycol, a polypropylene glycol, a salt-tolerant anionic surfactant, or a mixture thereof.
2. A composition as claimed in claim 1 wherein the internal olefin sulphonates comprise
at least 50% by weight of beta-hydroxy sulphonates.
3. A composition as claimed in claim 1 or 2 wherein the internal olefin sulphonates comprise
at least 70% by weight of beta-hydroxy sulphonates.
4. A composition as claimed in one or more of the claims 1-3, wherein the internal olefin
sulphonic acid moiety comprises from 13 to 24 carbon atoms.
5. A composition as claimed in one or more of the claims 1-4 wherein the lower alcohol
is methanol, ethanol, propanol, isopropanol, butanol, iso-butanol, tert.butanol, pentanol
or hexanol, ethylene glycol, propylene glycol, a linear or branched C₁ to C₆ mono-alkylether
of mono- or di-ethylene glycol, a linear or branched C₁ to C₆ mono-alkylether of mono-
or di-propylene glycol, or a mixture thereof.
6. A composition as claimed in one or more of the claims 1-4 wherein the nonionic surfactant
is a C₇ to C₁₈-alcohol that is alkoxylated with ethylene oxide and/or propylene oxide
with a minimum degree of alkoxylation of 2.
7. A composition as claimed in one or more of the claims 1-4 wherein the nonionic surfactant
comprises a C₆ to C₁₂-alkylphenol, alkoxylated with ethylene oxide and/or propylene
oxide with a minimum degree of alkoxylation of 2.
8. A composition as claimed in one or more of the claims 1-4 wherein the nonionic surfactant
comprises a hydrophilic C₈ to C₁₈-alkylpolyglycoside with 1 to 4 carbohydrate units.
9. A composition as claimed in one or more of the claims 1-4 comprising polyethylene
glycol with a molecular weight from 300 to 5000, preferably from 800 to 4000.
10. A composition as claimed in one or more of the claims 1-4 comprising polypropylene
glycol with a molecular weight from 250 to 4000, preferably from 400 to 2500.
11. A composition as claimed in one or more of the claims 1-4 wherein the salt-tolerant
anionic surfactant comprises a C₈ to C₁₈-alcoholalkoxy carboxylate salt with a degree
of alkoxylation of 1 to 10, or a C₆ to C₁₀ aliphatic or aromatic sulphonate.