Note: Descriptions are shown in the official language in which they were submitted.
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BACKGROUND OF THE INVENTION
The invention refers to thickening agents based upon
polyether derivatives. Thickening agents are used for the
thickening of natural and synthetic oils, aqueous electrolyte
solutions, and aqueous solutions of organic substances. Their use
facilitates the handling of liquids used as household chemicals.
Thickening agents are also customarily used in electrolyte
solutions, which are required in batteries. Heretofore, waxes,
carboxyalkyl celluloses, starch, xanthan gum, or high-molecular
esters have been used as thickening agents.
It is customary to use thickening agents for cosmetic,
detergent-containing preparations so as to stabilize the disperse
~systems and for better handling during use. In the case of ether
I sulfates it is customary to thicken the preparations with
1¦ inorganic electrolytes, preferably with common salt. In the case
¦lof other detergents, use is, for example, made of distearyl
¦polyglycolester, cellulose derivatives, or natural and synthetic
soluble polymers. The preparations obtained in this manner
lexhibit a behavior that is structurally viseous and/or
thixotropic.
According to DIN 53900, detergents are chemical
compounds which, when dissolved or dispersed in a liquid, are
¦preferentially adsorbed on an interface. A number of physico-
jchemical or chemical eharacteristics of praetieal signifieance
¦result. The expression "interfaee-aetive compound" is herein used
¦synonymously with "detergent". Further, "detergent-containing
¦preparations" are defined herein as mixtures containing deterg~n~s
as essential constituents.
The object of the present invention was to find a
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thickening agent having the viscosity behavior of a Newtonian
liquid and, in addition, having hydrolysis-resistance under
customary conditions of use.
SUMMARY OF THE INVENTION
The present invention is a thickening agent comprising a
polyether derivative prepared by the gradual addition of a
long-chain 1,2-epoxy having a chain length of 10 to 32 carbon
atoms, at temperatures from 100 to 200C, to either (1) a
polyethylene glycol monoether having an average molecular weight
of 800 to 5000, the monoether group being a substituted or
unsubstituted hydrocarbon radical having at least 10 carbon atoms;
or to (2) a polyethylene glycol-polypropylene glycol monoether
with an average molecular weight of 850 to 6300, and having
repeating ethylene oxide and propylene oxide units each forming a
polyethylene glycol and polypropylene glycol block, respectively,
the polypropylene glycol block having an average molecular weight
of no more than 1300, the monoether group forming the end of the
polyethylene glycol block and being a substituted or unsubstituted
hydrocarbon radical having at least 10 carbon atoms, and wherein
the agent is prepared using 0.1 to 1% by weight of an alkali
hydroxide, the ~eight being based upon the total weight of the
long-chain epoxy and the monoether. The polyether derivative
corresponds to the general formula:
CH3 12
1 (CH2CH2O)n (CH2CH-O)m (CH2CH-O) H,
wherein R1 is a substituted or unsubstituted hydrocarbon or
alkyl phenol radical having 10 or more carbon atoms, n is 10 to
100, m is 0 to 25 and p is 1 to 3, and wherein R2 is an alkyl
radical having 8 to 30 carbon atoms. The values o~ n, m, and p,
wherever they appear in the present specification and claims, are
to be understood as representing average values.
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Preferably, the ether group (Rl) is an aliphatic
hydrocarbon radical with 10 to 22 carbon atoms. Yet another
preferred embodiment is the present polyether derivatives wherein
the ether group (Rl) is a straight-chained hydrocarbon radical,
and good thickening agents are also obtained when the ether group
is an alkylphenol radical having an alkyl chain length of 7 to 15
carbon atoms. The preferred chain length of the long-chain epoxy
is from 12 to 20 carbon atoms, that is, where R2 contains from
10 to 18 carbon atoms.
D~SCRIPTION OF THE PRE~ERRED EMBODIMENTS
The manufacture is carried out in a manner analogous to
the reactions of alcohols with 1,2-epoxies described in Houben-
Weyl, Methoden der organischen Chemie (Methods of Organic
Chemistry), vol. 14.2, pp. 436-450. Pursuant to the invention,
the thickening agent is used for anhydrous, llquid systems, such
as polyalkylene glycols; special fatty acid esters like
trimethylol propaneoleate or diisodecyl adipate; organic salts,
for example, diethanolamine salts; or vegetable oils, such as
soybean oil or castor oil; for detergent-free aqueous solutions,
as for example acid solutions, electrolyte solutions or alcohol
solutions; or for detergent-containing preparations, whereby the
content of polyether derivative in the detergent-containing
preparation amounts to 0.5 to 10~ by weight, referred to the
llweight of the preparation. The detergent-containing preparation
¦ may be used as a household cleaning agent, cosmetic e~ulsion or
cosmetic gel, hairdressing preparation, foa~ bath~ or the like.
Detergent-containing preparations making use of the polyether
derivative pursuant to the invention may also be used in liquids
l for hydraulic purposes, in treatment liquids for the cutting or
1 non-cutting processing of materials, or the like.
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Preferably, the concentration of detergents in
detergent-containing preparations incorporating the present
polyether derivative is 1 to 40% by weight. At this
l concentration, the de-tergents partially solubilize the thickening
¦ agent. This effect is particularly pertinent to the detergent-
containing preparations such as hydraulic fluids or liquids for
the cutting or non-cutting type processing of materials. In
addition to the aforementioned applications, detergent-containing
preparations with thickening agents are also employed in the
foodstuff industry, for example, as a sugar anti-crystallant or
for the fixing of flavors. Such preparations are also useful in
paper making and the textile industry.
For an improvement of their handling, detergent-free or
l detergent-containing household chemicals may be thickened with the
~ thickening agents pursuant to the invention to reach higher
viccositiesO These include acids for cleaning purposes in
hospital areas, alcohol solutions for cleaning and care purposes,
and stripping agents for coats of paint. Naturally, the
thickening agents pursuant to the invention can also be used for
detergent-free preparations intended for the food industry, as
well as for electrolyte solutions for batteries, and also for
vegetable oils such as castor oil and soybean oil.
The following examples, while not intended to be
limiting, demonstrate several preferred embodiments of the
invention.
EXAMPLE 1
Thickening agents pursuant to the invention are prepared
by mixing at 80~C 0.2 mole of a fatty alcohol ethoxylate melt with
0.5% of 90% potassium hydroxide powder in a three-necked flask
equipped with stirrer and descending condenser. The percentage of
~2S~
the alkali hydroxide added herein is based upon the total weight
of al] ingredients used to manufacture the thickening agent, i.e.,
the fatty alcohol ethoxylate and the epoxyalkane. ~itrogen is
passed through the flask, while the temperature is held at 80C
for 30 minutes. The contents are then heated to 140C under a
water-jet vacuum (12 to 14 Torr), ma~ntaining the vacuum for 30
minutes. After releasing the vacuum by adding nitrogen, 0.2 mole
of epoxyalkane is added drop-by-drop over one hour. The epoxy
reaction is completed after an additional two hour reaction time.
10 The mix is cooled to 80C and the pH is adjusted to 6.5-7 with
glacial acetic acid. The products prepared according to this
procedure and their characteristics are listed in the following
table:
TABLE 1
Average
Product Rl n R2 Molecular Flow Range Appearance
Weiqht
A oleyl 40decyl 245044 - 45C yellowish
wax
B nonyl- 50decyl 215043 - 45C brownish
phenol wax
C tallow 60dodecyl 2800 48C clear wax
! radical
l ~ tallow 80decyl 340049 ~ 51C yellowish
25 1 radical wax
tallow radical = mixture of saturated hydrocarbon radicals
with 16 to 18 carbon atoms.
EXAMPLE_2
Using the thickening agents prepared in Example 1,
detl~ gent-containing preparations were iormulated with the v~rious
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detergents whose chemical compositions are shown in Table 3. The
viscosity of these preparationswas determined at 20~C with a
Couette rotation viscometer, model Haake CV 100.
Detergent-containing preparations similar to those of
the present invention but using sodium chloride and polyethylene
glycol-6000-distearate instead of the present polyether
derivatives were prepared for comparison purposes and are listed
at Examples 2(j), (k), (s), and (t). Examples 2(r) and (t) show
the difference in storage stabili-ty between detergent-containing
preparations containing the thickening agent pursuant to the
invention and that of detergent- containing preparations
containing the known stabilizer, polyethylene
glycol-6000-distearate. Upon measuring the viscosities of the two
detergent-containing preparations after 25 days of storage at
50C, the viscosity of the product pursuant to the invention
remained practically constant, whereas the viscosity of the
comparison product dropped to about 1/20th of its original
viscosity. The results of the viscosity measurements for Examples
2(a) to (t) have been compiled in Table 2, which also shows the
composition of the detergent-containing preparation in question.
Figure 1 demonstrates the dependence of the viscosity
upon the shear velocity for Example 2(k) (curve A) and 2(1) (curve
B). From the curves, it is apparent that the use of the present
thickening agent imparts Newtonian (shear-independent) viscosity
characteristics to detergent-containing preparations. In
contrast, when com~on salt is used in corresponding detergent-
containing preparations, the preparations exhibit a structurally
viscous (shear-dependent) behavior. Thickening agents are
intended to raise the viscosity of detergent-containing
preparations and maintain that viscosity regardless of external
factors, and it is thus undesirable when the viscosity declines at
higher shear velocities.
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~EXAMPLE 3
The thickening agent designated Product C in Example 1
~Table 1), which had first been melted at 75C, was added with
stirring to aqueous solutions of hydrochloric acid, sulfuric acid,
orthophosphoric acid, citric acid, common salt, calcium chloride,
urea, ethylene glycol, glycerin and D(-)sorbitol, which had been
heated to 75C. After cooling to room temperature, the solutions
are clear as water, stable, and viscous.
Viscous, aqueous solutions of ethanol and isopropanol
were prepared as follows. At 75C, the melted thickening agent
referred to as Product C in Example 1 (Table 1), was added with
stirring to water at 75C. After cooling to about 30C, ethanol
or isopropanol was added with stirring. After cooling to room
temperature, the solutions are clear as water, stable, and
viscous.
The viscosity of the aqueous, viscous systems was
measured at 25C with a KPG-Ubbelohde viscometer with suspended
ball level, DIN 51562. The kinematic viscosity is expressed in
cST. The compositions of the mixtures and the results of the
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EXAMPLE 4
The liquids numbered Wl to W8 in Table 5 were thickened
with thickening agent C in Example 1 (Table 1) by finely
dispersing the thickening agent with stirring at temperatures
between 70 and 90C. After cooling to room temperature, the
resulting dispersions were turbid, but stable and viscous. The
viscosities of these non-aqueous, stable, viscous dispersions, as
well as those of the corresponding liquids without the addition of
thickening agent, were measured at 25C with a Brookfield synchro-
lectric viscometer, model LVT. The dynamic viscosity is expressedin cP. The results are likewise compiled in Table 5.
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