CA1250003A - Thickening agent based on polyether derivatives - Google Patents

Abstract

THICKENING AGENT BASED ON POLYETHER DERIVATIVES
ABSTRACT OF THE DISCLOSURE
A thickening agent comprising polyether derivatives of the general formula:

wherein R1 is a substituted or unsubstituted hydrocarbon radical or an alkylphenol 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. These polyether derivatives are 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 200°C, to either (1) a polyethylene glycol monoether having an average molecular weight of 800 to 5000, the monoether group thereof 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, and 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.
This thickening agent is prepared using 0.1 to 1.0% by weight of an alkali hydroxide, referring to the total quantity of the long-chain epoxy and the monoether.

Description

lZ~ OD
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 gO

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:

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.

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:

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 I

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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.
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Claims (7)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A thickening agent comprising a polyether compound of the formula:

wherein:
R1 is a substituted or unsubstituted aliphatic hydrocarbon radical having 10 to 22 carbon atoms or alkyl-phenol radical having 7 to 15 carbon atoms;
R2 is an alkyl radical having 8 to 30 carbon atoms;
n = 40 to 80; and p = 1 to 3;
said compound being water soluble and solid at room temper-ature.

2. A thickening agent according to claim 1, wherein R1 is a tallow radical.

3. A thickening agent according to claim 1, wherein R2 is an alkyl radical having 10 to 18 carbon atoms.

4. A thickening agent according to claim 1, wherein p =
1.

5. A thickening agent according to claim 2, wherein p =
1.

6. A thickening agent according to claim 3, wherein p =
1.

7. A thickening agent according to claim 1, wherein said compound has an average molecular weight in the range of about 2150 to 3400.

14 .